JP2003295489A - Electrophotographic photoreceptor, process cartridge and electrophotographic device - Google Patents
Electrophotographic photoreceptor, process cartridge and electrophotographic deviceInfo
- Publication number
- JP2003295489A JP2003295489A JP2002095762A JP2002095762A JP2003295489A JP 2003295489 A JP2003295489 A JP 2003295489A JP 2002095762 A JP2002095762 A JP 2002095762A JP 2002095762 A JP2002095762 A JP 2002095762A JP 2003295489 A JP2003295489 A JP 2003295489A
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- Prior art keywords
- group
- photosensitive member
- electrophotographic photosensitive
- electrophotographic
- intermediate layer
- Prior art date
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- Photoreceptors In Electrophotography (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、電子写真感光体、
プロセスカートリッジ及び電子写真装置に関し、より詳
しくは、中間層に特定のレゾルシナレーン化合物を含有
する電子写真感光体、この電子写真感光体を有するプロ
セスカートリッジ及び電子写真装置に関する。TECHNICAL FIELD The present invention relates to an electrophotographic photoreceptor,
The present invention relates to a process cartridge and an electrophotographic apparatus, and more particularly, to an electrophotographic photosensitive member containing a specific resorcinarene compound in an intermediate layer, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.
【0002】[0002]
【従来の技術】有機電子写真感光体は、従来の無機電子
写真感光体に比べて無公害で製造が容易であり、構成材
料の選択の多様性から機能設計の自由度が高いという利
点を有する。近年のレーザービームプリンターの急速な
普及により広く市場で用いられるようになった。2. Description of the Related Art Organic electrophotographic photoconductors have the advantages that they are more pollution-free and easier to manufacture than conventional inorganic electrophotographic photoconductors, and that they have a high degree of freedom in functional design due to the variety of selection of constituent materials. . Due to the rapid spread of laser beam printers in recent years, it has become widely used in the market.
【0003】有機電子写真感光体の感光層には大きく次
の2種類がある。一方は電荷発生材料を含有する電荷発
生層と電荷輸送材料を含有する電荷輸送層とを積層した
積層型感光層であり、もう一方は電荷発生材料と電荷輸
送材料とを同一層中に分散又は溶解させた単層型感光層
である。The photosensitive layer of the organic electrophotographic photosensitive member is roughly classified into the following two types. One is a laminated photosensitive layer in which a charge generating layer containing a charge generating material and a charge transporting layer containing a charge transporting material are laminated, and the other is a charge generating material and a charge transporting material dispersed in the same layer. It is a dissolved single layer type photosensitive layer.
【0004】導電性支持体と感光層の間には、導電性支
持体上の欠陥の被覆、感光層の接着性付与、干渉縞の防
止、感光層の電気的破壊に対する保護、導電性支持体か
ら感光層へのホール注入の阻止等を目的に中間層が設け
られることが多い。Between the conductive support and the photosensitive layer, a defect on the conductive support is covered, adhesion of the photosensitive layer is imparted, interference fringes are prevented, electrical protection of the photosensitive layer is protected, and a conductive support is provided. An intermediate layer is often provided for the purpose of preventing the injection of holes into the photosensitive layer.
【0005】この中間層は、上述のメリットを有する反
面、電荷が蓄積され易いというデメリットも併せ持つ。
このため連続プリント時において電位変動が大きくなり
画像不具合が発生する。例えば、現在プリンターで広く
使用されている暗部電位部分を非現像部分とし明部電位
部分を現像部分とする現像プロセス(いわゆる反転現像
系)で使用した場合、明部電位や残留電位の低下により
前プリント時に光が当たった所の感度が速くなり、次プ
リント時に全面白画像をとると、前プリント部分が黒く
浮き出る、いわゆるゴースト現象(ポジゴースト)が顕
著に現れてしまう。This intermediate layer has the above-mentioned merit, but also has a demerit that charges are easily accumulated.
For this reason, the potential fluctuation becomes large during continuous printing, and image defects occur. For example, when used in a development process (so-called reversal development system) in which the dark potential portion is widely used in printers and the light potential portion is the development portion (so-called reversal development system), the light potential and the residual potential decrease and When printing, the sensitivity becomes faster when exposed to light, and when a white image is taken on the entire surface during the next printing, a so-called ghost phenomenon (positive ghost), in which the previously printed portion appears black, appears remarkably.
【0006】また、逆に明部電位の上昇により前プリン
ト時に光が当たった所の感度が遅くなり、次プリント時
に全面黒画像をとると、前プリント部分が白く浮き出
る、いわゆるゴースト現象(ネガゴースト)が顕著に現
れてしまう。On the contrary, due to the rise of the light potential, the sensitivity at the place exposed to the light at the time of the previous printing becomes slower, and when the whole black image is taken at the time of the next printing, the so-called ghost phenomenon (negative ghost) occurs. ) Appears remarkably.
【0007】中間層を設けた場合の連続プリント時にお
いて残留電位の上昇や初期電位の低下等による電位変動
を小さくし、耐久性を向上させるべく様々な方法が提案
されている。例えば、特開平9−258468号公報で
は多環キノン顔料を、特開平9−15889号公報では
ペリレン系顔料を、特開平5−27469号公報ではナ
フタレンテトラカルボン酸ジイミド化合物をそれぞれ中
間層に含有させた電子写真感光体が開示されているが、
完全に解決するには至っていないのが現状である。Various methods have been proposed in order to reduce the potential fluctuation due to the increase of the residual potential or the decrease of the initial potential during continuous printing when the intermediate layer is provided, and to improve the durability. For example, in JP-A-9-258468, a polycyclic quinone pigment, in JP-A-9-15889, a perylene-based pigment, and in JP-A-5-27469, a naphthalenetetracarboxylic acid diimide compound is contained in an intermediate layer. Although an electrophotographic photoreceptor is disclosed,
The current situation is that it has not been completely resolved.
【0008】[0008]
【発明が解決しようとする課題】本発明の目的は、連続
プリント時における電位変動が小さく、ゴースト等の画
像欠陥のない画像を供給する電子写真感光体、該電子写
真感光体を有するプロセスカートリッジ及び電子写真装
置を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member which supplies an image having a small potential fluctuation during continuous printing and having no image defect such as ghost, a process cartridge having the electrophotographic photosensitive member, and An object is to provide an electrophotographic apparatus.
【0009】[0009]
【課題を解決するための手段】本発明に従って、導電性
支持体上に電荷発生材料と電荷輸送材料を含有する感光
層を有する電子写真感光体において、該導電性支持体と
該感光層との間に設ける中間層に下記式(1)で示され
るレゾルシナレーン化合物を含有することを特徴とする
電子写真感光体、この電子写真感光体を有するプロセス
カートリッジ及び電子写真装置が提供される。According to the present invention, an electrophotographic photosensitive member having a photosensitive layer containing a charge generating material and a charge transporting material on a conductive support, wherein the conductive support and the photosensitive layer are Provided is an electrophotographic photosensitive member characterized by containing a resorcinarene compound represented by the following formula (1) in an intermediate layer provided therebetween, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.
【0010】[0010]
【化3】 [Chemical 3]
【0011】式中、R1は水素原子、置換基を有しても
よいアルキル基又はアリール基を示し、R2は水素原
子、置換基を有してもよいアルキル基、アリール基又は
Ar−N=N−基を示し、Arは同一又は異なって、置
換基を有してもよい芳香族炭化水素環、置換基を有して
もよい複素環又は置換基を有してもよい複数の芳香族炭
化水素環あるいは置換基を有してもよい複数の複素環を
結合したものの1価の基を示す。In the formula, R 1 represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group, and R 2 represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group or Ar-. N represents a N = N- group, Ar is the same or different, and an aromatic hydrocarbon ring which may have a substituent, a heterocycle which may have a substituent or a plurality of which may have a substituent. A monovalent group in which an aromatic hydrocarbon ring or a plurality of heterocycles which may have a substituent are bonded is shown.
【0012】本発明において、アルキル基としてはメチ
ル基、エチル基、プロピル基、ヘキシル基、ウンデシル
基及びトリデシル基等が挙げられ、アリール基としては
フェニル基及びナフチル基等が挙げられ、芳香族炭化水
素環としてはベンゼン基、ナフタレン基、フルオレン
基、フェナンスレン基、アンスラセン基、フルオランテ
ン基及びピレン基等が挙げられ、複素環としてはフラン
基、チオフェン基、ピリジン基、インドール基、ベンゾ
チアゾール基、カルバゾール基、ベンゾカルバゾール
基、アクリドン基、ジベンゾチオフェン基、ベンゾオキ
サゾール基、ベンゾトリアゾール基、オキサチアゾール
基、チアゾール基、フェナジン基、シンノリン基及びベ
ンゾシンノリン基等が挙げられ、複数の芳香族炭化水素
環あるいは複素環を結合したものとしては、トリフェニ
ルアミン基、ジフェニルアミン基、N−メチルジフェニ
ルアミン基、ビフェニル基、ターフェニル基、ビナフチ
ル基、フルオレノン基、フェナンスレンキノン基、アン
スラキノン基、ベンズアンスロン基、ジフェニルオキサ
ゾール基、フェニルベンズオキサゾール基、ジフェニル
メタン基、ジフェニルスルホン基、ジフェニルエーテル
基、ベンゾフェノン基、スチルベン基、ジスチリルベン
ゼン基、テトラフェニル−p−フェニレンジアミン基及
びテトラフェニルベンジジン基等が挙げられる。In the present invention, examples of the alkyl group include a methyl group, ethyl group, propyl group, hexyl group, undecyl group and tridecyl group, and examples of the aryl group include a phenyl group and a naphthyl group. Examples of the hydrogen ring include a benzene group, a naphthalene group, a fluorene group, a phenanthrene group, an anthracene group, a fluoranthene group, and a pyrene group, and examples of the heterocycle include a furan group, a thiophene group, a pyridine group, an indole group, a benzothiazole group, and carbazole. Group, benzocarbazole group, acridone group, dibenzothiophene group, benzoxazole group, benzotriazole group, oxathiazole group, thiazole group, phenazine group, cinnoline group, benzocinnoline group, etc., and multiple aromatic hydrocarbon rings. Or connect a heterocycle Examples of the compound include triphenylamine group, diphenylamine group, N-methyldiphenylamine group, biphenyl group, terphenyl group, binaphthyl group, fluorenone group, phenanthrenequinone group, anthraquinone group, benzanthrone group, diphenyloxazole group, Examples thereof include a phenylbenzoxazole group, a diphenylmethane group, a diphenylsulfone group, a diphenylether group, a benzophenone group, a stilbene group, a distyrylbenzene group, a tetraphenyl-p-phenylenediamine group and a tetraphenylbenzidine group.
【0013】置換基としては、メチル基、エチル基、プ
ロピル基及びブチル基等のアルキル基、フェニル基、ビ
フェニル基及びナフチル基等のアリール基、メトキシ基
及びエトキシ基等のアルコキシ基、ジメチルアミノ基及
びジエチルアミノ基等のジアルキルアミノ基、フェニル
アミノ基及びジフェニルアミノ基等のアリールアミノ
基、フッ素原子、塩素原子及び臭素原子等のハロゲン原
子、ヒドロキシ基、ニトロ基、シアノ基及びハロメチル
基等が挙げられる。As the substituent, an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an aryl group such as a phenyl group, a biphenyl group and a naphthyl group, an alkoxy group such as a methoxy group and an ethoxy group, and a dimethylamino group. And a dialkylamino group such as a diethylamino group, an arylamino group such as a phenylamino group and a diphenylamino group, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a hydroxy group, a nitro group, a cyano group and a halomethyl group. .
【0014】[0014]
【発明の実施の形態】以下に、本発明の実施の形態を詳
細に示す。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.
【0015】本発明において用いられるレゾルシナレー
ン化合物の例を下記に示すが、本発明においては、これ
らの化合物に限定されるものではない。Examples of the resorcinarene compound used in the present invention are shown below, but the present invention is not limited to these compounds.
【0016】[0016]
【表1】 [Table 1]
【0017】[0017]
【表2】 [Table 2]
【0018】[0018]
【表3】 [Table 3]
【0019】式(1)で示されるレゾルシナレーン化合
物は、公知例(例えばJ.Am.Chem.Soc.,
Vol.111,No.14,1989 p5397−
5404)に記載のように、レゾルシノール誘導体と各
種アルデヒド化合物を硫酸及び塩酸等の酸を用いて脱水
縮合することにより合成できる。更に、R2にアゾ基を
導入する方法は、R2が水素のレゾルシナレーン化合物
とジアゾ化合物誘導体とのアゾカプリング反応により合
成できる(文献例:CHEMISTRY LETTER
S,pp.1219−1222,1990)。The resorcinarene compound represented by the formula (1) is a known compound (for example, J. Am. Chem. Soc.,
Vol. 111, No. 14,1989 p5397-
5404), a resorcinol derivative and various aldehyde compounds can be synthesized by dehydration condensation using an acid such as sulfuric acid and hydrochloric acid. Furthermore, a method of introducing the azo group in R 2 may, R 2 can be synthesized by Azokapuringu reaction with Rezorushinaren compound and a diazo compound derivative of hydrogen (Reference Example: CHEMISTRY LETTER
S, pp. 1219-1222, 1990).
【0020】次に、レゾルシナレーン化合物の合成例を
説明する。ここで示す「%」及び「部」は、それぞれ
「質量%」及び「質量部」を意味する。Next, an example of synthesizing a resorcinarene compound will be described. "%" And "parts" shown here mean "mass%" and "parts by mass", respectively.
【0021】<合成例1…例示化合物15の合成>窒素
雰囲気下、冷却管を付けたナスフラスコにレゾルシノー
ル25.6部、ドデシルアルデヒド42.3部及びエタ
ノール230部を加え、その中へ濃塩酸37部を加え、
70℃で10時間処理した後で、冷却後ろ取し、得られ
た結晶を熱水で充分洗浄し、乾燥した後、メタノールで
再結晶して、白色結晶の例示化合物15を17.3部得
た。得られた化合物の1H−NMR及びIRのデータを
下記に示す。<Synthesis Example 1-Synthesis of Exemplified Compound 15> In a nitrogen atmosphere, 25.6 parts of resorcinol, 42.3 parts of dodecylaldehyde and 230 parts of ethanol were added to a round bottom flask equipped with a cooling tube, and concentrated hydrochloric acid was added thereto. Add 37 parts,
After treating at 70 ° C. for 10 hours, cooling and collecting the crystals, the obtained crystals were thoroughly washed with hot water, dried and then recrystallized from methanol to obtain 17.3 parts of Exemplified Compound 15 as white crystals. It was The 1 H-NMR and IR data of the obtained compound are shown below.
【0022】1H−NMR(CDCl3,40℃)δ=
0.91(t,12H)、1.30(brs,64
H)、1.41(brs,8H)、2.24(brs,
8H)、4.33(t,4H)、6.15(s,4
H)、7.24(s,4H)、9.27、9.37、
9.55、9.62(eachbrs,4H) 1 H-NMR (CDCl 3, 40 ° C.) δ =
0.91 (t, 12H), 1.30 (brs, 64
H), 1.41 (brs, 8H), 2.24 (brs, 8H)
8H), 4.33 (t, 4H), 6.15 (s, 4)
H), 7.24 (s, 4H), 9.27, 9.37,
9.55, 9.62 (eachbrs, 4H)
【0023】IR(KBr)cm-1=3548、349
2、2924、2852、1618、1508、146
5、1432、1302、1196、1167、90
3、837IR (KBr) cm -1 = 3548,349
2, 2924, 2852, 1618, 1508, 146
5, 1432, 1302, 1196, 1167, 90
3,837
【0024】<合成例2…例示化合物1の合成>窒素雰
囲気下、例示化合物15 4.4部をN,N−ジメチル
ホルムアミド(DMF)360部に溶解させた溶液を0
℃まで冷却した後、下記に示される化合物5.6部<Synthesis Example 2 ... Synthesis of Exemplified Compound 1> A solution prepared by dissolving 4.4 parts of Exemplified Compound 15 in 360 parts of N, N-dimethylformamide (DMF) under a nitrogen atmosphere was used.
After cooling to ℃, 5.6 parts of the compound shown below
【0025】[0025]
【化4】
とピリジン60部を加え、そのままの温度で6時間攪拌
した後、水1500部に注下し、析出物をろ取した。得
られた結晶を2%塩酸次いで水で充分洗浄し、乾燥した
後、テトラヒドロフランで再結晶して、赤色結晶の例示
化合物1を5部得た。得られた化合物のIRのデータを
下記に示す。[Chemical 4] And 60 parts of pyridine were added, and the mixture was stirred at the same temperature for 6 hours, poured into 1500 parts of water, and the precipitate was collected by filtration. The obtained crystals were thoroughly washed with 2% hydrochloric acid and then with water, dried and then recrystallized from tetrahydrofuran to obtain 5 parts of Exemplified Compound 1 as red crystals. The IR data of the obtained compound is shown below.
【0026】IR(KBr)cm-1=3101、292
5、1542、1491、1342IR (KBr) cm -1 = 3101,292
5, 1542, 1491, 1342
【0027】本発明の電子写真感光体の層構成は、導電
性支持体上に前記式(1)で示されるレゾルシナレーン
化合物を含有する中間層を有し、該中間層上に電荷発生
材料と電荷輸送材料を含有する感光層を有する層構成で
ある。また、感光層上には必要に応じて保護層を設けて
もよい。The layer structure of the electrophotographic photosensitive member of the present invention has an intermediate layer containing a resorcinarene compound represented by the above formula (1) on a conductive support, and the charge generating material and the charge are provided on the intermediate layer. It is a layer structure having a photosensitive layer containing a transport material. Further, a protective layer may be provided on the photosensitive layer, if necessary.
【0028】支持体としては、導電性を有するものであ
ればよく、アルミニウム、ステンレス及びニッケル等の
金属あるいは導電層を設けた金属、プラスチック及び紙
等が挙げられ、形状としては円筒状及びフィルム状等が
挙げられる。The support may be any one having conductivity, and examples thereof include metals such as aluminum, stainless steel, and nickel, metals provided with a conductive layer, plastics, paper, and the like. The shape is cylindrical or film-like. Etc.
【0029】中間層は、導電性支持体上の欠陥の被覆、
感光層の接着性付与、干渉縞の防止、感光層の電気的破
壊に対する保護、導電性支持体から感光層へのホール注
入の阻止等を目的に導電性支持体と感光層の間に設けら
れる。The intermediate layer is a coating of defects on the conductive support,
Provided between the conductive support and the photosensitive layer for the purpose of imparting adhesiveness to the photosensitive layer, preventing interference fringes, protecting the photosensitive layer against electrical breakdown, and preventing holes from being injected from the conductive support into the photosensitive layer. .
【0030】中間層は、前記式(1)で示されるレゾル
シナレーン化合物及び結着樹脂からなり、これらを溶剤
に溶解又は分散して塗布液を作製し、塗工により薄層が
設けられる。用いられる結着樹脂は特に限定されること
はなく、例えば、フェノール樹脂、エポキシ樹脂、ポリ
ウレタン、ポリカーボネート、ポリアリレート、ポリエ
ステル、ポリアミド、ポリイミド、ポリアミドイミド、
ポリアミド酸、ポリエチレン、ポリスチレン、スチレン
−アクリル共重合体、アクリル樹脂、ポリメタクリレー
ト、ポリビニルアルコール、ポリビニルアセタール、ポ
リビニルブチラール、ポリビニルホルマール、ポリアク
リロニトリル、ポリアクリルアミド、アクリロニトリル
−ブタジエン共重合体、ポリ塩化ビニル、塩化ビニル−
酢酸ビニル共重合体、セルロース、メラミン樹脂、アミ
ロース、アミロペクチン、ポリスルホン、ポリエーテル
スルホン又はシリコーン樹脂等が適宜用いられ、一種も
しくは二種以上のものを混合して用いることができる。
これらの中でも、フェノール樹脂、ポリウレタン、ポリ
アミド、ポリイミド、ポリアミドイミド、ポリアミド
酸、ポリビニルアセタール、ポリビニルブチラール、エ
ポキシ樹脂、アクリル樹脂、セルロース樹脂、メラミン
樹脂及びポリエステル等が好ましい。The intermediate layer comprises a resorcinarene compound represented by the above formula (1) and a binder resin, and these are dissolved or dispersed in a solvent to prepare a coating solution, and a thin layer is formed by coating. The binder resin used is not particularly limited, for example, phenol resin, epoxy resin, polyurethane, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyamideimide,
Polyamic acid, polyethylene, polystyrene, styrene-acrylic copolymer, acrylic resin, polymethacrylate, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, polyvinyl formal, polyacrylonitrile, polyacrylamide, acrylonitrile-butadiene copolymer, polyvinyl chloride, chloride Vinyl
Vinyl acetate copolymer, cellulose, melamine resin, amylose, amylopectin, polysulfone, polyether sulfone, silicone resin and the like are appropriately used, and one kind or a mixture of two or more kinds can be used.
Among these, phenol resin, polyurethane, polyamide, polyimide, polyamideimide, polyamic acid, polyvinyl acetal, polyvinyl butyral, epoxy resin, acrylic resin, cellulose resin, melamine resin and polyester are preferable.
【0031】また、中間層の体積抵抗や誘電率等の調整
を行うために、導電性物質を含有させてもよい。導電性
物質としては、アルミニウム粉末及び銅粉末等の金属、
酸化アルミニウム、酸化スズ、酸化インジウム、酸化チ
タン、酸化ジルコニウム、酸化亜鉛、酸化珪素、酸化タ
ンタル、酸化モリブデン及び酸化タングステン等の金属
酸化物、ジルコニウムテトラ−n−ブトキサイド、チタ
ニウムテトラ−n−ブトキサイド、アルミニウムイソプ
ロポキシド及びメチルメトキシシラン等の有機金属化合
物及びカーボンブラック等が挙げられる。更に、それら
の混合物等も用いることができる。Further, a conductive substance may be contained in order to adjust the volume resistance and the dielectric constant of the intermediate layer. As the conductive material, metals such as aluminum powder and copper powder,
Metal oxides such as aluminum oxide, tin oxide, indium oxide, titanium oxide, zirconium oxide, zinc oxide, silicon oxide, tantalum oxide, molybdenum oxide and tungsten oxide, zirconium tetra-n-butoxide, titanium tetra-n-butoxide, aluminum. Examples include organic metal compounds such as isopropoxide and methylmethoxysilane, and carbon black. Further, a mixture thereof or the like can be used.
【0032】また、中間層が前記導電性物質の少なくと
も1種を含有する第1中間層と、前記結着樹脂の少なく
とも1種を含有する第2中間層の積層からなり、第1中
間層と第2中間層の両層に前記式(1)で示されるレゾ
ルシナレーン化合物を含有させてもよい。The intermediate layer comprises a first intermediate layer containing at least one kind of the conductive material and a second intermediate layer containing at least one kind of the binder resin. Both layers of the second intermediate layer may contain the resorcinarene compound represented by the formula (1).
【0033】中間層を積層にする場合は、第1中間層上
に第2中間層を形成してもよいし、第2中間層上に第1
中間層を形成してもよい。When the intermediate layer is laminated, the second intermediate layer may be formed on the first intermediate layer, or the first intermediate layer may be formed on the second intermediate layer.
You may form an intermediate | middle layer.
【0034】前記式(1)で示されるレゾルシナレーン
化合物の含有量は中間層に対して0.01質量%〜10
0質量%であり、より好ましくは0.1質量%〜50質
量%である。100質量%の場合には塗工性や塗布液の
安定性が悪くなり好ましくない。また、0.01質量%
より少ない場合には前記式(1)で示されるレゾルシナ
レーン化合物の含有量が低くなり過ぎ、その効果が期待
できなくなる。また、前記式(1)で示されるレゾルシ
ナレーン化合物は、一種もしくは二種以上のものを混合
して用いることができる。The content of the resorcinarene compound represented by the above formula (1) is 0.01% by mass to 10% by mass with respect to the intermediate layer.
It is 0% by mass, more preferably 0.1% by mass to 50% by mass. When it is 100% by mass, the coatability and the stability of the coating solution are deteriorated, which is not preferable. Moreover, 0.01 mass%
If the amount is less, the content of the resorcinarene compound represented by the formula (1) becomes too low, and the effect cannot be expected. The resorcinarene compound represented by the formula (1) may be used alone or in combination of two or more.
【0035】中間層に用いる塗布液は、前記式(1)で
示されるレゾルシナレーン化合物と結着樹脂を適当な溶
剤に溶解又は分散させて得ることができる。The coating liquid used for the intermediate layer can be obtained by dissolving or dispersing the resorcinarene compound represented by the above formula (1) and the binder resin in a suitable solvent.
【0036】用いられる溶剤は特に限定されることはな
く、例えば、ベンゼン、トルエン、キシレン、テトラリ
ン、クロロベンゼン、ジクロロメタン、クロロホルム、
トリクロロエチレン、テトラクロロエチレン、四塩化炭
素、酢酸メチル、酢酸エチル、酢酸プロピル、ギ酸メチ
ル、ギ酸エチル、アセトン、メチルエチルケトン、シク
ロヘキサノン、ジエチルエーテル、ジプロピルエーテ
ル、ジオキサン、メチラール、テトラヒドロフラン、メ
タノール、エタノール、イソプロピルアルコール、ブチ
ルアルコール、メチルセロソルブ、メトキシプロパノー
ル、ジメチルホルムアミド、ジメチルアセトアミド及び
ジメチルスルホキシド等の溶剤を用いることができる。The solvent used is not particularly limited and includes, for example, benzene, toluene, xylene, tetralin, chlorobenzene, dichloromethane, chloroform,
Trichloroethylene, tetrachloroethylene, carbon tetrachloride, methyl acetate, ethyl acetate, propyl acetate, methyl formate, ethyl formate, acetone, methyl ethyl ketone, cyclohexanone, diethyl ether, dipropyl ether, dioxane, methylal, tetrahydrofuran, methanol, ethanol, isopropyl alcohol, butyl Solvents such as alcohol, methyl cellosolve, methoxypropanol, dimethylformamide, dimethylacetamide and dimethylsulfoxide can be used.
【0037】塗布方法としては、ディッピング法、スプ
レーコーティング法、スピンナーコーティング法、ビー
ドコーティング法、ブレードコーティング法及びビーム
コーティング法等の塗布方法が挙げられ、膜厚は0.0
1〜30μm程度が好ましく、特には0.1〜20μm
が好ましい。Examples of the coating method include dipping method, spray coating method, spinner coating method, bead coating method, blade coating method and beam coating method.
1 to 30 μm is preferable, and 0.1 to 20 μm is particularly preferable.
Is preferred.
【0038】感光層には大きく次の2種類がある。一方
は電荷発生材料を含有する電荷発生層と電荷輸送材料を
含有する電荷輸送層とを積層した積層型感光層であり、
もう一方は電荷発生材料と電荷輸送材料とを同一層中に
分散又は溶解させた単層型感光層である。なお、積層型
において電荷発生層と電荷輸送層の積層関係は逆であっ
てもよいが、電子写真特性的には電荷発生層の上に電荷
輸送層を積層した方が好ましい。The photosensitive layer is roughly classified into the following two types. One is a laminated photosensitive layer in which a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material are stacked,
The other is a single layer type photosensitive layer in which a charge generating material and a charge transporting material are dispersed or dissolved in the same layer. In the laminated type, the lamination relationship between the charge generation layer and the charge transport layer may be reversed, but it is preferable to laminate the charge transport layer on the charge generation layer in terms of electrophotographic characteristics.
【0039】電荷発生材料としては、アゾ顔料又はフタ
ロシアニン顔料を用いることが好ましい。用いられるア
ゾ顔料としては、ビスアゾ、トリスアゾ及びテトラキス
アゾ等いかなるアゾ顔料でも使用できるが、中でも特開
昭59−31962号公報や特開平1−183663号
公報に開示されているベンズアンスロン系アゾ顔料が優
れた感度特性を有しており、またゴーストも発生し易い
ので本発明が有効に作用し好ましい。An azo pigment or a phthalocyanine pigment is preferably used as the charge generating material. As the azo pigment to be used, any azo pigment such as bisazo, trisazo and tetrakisazo can be used. Among them, the benzanthrone type azo pigments disclosed in JP-A-59-31962 and JP-A-1-183663 can be used. Since the present invention has excellent sensitivity characteristics and easily causes ghost, the present invention works effectively and is preferable.
【0040】また、フタロシアニン顔料としては、無金
属フタロシアニン、軸配位子を有してもよい金属フタロ
シアニン等いかなるフタロシアニンでも使用でき、置換
基を有してもよいが、特にオキシチタニウムフタロシア
ニン及びガリウムフタロシアニンが優れた感度を有して
おり、ゴーストも発生し易いので本発明が有効に作用し
好ましい。更に、いかなる結晶形でもよいが、その中で
もCuKα特性X線回折におけるブラッグ角2θの7.
4°±0.2°及び28.2°±0.2°に強いピーク
を有する結晶形のヒドロキシガリウムフタロシアニン、
CuKα特性X線回折におけるブラッグ角2θ±0.2
°の7.4°、16.6°、25.5°及び28.3°
に強いピークを有する結晶形のクロロガリウムフタロシ
アニン、CuKα特性X線回折におけるブラッグ角2θ
の27.2°±0.2°に強いピークを有する結晶形の
オキシチタニウムフタロシアニンが特に優れた感度特性
を有しており、ゴーストも発生し易いので本発明が有効
に作用し好ましい。As the phthalocyanine pigment, any phthalocyanine such as metal-free phthalocyanine and metal phthalocyanine which may have an axial ligand can be used, and may have a substituent, but especially oxytitanium phthalocyanine and gallium phthalocyanine. Has excellent sensitivity, and ghosts easily occur, so that the present invention works effectively and is preferable. Further, although any crystal form may be used, among them, the Bragg angle 2θ in CuKα characteristic X-ray diffraction of 7.
Hydroxygallium phthalocyanine in crystalline form having strong peaks at 4 ° ± 0.2 ° and 28.2 ° ± 0.2 °,
Bragg angle 2θ ± 0.2 in CuKα characteristic X-ray diffraction
° 7.4 °, 16.6 °, 25.5 ° and 28.3 °
Form of chlorogallium phthalocyanine having a strong peak in the spectrum, Bragg angle 2θ in CuKα characteristic X-ray diffraction
The crystalline form of oxytitanium phthalocyanine having a strong peak at 27.2 ° ± 0.2 ° has particularly excellent sensitivity characteristics, and since ghosts are easily generated, the present invention effectively acts and is preferable.
【0041】電荷輸送材料としては、トリアリールアミ
ン系化合物、ヒドラゾン系化合物、スチルベン系化合
物、ピラゾリン系化合物、オキサゾール系化合物、チア
ゾール系化合物、トリアリルメタン系化合物、エナミン
系化合物及びブタジエン系化合物等が挙げられる。Examples of the charge transport material include triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, triallylmethane compounds, enamine compounds and butadiene compounds. Can be mentioned.
【0042】積層型からなる感光層を形成する場合、電
荷発生層は、顔料と適当な溶剤及び結着樹脂を共に溶解
又は分散させ、この塗布液を中間層上に塗布し乾燥して
形成する方法が挙げられる。電荷輸送層は、主として電
荷輸送材料と結着樹脂を溶剤中に溶解させた塗布液を電
荷発生層上に塗布し、乾燥して形成される。In the case of forming a laminated type photosensitive layer, the charge generation layer is formed by dissolving or dispersing a pigment, an appropriate solvent and a binder resin together, applying the coating solution on the intermediate layer and drying. There is a method. The charge-transporting layer is formed by applying a coating solution prepared by dissolving a charge-transporting material and a binder resin in a solvent onto the charge-generating layer and drying it.
【0043】単層型からなる感光層は、顔料と電荷輸送
材料を適当な溶剤及び結着樹脂に分散させて、この塗布
液を中間層上に塗布し、乾燥することによって形成され
る。The single-layer type photosensitive layer is formed by dispersing a pigment and a charge transporting material in an appropriate solvent and a binder resin, applying the coating solution on the intermediate layer, and drying.
【0044】感光層用の塗布液作製時に用いられる溶剤
や結着樹脂は中間層の塗布液作製時で挙げたものと同様
なものを用いることができる。感光層の塗布方法につい
ても中間層で挙げた方法と同様の方法が用いられる。As the solvent and the binder resin used in preparing the coating solution for the photosensitive layer, the same solvents and binder resins as those mentioned in preparing the coating solution for the intermediate layer can be used. As for the coating method of the photosensitive layer, the same method as the method mentioned for the intermediate layer is used.
【0045】感光層が積層型の場合、電荷発生層の膜厚
は0.01〜10μmであることが好ましく、特に0.
05〜5μmであることが好ましく、電荷輸送層の膜厚
は5〜40μmであることが好ましく、特に10〜30
μmであることが好ましい。感光層が単層型の場合、膜
厚は5〜40μmであることが好ましく、特に10〜3
0μmであることが好ましい。When the photosensitive layer is of a laminated type, the film thickness of the charge generation layer is preferably 0.01 to 10 μm, and particularly preferably 0.
The thickness of the charge transport layer is preferably from 5 to 40 μm, and more preferably from 10 to 30 μm.
It is preferably μm. When the photosensitive layer is a single layer type, the film thickness is preferably 5 to 40 μm, particularly 10 to 3
It is preferably 0 μm.
【0046】感光層上には必要に応じて保護層を設けて
もよい。保護層は、ポリビニルブチラール、ポリエステ
ル、ポリカーボネート(ポリカーボネートZや変性ポリ
カーボネート等)、ポリアミド、ポリイミド、ポリアリ
レート、ポリウレタン、フェノール、スチレン−ブタジ
エンコポリマー、エチレン−アクリル酸コポリマー又は
スチレン−アクリロニトリルコポリマー等の樹脂を適当
な有機溶剤によって溶解し、感光層の上に塗布乾燥して
形成される。保護層の膜厚は0.05〜20μmが好ま
しい。また、保護層中に導電性粒子や紫外線吸収剤等を
含有させてもよい。導電性粒子としては、例えば酸化ス
ズ粒子等の金属酸化物が好ましい。If desired, a protective layer may be provided on the photosensitive layer. For the protective layer, a resin such as polyvinyl butyral, polyester, polycarbonate (polycarbonate Z or modified polycarbonate, etc.), polyamide, polyimide, polyarylate, polyurethane, phenol, styrene-butadiene copolymer, ethylene-acrylic acid copolymer or styrene-acrylonitrile copolymer is suitable. It is formed by dissolving it in a different organic solvent, coating it on the photosensitive layer and drying it. The thickness of the protective layer is preferably 0.05 to 20 μm. Further, the protective layer may contain conductive particles, an ultraviolet absorber or the like. The conductive particles are preferably metal oxides such as tin oxide particles.
【0047】図1に本発明の電子写真感光体を有するプ
ロセスカートリッジを備えた電子写真装置の概略構成を
示す。FIG. 1 shows a schematic structure of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.
【0048】図1において、1はドラム状の本発明の電
子写真感光体であり、軸2を中心に矢印方向に所定の周
速度(プロセススピード)をもって回転駆動される。電
子写真感光体1は、回転過程において、一次帯電手段3
によりその周面に正又は負の所定電位の均一帯電を受
け、次いで、スリット露光やレーザービーム走査露光等
の露光手段(不図示)から出力される目的の画像情報の
時系列電気デジタル画像信号に対応して強度変調された
露光光4を受ける。こうして電子写真感光体1の周面に
対し、目的の画像情報に対応した静電潜像が順次形成さ
れていく。In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven around a shaft 2 in a direction of an arrow at a predetermined peripheral speed (process speed). The electrophotographic photosensitive member 1 is rotated by the primary charging means 3 during the rotation process.
The peripheral surface thereof is uniformly charged with a positive or negative predetermined potential, and then converted into a time-series electric digital image signal of the target image information output from exposure means (not shown) such as slit exposure or laser beam scanning exposure. Corresponding intensity-modulated exposure light 4 is received. In this way, electrostatic latent images corresponding to target image information are sequentially formed on the peripheral surface of the electrophotographic photosensitive member 1.
【0049】形成された静電潜像は、次いで現像手段5
内の荷電粒子(トナー)で正規現像又は反転現像により
可転写粒子像(トナー像)として顕画化され、不図示の
給紙部から電子写真感光体1と転写手段6との間に電子
写真感光体1の回転と同期して取り出されて給送された
転写材7に、電子写真感光体1の表面に形成担持されて
いるトナー像が転写手段6により順次転写されていく。
この時、転写手段にはバイアス電源(不図示)からトナ
ーの保有電荷とは逆極性のバイアス電圧が印加される。The formed electrostatic latent image is then developed by the developing means 5.
The image is visualized as a transferable particle image (toner image) by charged particles (toner) in the inside by normal development or reversal development, and an electrophotographic image is formed between the electrophotographic photosensitive member 1 and the transfer unit 6 from a sheet feeding unit (not shown). The toner image formed and carried on the surface of the electrophotographic photosensitive member 1 is sequentially transferred by the transfer unit 6 to the transfer material 7 that is taken out and fed in synchronization with the rotation of the photosensitive member 1.
At this time, a bias power source (not shown) applies a bias voltage having a polarity opposite to that of the charge held by the toner to the transfer unit.
【0050】トナー画像の転写を受けた転写材7は、電
子写真感光体面から分離されて像定着手段8へ搬送され
てトナー像の定着処理を受けることにより画像形成物
(プリント、コピー)として装置外へプリントアウトさ
れる。The transfer material 7 to which the toner image has been transferred is separated from the surface of the electrophotographic photosensitive member and conveyed to the image fixing means 8 to be subjected to the fixing process of the toner image, so that the image forming material (print, copy) is formed. Printed out.
【0051】トナー像転写後の電子写真感光体1の表面
は、クリーニング手段9によって転写残りトナー等の付
着物の除去を受けて清浄面化される。近年、クリーナレ
スシステムも研究され、転写残りトナーを直接、現像器
等で回収することもできる。更に、前露光手段(不図
示)からの前露光光10により除電処理された後、繰り
返し画像形成に使用される。なお、一次帯電手段3が帯
電ローラー等を用いた接触帯電手段である場合は、前露
光は必ずしも必要ではない。After the transfer of the toner image, the surface of the electrophotographic photosensitive member 1 is cleaned by the cleaning means 9 to remove adhered matters such as transfer residual toner. In recent years, cleanerless systems have also been studied, and the transfer residual toner can be directly collected by a developing device or the like. Further, after the charge is removed by the pre-exposure light 10 from the pre-exposure means (not shown), it is repeatedly used for image formation. If the primary charging means 3 is a contact charging means using a charging roller or the like, pre-exposure is not always necessary.
【0052】本発明においては、上述の電子写真感光体
1、一次帯電手段3、現像手段5及びクリーニング手段
9等の構成要素のうち、複数のものを容器に納めてプロ
セスカートリッジとして一体に結合して構成し、このプ
ロセスカートリッジを複写機やレーザービームプリンタ
ー等の電子写真装置本体に対して着脱自在に構成しても
よい。例えば、一次帯電手段3、現像手段5及びクリー
ニング手段9の少なくとも1つを電子写真感光体1と共
に一体に支持してカートリッジ化して、装置本体のレー
ル等の案内手段12を用いて装置本体に着脱自在なプロ
セスカートリッジ11とすることができる。In the present invention, among the above-mentioned electrophotographic photosensitive member 1, primary charging means 3, developing means 5, cleaning means 9 and the like, a plurality of components are housed in a container and integrally combined as a process cartridge. The process cartridge may be detachably attached to the main body of the electrophotographic apparatus such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the electrophotographic photosensitive member 1 to form a cartridge, and the cartridge is attached to and detached from the apparatus main body by using a guide unit 12 such as a rail of the apparatus main body. The process cartridge 11 can be freely used.
【0053】また、露光光4は、電子写真装置が複写機
やプリンターである場合には、原稿からの反射光や透過
光、あるいは、センサーで原稿を読取り、信号化し、こ
の信号に従って行われるレーザービームの走査、LED
アレイの駆動又は液晶シャッターアレイの駆動等により
照射される光である。When the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 is reflected light or transmitted light from the original, or the original is read by a sensor, converted into a signal, and the laser is generated in accordance with this signal. Beam scanning, LED
Light emitted by driving the array or driving the liquid crystal shutter array.
【0054】本発明の電子写真感光体は、電子写真複写
機に利用するのみならず、レーザービームプリンター、
CRTプリンター、LEDプリンター、FAX、液晶プ
リンター及びレーザー製版等の電子写真応用分野にも幅
広く適用し得るものである。The electrophotographic photoreceptor of the present invention can be used not only in electrophotographic copying machines but also in laser beam printers,
It can be widely applied to electrophotographic application fields such as CRT printers, LED printers, FAX machines, liquid crystal printers, and laser plate making.
【0055】[0055]
【実施例】以下に、具体的な実施例を挙げて本発明を更
に詳細に説明する。ただし、本発明の実施の形態は、こ
れらに限定されるものではない。なお、実施例中の
「%」及び「部」は、それぞれ「質量%」及び「質量
部」を意味する。EXAMPLES The present invention will be described in more detail with reference to specific examples. However, the embodiment of the present invention is not limited to these. In addition, "%" and "part" in an Example mean "mass%" and "mass part", respectively.
【0056】(実施例1)10%の酸化アンチモンを含
有する酸化スズで被覆した酸化チタン粉体50部、レゾ
ール型フェノール樹脂25部、例示化合物No.1 1
部、メチルセロソルブ20部、メタノール5部及びシリ
コーンオイル(ポリジメチルシロキサン・ポリオキシア
ルキレン共重合体、平均分子量3000)0.002部
を直径1mmガラスビーズを用いたサンドミル装置で2
時間分散して、第1中間層用塗布液を調製した。アルミ
ニウムシリンダー(直径30mm×長さ260.5m
m)上に、この塗布液を浸漬塗布し、140℃で30分
間乾燥させ、膜厚が15μmの第1中間層を形成した。(Example 1) 50 parts of titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts of resol type phenol resin, exemplified compound No. 1 1
Parts, 20 parts of methyl cellosolve, 5 parts of methanol and 0.002 parts of silicone oil (polydimethylsiloxane-polyoxyalkylene copolymer, average molecular weight 3000) in a sand mill apparatus using glass beads of 1 mm in diameter.
The dispersion liquid was dispersed over time to prepare a coating liquid for the first intermediate layer. Aluminum cylinder (diameter 30mm x length 260.5m
m) was coated with this coating solution by dip coating and dried at 140 ° C. for 30 minutes to form a first intermediate layer having a film thickness of 15 μm.
【0057】この上に6−66−610−12四元系ポ
リアミド共重合体樹脂5部をメタノール70部/ブタノ
ール25部の混合溶媒に溶解した溶液を第1中間層上に
浸漬塗布し、膜厚が1μmの第2中間層を形成した。A solution of 5 parts of 6-66-610-12 quaternary polyamide copolymer resin dissolved in a mixed solvent of 70 parts of methanol / 25 parts of butanol was dip-coated on the first intermediate layer to form a film. A second intermediate layer having a thickness of 1 μm was formed.
【0058】次に、CuKα特性X線回折におけるブラ
ッグ角(2θ±0.2°)の7.5°、9.9°、1
6.3°、18.6°、25.1°及び28.3°に強
いピークを有する結晶形のヒドロキシガリウムフタロシ
アニン10部とポリビニルブチラール樹脂(商品名:エ
スレックBX−1、積水化学工業社製)5部をシクロヘ
キサノン250部に添加し、直径1mmのガラスビーズ
を用いたサンドミル装置で3時間分散し、これに250
部の酢酸エチルを添加して希釈し、この塗布液を第2中
間層上に浸漬塗布し、100℃で10分間乾燥して、膜
厚が0.16μmの電荷発生層を形成した。Next, the Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 7.5 °, 9.9 °, and 1
10 parts of crystalline hydroxygallium phthalocyanine having a strong peak at 6.3 °, 18.6 °, 25.1 ° and 28.3 ° and a polyvinyl butyral resin (trade name: S-REC BX-1, manufactured by Sekisui Chemical Co., Ltd.) ) 5 parts of cyclohexanone was added to 250 parts of the mixture, and the mixture was dispersed for 3 hours in a sand mill using glass beads having a diameter of 1 mm.
Part of ethyl acetate was added to dilute, the coating solution was applied onto the second intermediate layer by dip coating, and dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.16 μm.
【0059】次に、下記に示される電荷輸送材料10
部、Next, the charge transport material 10 shown below is used.
Department,
【0060】[0060]
【化5】
ポリカーボネート樹脂(商品名:ユーピロンZ−20
0、三菱ガス化学社製)10部をモノクロロベンゼン7
0部に溶解した溶液を調製し、電荷発生層上に浸漬塗布
し、110℃で1時間乾燥して、膜厚25μmの電荷輸
送層を形成し、電子写真感光体を作製した。[Chemical 5] Polycarbonate resin (Product name: Iupilon Z-20
0, manufactured by Mitsubishi Gas Chemical Co., Inc.) 10 parts of monochlorobenzene 7
A solution dissolved in 0 part was prepared, dip-coated on the charge generation layer, and dried at 110 ° C. for 1 hour to form a charge transport layer having a film thickness of 25 μm, and an electrophotographic photosensitive member was produced.
【0061】(実施例2)実施例1において例示化合物
No.1 1部を例示化合物No.2 1部に代えた以
外は、実施例1と全く同様にして実施例2の電子写真感
光体を作製した。Example 2 Exemplified compound No. 1 1 part was used as the exemplified compound No. An electrophotographic photosensitive member of Example 2 was manufactured in exactly the same manner as in Example 1 except that 21 parts were replaced.
【0062】(実施例3)実施例1において例示化合物
No.1 1部を例示化合物No.3 5部に代えた以
外は、実施例1と全く同様にして実施例3の電子写真感
光体を作製した。Example 3 Exemplified compound No. 1 in Example 1 was used. 1 1 part was used as the exemplified compound No. An electrophotographic photosensitive member of Example 3 was manufactured in the same manner as in Example 1 except that 35 parts were replaced.
【0063】(実施例4)実施例3において第1中間層
には例示化合物No.3 5部を含有させたままの状態
で、更に第2中間層に例示化合物No.15 0.5部
を含有させた以外は、実施例3と全く同様にして実施例
4の電子写真感光体を作製した。(Example 4) In Example 3, the compound No. In the state where 35 parts were included, the compound No. 3 was added to the second intermediate layer. An electrophotographic photosensitive member of Example 4 was produced in exactly the same manner as in Example 3, except that 15 0.5 parts was contained.
【0064】(実施例5)実施例4において第1中間層
に例示化合物No.3を含有させなかった以外は、実施
例4と全く同様にして実施例5の電子写真感光体を作製
した。Example 5 In Example 4, the compound No. An electrophotographic photosensitive member of Example 5 was produced in exactly the same manner as in Example 4 except that 3 was not included.
【0065】(比較例1)実施例1において第1中間層
に例示化合物No.1を含有させなかった以外は、実施
例1と全く同様にして比較例1の電子写真感光体を作製
した。(Comparative Example 1) In Example 1, the compound No. An electrophotographic photoreceptor of Comparative Example 1 was produced in exactly the same manner as in Example 1 except that 1 was not included.
【0066】(実施例6)ポリアミド樹脂(商品名:ア
ミランCM−8000、東レ社製)5部、例示化合物N
o.4 0.5部をメタノール60部/ブタノール30
部の混合溶媒に溶解して直径1mmガラスビーズを用い
たサンドミル装置で1時間分散して中間層用塗布液を調
製した。この塗布液をアルミニウムシリンダー(直径3
0mm×長さ260.5mm)上に浸漬塗布し、膜厚が
0.3μmの中間層を形成した。Example 6 Polyamide resin (trade name: Amilan CM-8000, manufactured by Toray) 5 parts, exemplified compound N
o. 4 0.5 parts methanol 60 parts / butanol 30
Part of the mixed solvent and dispersed for 1 hour in a sand mill using glass beads having a diameter of 1 mm to prepare a coating solution for the intermediate layer. Apply this coating solution to an aluminum cylinder (diameter 3
0 mm × length 260.5 mm) and applied by dip coating to form an intermediate layer having a film thickness of 0.3 μm.
【0067】次に、CuKα特性X線回折におけるブラ
ッグ角(2θ±0.2°)の9.0°、14.2°、2
3.9°及び27.1°に強いピークを有する結晶形の
オキシチタニウムフタロシアニン10部とポリビニルブ
チラール樹脂(商品名:エスレックBX−1、積水化学
工業社製)5部をシクロヘキサノン250部に添加し、
直径1mmのガラスビーズを用いたサンドミル装置で3
時間分散し、これに250部の酢酸エチルを添加して希
釈し、この塗布液を中間層上に浸漬塗布し、100℃で
10分間乾燥して、膜厚が0.16μmの電荷発生層を
形成した。Next, the Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 9.0 °, 14.2 °, 2
10 parts of crystalline oxytitanium phthalocyanine having strong peaks at 3.9 ° and 27.1 ° and 5 parts of polyvinyl butyral resin (trade name: S-REC BX-1, manufactured by Sekisui Chemical Co., Ltd.) were added to 250 parts of cyclohexanone. ,
3 with a sand mill device using glass beads with a diameter of 1 mm
Disperse for a period of time, add 250 parts of ethyl acetate to dilute it, dip-coat the coating solution on the intermediate layer, and dry at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.16 μm. Formed.
【0068】次に、下記に示される電荷輸送材料10
部、Next, the charge transport material 10 shown below is shown.
Department,
【0069】[0069]
【化6】
ポリカーボネート樹脂(商品名:ユーピロンZ−40
0、三菱ガス化学社製)10部をモノクロロベンゼン7
0部に溶解した溶液を調製し、電荷発生層上に浸漬塗布
し、110℃で1時間乾燥して、膜厚が25μmの電荷
輸送層を形成し、実施例6の電子写真感光体を作製し
た。[Chemical 6] Polycarbonate resin (Product name: Iupilon Z-40
0, manufactured by Mitsubishi Gas Chemical Co., Inc.) 10 parts of monochlorobenzene 7
A solution dissolved in 0 part was prepared, dip-coated on the charge generation layer, and dried at 110 ° C. for 1 hour to form a charge transport layer having a film thickness of 25 μm, and an electrophotographic photoreceptor of Example 6 was prepared. did.
【0070】(比較例2)実施例6において中間層に例
示化合物No.4を含有させなかった以外は、実施例6
と全く同様にして比較例2の電子写真感光体を作製し
た。(Comparative Example 2) In Example 6, the compound No. Example 6 except that 4 was not included
An electrophotographic photoreceptor of Comparative Example 2 was produced in exactly the same manner as.
【0071】(実施例7)ポリアミド樹脂(商品名:ア
ミランCM−4000、東レ社製)7部、二酸化チタン
粉末(商品名:タイペークR−670、石原産業社製)
15部、例示化合物No.19 0.5部をメタノール
50部/イソプロピルアルコール20部のの混合溶媒に
溶解して直径1mmのガラスビーズを用いたサンドミル
装置で1時間分散して中間層用塗布液を調製した。この
塗布液をアルミニウムシリンダー(直径30mm×長さ
260.5mm)上に浸漬塗布し、膜厚が0.7μmの
中間層を形成した。Example 7 7 parts of polyamide resin (trade name: Amilan CM-4000, manufactured by Toray), titanium dioxide powder (trade name: Taipaque R-670, manufactured by Ishihara Sangyo Co., Ltd.)
15 parts, exemplified compound No. 19 0.5 parts was dissolved in a mixed solvent of 50 parts of methanol / 20 parts of isopropyl alcohol and dispersed for 1 hour by a sand mill using glass beads having a diameter of 1 mm to prepare a coating solution for intermediate layer. This coating liquid was dip-coated on an aluminum cylinder (diameter 30 mm × length 260.5 mm) to form an intermediate layer having a film thickness of 0.7 μm.
【0072】次に、この中間層上に実施例6と同様にし
て電荷発生層と電荷輸送層を順次塗工し、実施例7の電
子写真感光体を作製した。Next, a charge generation layer and a charge transport layer were sequentially coated on this intermediate layer in the same manner as in Example 6 to prepare an electrophotographic photosensitive member of Example 7.
【0073】(比較例3)実施例7において中間層に例
示化合物No.19を含有させなかった以外は、実施例
7と全く同様にして比較例3の電子写真感光体を作製し
た。(Comparative Example 3) In Example 7, the compound No. An electrophotographic photosensitive member of Comparative Example 3 was produced in exactly the same manner as in Example 7 except that 19 was not included.
【0074】(比較例4)実施例7において中間層に例
示化合物No.19 0.5部を下記化合物に代えた以
外は、実施例7と全く同様にして比較例4の電子写真感
光体を作製した。(Comparative Example 4) In Example 7, the compound No. 19 An electrophotographic photosensitive member of Comparative Example 4 was produced in exactly the same manner as in Example 7 except that 0.5 parts of the following compounds were replaced.
【0075】[0075]
【化7】 [Chemical 7]
【0076】(実施例8)ヒドロキシプロピルセルロー
ス(東京化成工業社製)75部、ジルコニウムテトラ−
n−ブトキサイド(関東化学社製)25部、例示化合物
No.10 10部、アセチルアセトン10部及び水5
部をトルエン300部/ブタノール300部の混合溶媒
に溶解、混合して塗布液を調製した。この塗布液をアル
ミニウムシリンダー(直径30mm×長さ260.5m
m)上に浸漬塗布し、膜厚が0.3μmの中間層を形成
した。(Example 8) 75 parts of hydroxypropyl cellulose (manufactured by Tokyo Chemical Industry Co., Ltd.), zirconium tetra-
25 parts of n-butoxide (manufactured by Kanto Chemical Co., Inc.), exemplified compound No. 10 10 parts, acetylacetone 10 parts and water 5
Parts were dissolved and mixed in a mixed solvent of 300 parts of toluene / 300 parts of butanol to prepare a coating solution. Apply this coating solution to an aluminum cylinder (diameter 30 mm x length 260.5 m
m) was applied by dip coating to form an intermediate layer having a thickness of 0.3 μm.
【0077】次に、この中間層上に実施例6と同様にし
て電荷発生層と電荷輸送層を順次塗工し、実施例8の電
子写真感光体を作製した。Then, a charge generation layer and a charge transport layer were sequentially coated on this intermediate layer in the same manner as in Example 6 to prepare an electrophotographic photosensitive member of Example 8.
【0078】(比較例5)実施例8において中間層に例
示化合物No.10を含有させなかった以外は、実施例
8と全く同様にして比較例5の電子写真感光体を作製し
た。(Comparative Example 5) In Example 8, the compound No. An electrophotographic photosensitive member of Comparative Example 5 was produced in exactly the same manner as in Example 8 except that 10 was not included.
【0079】これら作製した各電子写真感光体を用いて
明部電位測定及びゴースト画像評価を行った。評価機に
はレーザービームプリンター(商品名:レーザージェッ
ト4000、ヒューレットパッカード社製)を現像バイ
アスが可変できるように改造して使用した。Using each of the electrophotographic photoconductors produced as described above, the light potential was measured and the ghost image was evaluated. A laser beam printer (trade name: Laserjet 4000, manufactured by Hewlett Packard) was used as an evaluation machine after being modified so that the developing bias could be changed.
【0080】明部電位の測定は、評価機から現像用カー
トリッジを抜き取り、そこに電位測定装置を挿入して行
った。電位測定装置は、現像用カートリッジの現像位置
に電位測定プローブを配置することで構成されており、
電子写真感光体に対する電位測定プローブの位置は、電
子写真感光体軸方向のほぼ中央、電子写真感光体表面か
らのギャップを3mmとした。画像データは全面黒画像
とした。The light potential was measured by removing the developing cartridge from the evaluation machine and inserting a potential measuring device therein. The potential measuring device is configured by disposing a potential measuring probe at the developing position of the developing cartridge,
The position of the potential measuring probe with respect to the electrophotographic photosensitive member was approximately the center in the axial direction of the electrophotographic photosensitive member, and the gap from the surface of the electrophotographic photosensitive member was 3 mm. The image data was a black image over the entire surface.
【0081】ゴースト画像評価は以下のようにした。ゴ
ースト画像は5mm角の黒四角パターンをドラム一周分
任意の数だけ印字し、その後、全面ハーフトーン画像
(1ドット1スペースのドット密度の画像)又は全面白
画像とした。ゴースト画像サンプルは、3通りの現像バ
イアスボリューム、F1(濃度高い)、F5(中心
値)、F9(濃度薄い)の各モードでサンプリングし
た。評価は目視で行い、ゴーストの程度で、
ランク1:いずれのモードでもゴーストは全く見えない
レベル
ランク2:いずれかのモードでゴーストがうっすら見え
るレベル
ランク3:いずれのモードでもゴーストがうっすら見え
るレベル
ランク4:いずれのモードでもゴーストが見えるレベル
のようにランク付けした。The ghost image evaluation is as follows. As a ghost image, a black square pattern of 5 mm square was printed by an arbitrary number for one round of the drum, and then a full-face halftone image (image of dot density of 1 dot 1 space) or a full-white image was formed. The ghost image sample was sampled in each of three types of development bias volume, F1 (high density), F5 (center value), and F9 (low density) modes. The evaluation is done visually, and it is a ghost degree. Rank 1: No ghost is visible in any mode Rank 2: Ghost is slightly visible in any mode Level 3: Ghost is slightly visible in any mode 4: In each mode, it was ranked like a level at which a ghost can be seen.
【0082】23℃/55%RH環境下での初期の明部
電位の測定及びゴースト画像評価を行った後、同環境下
で1分間4枚プリントの間欠モードで約0.5mm幅の
線を縦10mm間隔のパターンを印字するモードで10
00枚の通紙耐久試験を行い、耐久直後及び15時間後
での明部電位の測定及びゴースト画像の評価を行った。After measuring the initial bright part potential and evaluating the ghost image under the environment of 23 ° C./55% RH, a line of about 0.5 mm width was printed in the intermittent environment for four minutes in the same environment for four minutes. 10 in the mode that prints a pattern with vertical 10 mm intervals
A paper passing durability test of 00 sheets was performed, and the light area potential was measured and the ghost image was evaluated immediately after the durability test and 15 hours after the durability test.
【0083】次に、作製した各電子写真感光体を評価機
と共に、15℃/10%RHの低温低湿(L/L)環境
下で3日間放置した後、明部電位の測定及びゴースト画
像の評価を行った。Next, each of the produced electrophotographic photoconductors was allowed to stand for 3 days together with an evaluation machine in a low temperature and low humidity (L / L) environment of 15 ° C./10% RH, after which the light potential was measured and the ghost image was taken. An evaluation was made.
【0084】以上の結果を表4に示す。The above results are shown in Table 4.
【0085】[0085]
【表4】 [Table 4]
【0086】[0086]
【発明の効果】上述のように、本発明の電子写真感光体
は、連続プリント時における電位変動が少なく、ゴース
ト等の画像欠陥のない画像を提供できるという顕著な効
果を奏する。また、この電子写真感光体を有するプロセ
スカートリッジならびに電子写真装置においても同様の
効果を奏する。As described above, the electrophotographic photosensitive member of the present invention has a remarkable effect that an electric potential fluctuation during continuous printing is small and an image having no image defects such as ghost can be provided. Further, the same effect can be obtained in the process cartridge and the electrophotographic apparatus having the electrophotographic photosensitive member.
【図1】本発明の電子写真感光体を有するプロセスカー
トリッジを備えた電子写真装置の概略構成の例を示す図
である。FIG. 1 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having an electrophotographic photosensitive member of the present invention.
【符号の説明】 1 電子写真感光体 2 軸 3 帯電手段 4 露光光 5 現像手段 6 転写手段 7 転写材 8 定着手段 9 クリーニング手段 10 前露光光 11 プロセスカートリッジ 12 案内手段[Explanation of symbols] 1 Electrophotographic photoreceptor 2 axes 3 charging means 4 exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 guidance means
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) G03G 5/14 G03G 5/14 102C 102Z (72)発明者 平野 秀敏 東京都大田区下丸子3丁目30番2号 キヤ ノン株式会社内 (72)発明者 東 隆司 東京都大田区下丸子3丁目30番2号 キヤ ノン株式会社内 Fターム(参考) 2H068 AA21 AA42 AA43 AA44 AA45 AA50 BA12 BA57 BA58 BB06 BB16 BB17 BB23 BB28 BB29 BB30 BB35 BB37 BB50 CA02 CA29 CA33 CA37 FA18 FA27─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) G03G 5/14 G03G 5/14 102C 102Z (72) Inventor Hidetoshi Hirano 3-30-2 Shimomaruko, Ota-ku, Tokyo No. Canon Inc. (72) Inventor Ryuji Higashi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. F-term (reference) 2H068 AA21 AA42 AA43 AA44 AA45 AA50 BA12 BA57 BA58 BB06 BB16 BB17 BB23 BB28 BB29 BB30 BB35 BB37 BB50 CA02 CA29 CA33 CA37 FA18 FA27
Claims (10)
送材料を含有する感光層を有する電子写真感光体におい
て、該導電性支持体と該感光層との間に設ける中間層に
下記式(1)で示されるレゾルシナレーン化合物を含有
することを特徴とする電子写真感光体。 【化1】 (式中、R1は水素原子、置換基を有してもよいアルキ
ル基又はアリール基を示し、R2は水素原子、置換基を
有してもよいアルキル基、アリール基又はAr−N=N
−基を示し、Arは同一又は異なって、置換基を有して
もよい芳香族炭化水素環、置換基を有してもよい複素環
又は置換基を有してもよい複数の芳香族炭化水素環ある
いは置換基を有してもよい複数の複素環を結合したもの
の1価の基を示す)1. An electrophotographic photoreceptor having a photosensitive layer containing a charge generating material and a charge transporting material on a conductive support, wherein an intermediate layer provided between the conductive support and the photosensitive layer has the following formula: An electrophotographic photoreceptor containing the resorcinarene compound represented by (1). [Chemical 1] (In the formula, R 1 represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group, and R 2 represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group or Ar-N = N
Represents a group, and Ar is the same or different, and may have an aromatic hydrocarbon ring which may have a substituent, a heterocycle which may have a substituent, or a plurality of aromatic hydrocarbon which may have a substituent. A monovalent group of a hydrogen ring or a plurality of heterocycles which may have a substituent is bonded)
で示される化合物である請求項1に記載の電子写真感光
体。 【化2】 (式中、R1は水素原子、置換基を有してもよいアルキ
ル基又はアリール基を示し、Arは同一又は異なって、
置換基を有してもよい芳香族炭化水素環、置換基を有し
てもよい複素環又は置換基を有してもよい複数の芳香族
炭化水素環あるいは置換基を有してもよい複数の複素環
を結合したものの1価の基を示す)2. A resorcinarene compound represented by the following formula (2):
The electrophotographic photoreceptor according to claim 1, which is a compound represented by [Chemical 2] (In the formula, R 1 represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group, and Ar is the same or different;
Aromatic hydrocarbon ring which may have a substituent, heterocyclic ring which may have a substituent or a plurality of aromatic hydrocarbon rings which may have a substituent or a plurality which may have a substituent. Represents a monovalent group of the heterocycles)
脂、ポリウレタン、ポリアミド、ポリイミド、ポリアミ
ドイミド、ポリアミド酸、ポリビニルアセタール、ポリ
ビニルブチラール、エポキシ樹脂、アクリル樹脂、セル
ロース樹脂、メラミン樹脂及びポリエステルからなる群
より選ばれる少なくとも1種を含有する請求項1又は2
に記載の電子写真感光体。3. A group consisting of phenol resin, polyurethane, polyamide, polyimide, polyamide imide, polyamic acid, polyvinyl acetal, polyvinyl butyral, epoxy resin, acrylic resin, cellulose resin, melamine resin and polyester as the binder resin for the intermediate layer. 3. At least one selected from the group consisting of
The electrophotographic photosensitive member according to 1.
〜3のいずれかに記載の電子写真感光体。4. The intermediate layer contains a conductive substance.
The electrophotographic photosensitive member according to any one of 1 to 3.
着樹脂として、フェノール樹脂、ポリウレタン、ポリア
ミド、ポリイミド、ポリアミドイミド、ポリアミド酸、
ポリビニルアセタール、ポリビニルブチラール、エポキ
シ樹脂、アクリル樹脂、セルロース樹脂、メラミン樹脂
及びポリエステルからなる群より選ばれる少なくとも1
種を含有する第2中間層からなる積層中間層を有する電
子写真感光体において、第1中間層と第2中間層の両層
に上記式(1)で示されるレゾルシナレーン化合物を含
有する請求項1〜4のいずれかに記載の電子写真感光
体。5. A first intermediate layer containing a conductive substance, and as a binder resin, phenol resin, polyurethane, polyamide, polyimide, polyamideimide, polyamic acid,
At least one selected from the group consisting of polyvinyl acetal, polyvinyl butyral, epoxy resin, acrylic resin, cellulose resin, melamine resin and polyester.
An electrophotographic photoreceptor having a laminated intermediate layer comprising a second intermediate layer containing a seed, wherein both the first intermediate layer and the second intermediate layer contain a resorcinarene compound represented by the above formula (1). 4. The electrophotographic photosensitive member according to any one of to 4.
属酸化物及びカーボンブラックからなる群より選ばれる
少なくとも1種である請求項1〜5のいずれかに記載の
電子写真感光体。6. The electrophotographic photosensitive member according to claim 1, wherein the conductive substance is at least one selected from the group consisting of metals, organometallic compounds, metal oxides and carbon black.
n−ブトキサイド、チタニウムテトラ−n−ブトキサイ
ド、アルミニウムイソプロポキシド及びメチルメトキシ
シランからなる群より選ばれる少なくとも1種である請
求項6に記載の電子写真感光体。7. The organometallic compound is zirconium tetra-
The electrophotographic photosensitive member according to claim 6, which is at least one selected from the group consisting of n-butoxide, titanium tetra-n-butoxide, aluminum isopropoxide, and methylmethoxysilane.
酸化アルミニウムからなる群より選ばれる少なくとも1
種である請求項6に記載の電子写真感光体。8. The metal oxide is at least one selected from the group consisting of titanium oxide, tin oxide and aluminum oxide.
The electrophotographic photosensitive member according to claim 6, which is a seed.
真感光体を、該電子写真感光体を帯電させる帯電手段、
静電潜像の形成された電子写真感光体をトナーで現像す
る現像手段及び転写工程後の電子写真感光体上に残余す
るトナーを回収するクリーニング手段からなる群より選
ばれた少なくとも1つの手段と共に一体に支持し、電子
写真装置本体に着脱自在であることを特徴とするプロセ
スカートリッジ。9. A charging means for charging the electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member is charged.
Along with at least one means selected from the group consisting of a developing means for developing an electrophotographic photosensitive member on which an electrostatic latent image is formed with toner and a cleaning means for recovering residual toner on the electrophotographic photosensitive member after the transfer step. A process cartridge which is integrally supported and is detachable from the main body of the electrophotographic apparatus.
写真感光体、該電子写真感光体を帯電させる帯電手段、
帯電した電子写真感光体に対し露光を行い静電潜像を形
成する露光手段、静電潜像の形成された電子写真感光体
にトナーで現像する現像手段及び電子写真感光体上のト
ナー像を転写材上に転写する転写手段を備えることを特
徴とする電子写真装置。10. The electrophotographic photosensitive member according to claim 1, a charging unit for charging the electrophotographic photosensitive member,
An exposure unit that exposes a charged electrophotographic photosensitive member to form an electrostatic latent image, a developing unit that develops with a toner on the electrophotographic photosensitive member on which the electrostatic latent image is formed, and a toner image on the electrophotographic photosensitive member. An electrophotographic apparatus comprising a transfer means for transferring onto a transfer material.
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JP2002095762A JP3774673B2 (en) | 2002-03-29 | 2002-03-29 | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
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JP2003295489A true JP2003295489A (en) | 2003-10-15 |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7097950B2 (en) | 2004-05-27 | 2006-08-29 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
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2002
- 2002-03-29 JP JP2002095762A patent/JP3774673B2/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7097950B2 (en) | 2004-05-27 | 2006-08-29 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
US7452644B2 (en) | 2004-05-27 | 2008-11-18 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
EP2264539A1 (en) | 2004-05-27 | 2010-12-22 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
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Publication number | Publication date |
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JP3774673B2 (en) | 2006-05-17 |
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