JPH06332220A - Electrophotographic sensitive body - Google Patents
Electrophotographic sensitive bodyInfo
- Publication number
- JPH06332220A JPH06332220A JP12148893A JP12148893A JPH06332220A JP H06332220 A JPH06332220 A JP H06332220A JP 12148893 A JP12148893 A JP 12148893A JP 12148893 A JP12148893 A JP 12148893A JP H06332220 A JPH06332220 A JP H06332220A
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- JP
- Japan
- Prior art keywords
- group
- charge
- layer
- substance
- transporting
- 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.)
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- Photoreceptors In Electrophotography (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は電子写真感光体に関し、
特に改良された保護層を有する正帯電用感光体に関す
る。FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor,
In particular, the present invention relates to a positive charging photoreceptor having an improved protective layer.
【0002】[0002]
【従来の技術】従来、有機光導電性材料を用いた電子写
真感光体は、無公害,低コスト,高生産性等の利点を有
するため、研究,開発が進められ、既に中速複写機の感
光体として使用されており、高速複写機用の感光体とし
ても実用化が進められている。2. Description of the Related Art Conventionally, an electrophotographic photosensitive member using an organic photoconductive material has advantages such as no pollution, low cost and high productivity. It is used as a photoconductor and is being put into practical use as a photoconductor for high-speed copying machines.
【0003】前記感光体は高性能の電子写真性能を確保
する上で、電荷を発生する機能を有する電荷発生物質
(CGM)と、電荷を輸送する機能を有する電荷輸送物
質(CTM)とを含有する感光体とするのが好ましい。
前記感光体としては、感光層中にCGMとCTMを共存
させた単層構成型又は主要成分としてCTMを含有する
電荷輸送層(CTL)とCGMを含有する電荷発生層
(CGL)とを有する二層構成の機能分離型感光体とが
ある。In order to ensure high-performance electrophotographic performance, the photoreceptor contains a charge generating material (CGM) having a function of generating electric charges and a charge transporting material (CTM) having a function of transferring electric charges. It is preferable to use a photoconductor.
The photoconductor has a single layer constitution type in which CGM and CTM coexist in the photosensitive layer or a charge transport layer (CTL) containing CTM as a main component and a charge generation layer (CGL) containing CGM. There is a function-separated type photoreceptor having a layer structure.
【0004】前記機能分離型感光体に含有されるCTM
としては、従来ホール輸送機能に優れたP型CTMが多
数開発されている。CTM contained in the function-separated type photoreceptor
As a conventional method, many P-type CTMs having excellent hole transporting functions have been developed.
【0005】そこで従来電荷発生機能に優れたCGMを
含有するCGLを下層とし、前記ホール輸送機能に優れ
たP型CTMを含有するCTLを上層とする負帯電性の
感光体が主流とされた。Therefore, a negatively-charged photoreceptor having a CGL containing CGM having an excellent charge generating function as a lower layer and a CTL containing P-type CTM having an excellent hole transporting function as an upper layer has been mainly used.
【0006】しかしながら前記感光体では、負の帯電時
多量のオゾンを発生して環境を害するばかりでなく、感
光体表面を変質して疲労劣化せしめると云う問題があっ
た。However, the above-mentioned photoconductor has a problem that a large amount of ozone is generated at the time of negative electrification, which not only harms the environment, but also deteriorates the photoconductor surface to cause fatigue deterioration.
【0007】そこで前記感光体の層構成を逆にして、C
TLを下層とし、CGLを上層とする正帯電用二層構成
の感光体の研究開発が進められている。又前記単層構成
の感光体は、CTMとしてP型CTMを用いているの
で、負帯電用として使用する場合よりも正帯電用として
使用する方が電子写真性能が優れている。Therefore, by reversing the layer structure of the photoreceptor, C
Research and development of a photoconductor having a two-layer structure for positive charging, in which TL is the lower layer and CGL is the upper layer, is underway. Further, since the photoreceptor having the single-layer structure uses the P-type CTM as the CTM, the electrophotographic performance is better when used for positive charging than when used for negative charging.
【0008】しかしながらこれらの感光体は何れもCG
Mが感光体の表面層に存在することとなるため、光,コ
ロナ放電,湿度,機械的摺擦等による変質又は摩耗によ
り感光体が疲労劣化し易いと云う問題がある。However, all of these photoreceptors are CG
Since M is present in the surface layer of the photoconductor, there is a problem that the photoconductor is easily fatigue-degraded due to deterioration or abrasion due to light, corona discharge, humidity, mechanical rubbing, or the like.
【0009】そこで例えば絶縁性で透明な樹脂の保護層
を設けることが提案され、かつ光照射時、前記保護層に
電子受容性物質を含有せしめ、該保護層による電荷のブ
ロッキングを防止するようにした技術が提案されてい
る。Therefore, for example, it is proposed to provide a protective layer of an insulating and transparent resin, and at the time of light irradiation, the protective layer contains an electron-accepting substance so as to prevent the blocking of charges by the protective layer. The technology which was done is proposed.
【0010】例えば、特開昭62-157047号公報には、導
電性支持体上にCTL,CGLをこの順に設けた正帯電
用感光体上に電子受容性物質を含有する保護層を設ける
技術が提案されている。又前記公報には前記電子受容性
物質が電子輸送機能を有することから、光照射時発生す
る光電子が保護層中を速やかに移動可能となり、感光体
の表面正電荷を効率よく打ち消し、良質の画像が得られ
ることが記載されている。For example, JP-A-62-157047 discloses a technique of providing a protective layer containing an electron-accepting substance on a positive charging photoreceptor having a conductive support and CTL and CGL provided in this order. Proposed. Further, in the above-mentioned publication, since the electron-accepting substance has an electron-transporting function, photoelectrons generated at the time of light irradiation can move quickly in the protective layer, and the surface positive charges of the photoconductor can be effectively canceled, resulting in a high-quality image. Is obtained.
【0011】[0011]
【発明が解決しようとする課題】しかしながら、従来公
知の前記電子受容性物質は必ずしも電子輸送機能が十分
ではなく、そのため保護層の膜厚を薄くせざるを得ず、
機械的耐摩耗性が不十分となる。又比較的に電子輸送機
能に優れたものであってもバインダー樹脂又は溶剤への
溶解性が悪く、本来の電子輸送機能が発揮されず、かつ
保護層中における前記電子受容性物質の分布が不均一と
なる。そのため光照射時発生した電荷が保護層中にブロ
ッキングされて感光体の表面電荷が消散されずかぶりの
多い画像が得られるとか、像形成の過程で感光体が早め
に疲労劣化し、耐刷性が悪いなどの問題を生じていた。However, the conventionally known electron-accepting substance does not always have a sufficient electron-transporting function, so that the protective layer must be thinned.
Mechanical wear resistance becomes insufficient. Even if it has a relatively excellent electron-transporting function, it has poor solubility in a binder resin or a solvent, the original electron-transporting function is not exhibited, and the distribution of the electron-accepting substance in the protective layer is poor. Be uniform. Therefore, the charge generated during light irradiation is blocked in the protective layer and the surface charge of the photoconductor is not dissipated, resulting in an image with a lot of fog. Was causing problems such as bad.
【0012】そこで近年電子受容性物質として周知の2,
4,7-トリニトロ-9-フルオレノンの改良研究が行なわ
れ、該化合物の構造中に可溶化基を導入し、バインダー
樹脂及び溶剤との相溶性を増大して特性を改良する技術
が、例えば特開平1-206349号,同2-135362号,同2-2148
66号,同3-290666号の各号公報及び「Japam Hardcopy,
92論文集,173,(1922)」等に提案されている。[0012] Therefore, recently known as an electron-accepting substance,
Improvement studies on 4,7-trinitro-9-fluorenone have been carried out, and a technique of introducing a solubilizing group into the structure of the compound to increase the compatibility with the binder resin and the solvent to improve the properties has been described in, for example, Kaihei 1-206349, 2-135362, 2-2148
Nos. 66 and 3-290666, and "Japam Hardcopy,"
92 papers, 173, (1922) ”, etc.
【0013】しかしながら、前記各号公報及び文献に記
載される何れの化合物も正帯電用感光体の保護層に用い
たとき繰り返し像形成の過程で前記感光体疲労劣化し、
満足できるものではなかった。However, when any of the compounds described in the above publications and documents is used for the protective layer of the positive charging photoreceptor, the photoreceptor fatigue deteriorates in the course of repeated image formation,
I was not satisfied.
【0014】本発明は前記実情に鑑みて提案されたもの
であり、本発明の目的は、帯電特性,光減衰特性,残留
電位特性等に優れていると共に、像形成時のオゾン発生
がなく、かつ耐刷性に優れていて、繰り返し像形成の過
程で疲労劣化のない正帯電用の感光体を提供することに
ある。The present invention has been proposed in view of the above circumstances, and an object of the present invention is that it is excellent in charging characteristics, light attenuation characteristics, residual potential characteristics, and the like, and does not generate ozone during image formation. Another object of the present invention is to provide a photoconductor for positive charging, which has excellent printing durability and is free from fatigue deterioration during repeated image formation.
【0015】[0015]
【課題を解決するための手段】前記の目的は、導電性支
持体上に感光層を設け、該感光層上に保護層を設けた電
子写真感光体において、前記保護層に電子受容性物質と
して、構造諸元を特定した「化23」,「化24」,「化2
5」,「化26」,「化27」,「化28」,「化29」,「化3
0」,「化31」,「化32」,「化33」に記載の一般式
〔A〕,〔B〕,〔C〕,〔D〕,〔E〕,〔F〕,
〔G〕,〔H〕,〔J〕,〔K〕及び〔L〕で表わされ
る何れかの化合物を含有して成る各電子写真感光体によ
り達成される。The above object is to provide an electrophotographic photoreceptor having a photosensitive layer provided on a conductive support and a protective layer provided on the photosensitive layer. , "Chemical 23,""Chemical24,""Chemical2"
5 ”,“ 26 ”,“ 27 ”,“ 28 ”,“ 29 ”,“ 3 ”
0 ”,“ Chemical formula 31 ”,“ Chemical formula 32 ”,“ Chemical formula 33 ”, the general formulas [A], [B], [C], [D], [E], [F],
This is achieved by each electrophotographic photosensitive member containing any of the compounds represented by [G], [H], [J], [K] and [L].
【0016】[0016]
【化23】 [Chemical formula 23]
【0017】式中、RAはハロゲン原子,ヒドロキシ
基,ニトロ基,CF3基,COORA′基,OCORA′
基,CONH2基,CONHRA′基,CON(RA′)2
基,CORA′基又は置換基を有してもよいアルキル
基,アルコキシ基,アリール基,アラルキル基若しくは
アルキルアミノ基を表し、RA′は置換基を有してもよ
いアルキル基,アリール基又はアラルキル基を表す。
l,m及びnはそれぞれ0又は正の整数を表し、lが0
のときmは2以上の整数を表し、lが1以上の整数のと
きmは0又は正の整数を表す。又複数個あるRAで表す
基は互いに同じでも異なってもよい。In the formula, R A is a halogen atom, a hydroxy group, a nitro group, a CF 3 group, a COOR A ′ group, an OCOR A ′.
Group, CONH 2 group, CONHR A ′ group, CON (R A ′) 2
Group, COR A 'group or an optionally substituted alkyl group, an alkoxy group, an aryl group, an aralkyl group or an alkylamino group, R A' represents an alkyl group which may have a substituent, an aryl group Alternatively, it represents an aralkyl group.
l, m and n each represent 0 or a positive integer, and l is 0
In the case of, m represents an integer of 2 or more, and when 1 is an integer of 1 or more, m represents 0 or a positive integer. The plural groups represented by R A may be the same or different.
【0018】[0018]
【化24】 [Chemical formula 24]
【0019】式中、YBはシアノ基又はCF3基を表し、
RBはハロゲン原子,ヒドロキシ基,ニトロ基,CF
3基,COORB′基,OCORB′基,CONH2基,C
ONHRB′基,CON(RB′)2基,CORB′基又は
置換基を有してもよいアルキル基,アルコキシ基,アリ
ール基,アラルキル基若しくはアルキルアミノ基を表
し、RB′は置換基を有してもよいアルキル基,アリー
ル基又はアラルキル基を表す。l,m及びnはそれぞれ
1以上の整数を表す。又複数個有るYB,RBの各基はそ
れぞれ同じ基から成ってもよく、異なる基から成っても
よい。In the formula, Y B represents a cyano group or a CF 3 group,
R B is a halogen atom, hydroxy group, nitro group, CF
3 group, COOR B 'group, OCOR B' group, CONH 2 group, C
ONHR B ′ group, CON (R B ′) 2 group, COR B ′ group or an optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group or alkylamino group, wherein R B ′ is substituted Represents an alkyl group, an aryl group or an aralkyl group which may have a group. l, m and n each represent an integer of 1 or more. The plural groups of Y B and R B may be the same or different.
【0020】[0020]
【化25】 [Chemical 25]
【0021】式中、XCはCOORC′基,OCORC′
基,CONH2基,CONHRC′基,CON(RC′)2
基,CORC′基又はCHO基を表し、YCはハロゲン原
子,シアノ基,ニトロ基,CF3基,COOH基,SO2
NH2基,SO2RC′基又はSORC′基を表し、RCは
ハロゲン原子,ヒドロキシ基,ニトロ基,CF3基,C
OORC′基,OCORC′基,CONH2基,CONH
RC′基,CON(RC′)2基,CORC′基又は置換基
を有してもよいアルキル基,アルコキシ基,アリール
基,アラルキル基若しくはアルキルアミノ基を表し、R
C′は置換基を有してもよいアルキル基,アリール基又
はアラルキル基を表す。l及びnは1以上の整数を表
し、mは0又は正の整数を表し、l+mは2以上の整数
を表す。又複数個あるXC,YC,RCの各基はそれぞれ
同じ基から成ってもよく、異なる基から成ってもよい。[0021] In the formula, X C is COOR C 'group, OCOR C'
Group, CONH 2 group, CONHR C ′ group, CON (R C ′) 2
Group, a COR C ′ group or a CHO group, and Y C is a halogen atom, a cyano group, a nitro group, a CF 3 group, a COOH group, SO 2
NH 2 group, SO 2 R C ′ group or SOR C ′ group, wherein R C is a halogen atom, a hydroxy group, a nitro group, a CF 3 group, C
OOR C ′ group, OCOR C ′ group, CONH 2 group, CONH
R C ′ group, CON (R C ′) 2 group, COR C ′ group or alkyl group, alkoxy group, aryl group, aralkyl group or alkylamino group which may have a substituent,
C 'represents an optionally substituted alkyl group, an aryl group or an aralkyl group. l and n represent an integer of 1 or more, m represents 0 or a positive integer, and l + m represents an integer of 2 or more. The plural groups of X C , Y C and R C may be the same or different.
【0022】[0022]
【化26】 [Chemical formula 26]
【0023】式中、XDはCOOH基,SO2NH2基,
SORD′基又はSO2RD′基を表し、YDはハロゲン原
子,シアノ基,ニトロ基又はCF3基を表し、RDはハロ
ゲン原子,ヒドロキシ基,ニトロ基,CF3基,COO
RD′基、OCORD′基,CONH2基,CONHRD′
基,CON(RD′)2基,CORD′基又は置換基を有
してもよいアルキル基,アルコキシ基,アリール基,ア
ラルキル基若しくはアルキルアミノ基を表し、RD′は
置換基を有してもよいアルキル基,アリール基又はアラ
ルキル基を表す。l及びnは1以上の整数を表し、mは
0又は正の整数を表し、l+mは2以上の整数を表す。
又複数個あるXD,YD,RDの各基はそれぞれ同じ基か
ら成ってもよく、異なる基から成ってもよい。In the formula, X D is a COOH group, SO 2 NH 2 group,
Represents a SOR D ′ group or a SO 2 R D ′ group, Y D represents a halogen atom, a cyano group, a nitro group or a CF 3 group, and R D represents a halogen atom, a hydroxy group, a nitro group, a CF 3 group or COO
R D ′ group, OCOR D ′ group, CONH 2 group, CONHR D ′
Group, CON (R D ′) 2 group, COR D ′ group or an optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group or alkylamino group, and R D ′ has a substituent group. Represents an alkyl group, an aryl group or an aralkyl group which may be present. l and n represent an integer of 1 or more, m represents 0 or a positive integer, and l + m represents an integer of 2 or more.
The plural groups of X D , Y D and R D may be the same or different.
【0024】[0024]
【化27】 [Chemical 27]
【0025】式中、XEはハロゲン原子を表し、YEはシ
アノ基,ニトロ基又はCF3基を表し、REはハロゲン原
子,ヒドロキシ基,ニトロ基,CF3基,COORE′
基,OCORE′基,CONH2基,CONHRE′基,
CON(RE′)2基,CORE′基又は置換基を有して
もよいアルキル基,アルコキシ基,アリール基,アラル
キル基若しくはアルキルアミノ基を表し、RE′は置換
基を有してもよいアルキル基,アリール基又はアラルキ
ル基を表す。l及びnは1以上の整数を表し、mは0又
は正の整数を表し、l+mは2以上の整数を表す。又複
数個あるXE,YE,REの各基はそれぞれ同じ基から成
ってもよく、異なる基から成ってもよい。In the formula, X E represents a halogen atom, Y E represents a cyano group, a nitro group or a CF 3 group, and R E represents a halogen atom, a hydroxy group, a nitro group, a CF 3 group or COOR E ′.
Group, OCOR E ′ group, CONH 2 group, CONHR E ′ group,
A CON (R E ′) 2 group, a COR E ′ group or an optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group or alkylamino group, R E ′ having a substituent group Represents an alkyl group, an aryl group or an aralkyl group. l and n represent an integer of 1 or more, m represents 0 or a positive integer, and l + m represents an integer of 2 or more. The plural groups of X E , Y E and R E may be the same or different.
【0026】[0026]
【化28】 [Chemical 28]
【0027】式中、XFはハロゲン原子,シアノ基,ニ
トロ基,CF3基,COOH基,COORF′基,OCO
RF′基,CONH2基,CONHRF′基,CON
(RF′)2基,CORF′基,SO2NH2基,SORF′
基,SO2RF′基又はCHO基を表し、YFは置換基を
有してもよいアルキル基,アリール基又はアラルキル基
を表し、RFはハロゲン原子,ヒドロキシ基,ニトロ
基,CF3基,COORF′基,OCORF′基,CON
H2基,CONHRF′基,CON(RF′)2基,COR
F′基又は置換基を有してもよいアルキル基,アルコキ
シ基,アリール基,アラルキル基若しくはアルキルアミ
ノ基を表し、RF′は置換基を有してもよいアルキル
基,アリール基又はアラルキル基を表す。又複数個ある
XF,YF,RFの各基はそれぞれ同じ基から成ってもよ
く、異なる基から成ってもよい。In the formula, X F is a halogen atom, a cyano group, a nitro group, a CF 3 group, a COOH group, a COOR F ′ group, or an OCO.
R F ′ group, CONH 2 group, CONHR F ′ group, CON
(R F ′) 2 group, COR F ′ group, SO 2 NH 2 group, SOR F ′
Group, SO 2 R F ′ group or CHO group, Y F represents an alkyl group which may have a substituent, an aryl group or an aralkyl group, and R F represents a halogen atom, a hydroxy group, a nitro group or CF 3 group, COOR F 'group, OCOR F' group, CON
H 2 group, CONHR F ′ group, CON (R F ′) 2 group, COR
F 'group or an alkyl group which may have a substituent, an alkoxy group, an aryl group, an aralkyl group or an alkylamino group, R F' is an optionally substituted alkyl group, an aryl group or an aralkyl group Represents The plural groups of X F , Y F and R F may be the same or different.
【0028】[0028]
【化29】 [Chemical 29]
【0029】式中、Y1Gは置換基を有してもよいアルキ
ル基を表し、R2Gはハロゲン原子,ヒドロキシ基,シア
ノ基,ニトロ基,N(RG′)2基,ORG′基,COO
RG′基,OCORG′基,CORG′基,CONHRG′
基,CON(RG′)2基,SORG′基,SO2RG′基
又は置換基を有してもよいアリール基若しくはアラルキ
ル基を表し、RG′は置換基を有してもよいアルキル
基,アリール基又はアラルキル基を表す。lは0又は正
の整数を表し、mは2以上の整数を表し、nは1以上の
整数を表す。又複数個あるY1G,R2Gの各基はそれぞれ
同じ基から成ってもよく、異なる基から成ってもよい。In the formula, Y 1G represents an alkyl group which may have a substituent, R 2G represents a halogen atom, a hydroxy group, a cyano group, a nitro group, an N (R G ′) 2 group, an OR G ′ group. , COO
R G ′ group, OCOR G ′ group, COR G ′ group, CONHR G ′
Group, CON (R G ′) 2 group, SOR G ′ group, SO 2 R G ′ group, or an aryl group or aralkyl group which may have a substituent, and R G ′ may have a substituent. Represents a good alkyl group, aryl group or aralkyl group. l represents 0 or a positive integer, m represents an integer of 2 or more, and n represents an integer of 1 or more. The plurality of Y 1G and R 2G groups may be the same or different.
【0030】[0030]
【化30】 [Chemical 30]
【0031】式中、XHはヒドロキシ基,ORH′基,N
(RH′)2基又は置換基を有してもよいアルキル基,ア
リール基若しくはアラルキル基を表し、YHはハロゲン
原子,シアノ基,ニトロ基,CF3基,CORH′基,C
OORH′基,OCORH′基,CONHRH′基,CO
N(RH′)2基,SORH′基又はSO2RH′基を表
し、RHは置換基を有してもよいアルキル基又はアラル
キル基を表し、RH′は置換基を有してもよいアルキル
基又はアリール基を表す。lは0又は正の整数を表し、
mは2以上の整数を表し、l+mは2から8の整数を表
す。又複数個あるXH,YH,RH′の各基はそれぞれ同
じ基から成ってもよく、異なる基から成ってもよい。In the formula, X H is a hydroxy group, an OR H ′ group, N
(R H ′) 2 group or an optionally substituted alkyl group, aryl group or aralkyl group, Y H is a halogen atom, a cyano group, a nitro group, a CF 3 group, a COR H ′ group, C
OOR H ′ group, OCOR H ′ group, CONHR H ′ group, CO
Represents an N (R H ′) 2 group, a SOR H ′ group or a SO 2 R H ′ group, R H represents an optionally substituted alkyl group or an aralkyl group, and R H ′ has a substituent. Represents an alkyl group or an aryl group which may be present. l represents 0 or a positive integer,
m represents an integer of 2 or more, and l + m represents an integer of 2 to 8. The plural groups of X H , Y H and R H ′ may be the same or different.
【0032】又前記一般式〔H〕における置換基がアル
キル基であるか、又はアルキル基を含む時、特に規定の
ない限り、アルキル基は直鎖状、分岐鎖状又は環状の置
換されていても、不飽和結合を含んでいても良いアルキ
ル基(たとえば、メチルエチル基,iso−プロピル
基,t−ブチル基,ペンチル基,2−エチルヘキシル
基,ドデシル基,アリル基,オレイル基,ベンジル基,
ヒドロキシエチル基,メトキシエチル基,フェノキシエ
チル基)を意味する。When the substituent in the above formula [H] is an alkyl group or contains an alkyl group, the alkyl group may be linear, branched or cyclic unless otherwise specified. Or an alkyl group which may contain an unsaturated bond (eg, methylethyl group, iso-propyl group, t-butyl group, pentyl group, 2-ethylhexyl group, dodecyl group, allyl group, oleyl group, benzyl group,
Hydroxyethyl group, methoxyethyl group, phenoxyethyl group).
【0033】又前記一般式〔H〕における置換基がアリ
ール基であるか、又はアリール基を含む時、特に規定の
ない限り、アリール基は置換されていてもよく単環若し
くは縮合環のアリール基(たとえば、フェニル基,1−
ナフチル基,p−トリル基,p−クロロフェニル基,4
−メトキシフェニル基,ペンタフルオロフェニル基,p
−ヒドロキシフェニル基,p−シアノフェニル基,p−
メタンスルホンアミドフェニル基,3,4−ジクロロフ
ェニル基)を意味する。When the substituent in the above formula [H] is an aryl group or contains an aryl group, the aryl group may be substituted unless otherwise specified, and is a monocyclic or condensed ring aryl group. (For example, phenyl group, 1-
Naphthyl group, p-tolyl group, p-chlorophenyl group, 4
-Methoxyphenyl group, pentafluorophenyl group, p
-Hydroxyphenyl group, p-cyanophenyl group, p-
Methanesulfonamide phenyl group, 3,4-dichlorophenyl group).
【0034】[0034]
【化31】 [Chemical 31]
【0035】式中、XJはヒドロキシ基、ORJ′基,N
(RJ′)2基又は置換基を有してもよいアルキル基,ア
リール基若しくはアラルキル基を表し、YJ,RFはハロ
ゲン原子,シアノ基,ニトロ基,CF3基,COORJ′
基,OCORJ′基,CONHRJ′基,SORJ′基又
はSO2RJ′基を表し、RJ′は置換基を有してもよい
アルキル基,アリール基又はアラルキル基を表し、Aは
縮合多環式芳香族炭素環を形成するに必要な原子群を表
す。l,m及びnは0又は正の整数を表し、n+mは2
以上の整数を表し、l+mは2から8の整数を表す。又
複数個あるXJ,YJ,RFの各基はそれぞれ同じ基から
成ってもよく、異なる基から成ってもよい。In the formula, X J is a hydroxy group, OR J ′ group, N
(R J ′) 2 represents an alkyl group, an aryl group or an aralkyl group which may have a substituent, and Y J and R F are a halogen atom, a cyano group, a nitro group, a CF 3 group and COOR J ′.
Group, OCOR J ′ group, CONHR J ′ group, SOR J ′ group or SO 2 R J ′ group, R J ′ represents an optionally substituted alkyl group, aryl group or aralkyl group, and A Represents an atomic group necessary for forming a condensed polycyclic aromatic carbocycle. l, m and n represent 0 or a positive integer, and n + m is 2
The above integers are represented, and l + m represents an integer of 2 to 8. The plural groups of X J , Y J and R F may be the same or different.
【0036】又前記一般式〔J〕における置換基がアル
キル基であるか、又はアルキル基を含む時、特に規定の
ない限り、アルキル基は直鎖状、分岐鎖状又は架橋され
ていてもよい脂環式環であり、置換されていても不飽和
結合を含んでいてもよいアルキル基(たとえば、メチル
基,エチル基,iso−プロピル基,t−ブチル基,ペ
ンチル基,2−エチルヘキシル基,ドデシル基,アリル
基,オレイル基,ベンジル基,ヒドロキシエチル基,メ
トキシエチル基,フェノキシエチル基,シクロペンチル
基,シクロヘキシル基,ノルボルニル基)を意味する。When the substituent in the above general formula [J] is an alkyl group or contains an alkyl group, the alkyl group may be linear, branched or crosslinked, unless otherwise specified. An alicyclic ring, which may be substituted or may contain an unsaturated bond (for example, a methyl group, an ethyl group, an iso-propyl group, a t-butyl group, a pentyl group, a 2-ethylhexyl group, Dodecyl group, allyl group, oleyl group, benzyl group, hydroxyethyl group, methoxyethyl group, phenoxyethyl group, cyclopentyl group, cyclohexyl group, norbornyl group).
【0037】又前記一般式〔J〕における置換基がアリ
ール基であるか、又はアリール基を含む時、特に規定の
ない限り、アリール基は置換されていても良く単環若し
くは縮合環のアリール基(たとえば、フェニル基,1−
ナフチル基,p−トリル基,p−クロロフェニル基,4
−メトキシフェニル基,ペンタフルオロフェニル基,p
−ヒドロキシフェニル基,p−シアノフェニル基,p−
メタンスルホンアミドフェニル基,3,4−ジクロロフ
ェニル基)を意味する。When the substituent in the above formula [J] is an aryl group or contains an aryl group, the aryl group may be substituted unless otherwise specified, and is a monocyclic or condensed ring aryl group. (For example, phenyl group, 1-
Naphthyl group, p-tolyl group, p-chlorophenyl group, 4
-Methoxyphenyl group, pentafluorophenyl group, p
-Hydroxyphenyl group, p-cyanophenyl group, p-
Methanesulfonamide phenyl group, 3,4-dichlorophenyl group).
【0038】[0038]
【化32】 [Chemical 32]
【0039】式中、XKはヒドロキシ基,ORK′基,N
(RK′)2基又は置換基を有してもよいアルキル基,ア
リール基若しくはアラルキル基を表し、YK,RKはハロ
ゲン原子,シアノ基,ニトロ基,CF3基,CORK′
基,COORK′基,OCORK′基,CONHRK′
基,SORK′基又はSO2RK′基を表し、RK′は置換
基を有してもよいアルキル基,アリール基又はアラルキ
ル基を表し、Bはベンゼン環の炭素原子とともに脂肪族
環を形成するに必要な炭化水素原子群を表す。l,m及
びnは0又は正の整数を表し、n+mは2以上の整数を
表し、l+mは2から8の整数を表す。又複数個あるR
K,YK,RKの各基はそれぞれ同じ基から成ってもよ
く、異なる基から成ってもよい。In the formula, X K is a hydroxy group, an OR K ′ group, N
(R K ′) 2 represents an alkyl group, an aryl group or an aralkyl group which may have a substituent, and Y K and R K are a halogen atom, a cyano group, a nitro group, a CF 3 group and a COR K ′.
Group, COOR K ′ group, OCOR K ′ group, CONHR K ′
Group, SOR K ′ group or SO 2 R K ′ group, R K ′ represents an alkyl group which may have a substituent, an aryl group or an aralkyl group, and B represents an aliphatic ring together with the carbon atom of the benzene ring. Represents a hydrocarbon atom group necessary for forming. l, m and n represent 0 or a positive integer, n + m represents an integer of 2 or more, and l + m represents an integer of 2 to 8. There are multiple R
The groups K 1 , Y K and R K may be the same or different.
【0040】又前記一般式〔K〕における置換基がアル
キル基であるか、又はアルキル基を含む時、特に規定の
ない限り、アルキル基は直鎖状、分岐鎖状又は架橋され
ていてもよい脂環式環であり、置換されていても不飽和
結合を含んでいてもよいアルキル基(たとえば、メチル
基,エチル基,iso−プロピル基,t−ブチル基,ペ
ンチル基,2−エチルヘキシル基,ドデシル基,アリル
基,オレイル基,ベンジル基,ヒドロキシエチル基,メ
トキシエチル基,フェノキシエチル基,シクロペンチル
基,シクロヘキシル基,ノルボルニル基)を意味する。When the substituent in the general formula [K] is an alkyl group or contains an alkyl group, the alkyl group may be linear, branched or crosslinked unless otherwise specified. An alicyclic ring, which may be substituted or may contain an unsaturated bond (for example, a methyl group, an ethyl group, an iso-propyl group, a t-butyl group, a pentyl group, a 2-ethylhexyl group, Dodecyl group, allyl group, oleyl group, benzyl group, hydroxyethyl group, methoxyethyl group, phenoxyethyl group, cyclopentyl group, cyclohexyl group, norbornyl group).
【0041】又前記一般式〔K〕における置換基がアリ
ール基であるか、又はアリール基を含む時、特に規定の
ない限り、アリール基は置換されていてもよく単環若し
くは縮合環のアリール基(たとえば、フェニル基,1−
ナフチル基,p−トリル基,p−クロロフェニル基,4
−メトキシフェニル基,ペンタフルオロフェニル基,p
−ヒドロキシフェニル基,p−シアノフェニル基,p−
メタンスルホンアミドフェニル基,3,4−ジクロロフ
ェニル基)を意味する。When the substituent in the above general formula [K] is an aryl group or contains an aryl group, the aryl group may be substituted unless otherwise specified, and is a monocyclic or condensed ring aryl group. (For example, phenyl group, 1-
Naphthyl group, p-tolyl group, p-chlorophenyl group, 4
-Methoxyphenyl group, pentafluorophenyl group, p
-Hydroxyphenyl group, p-cyanophenyl group, p-
Methanesulfonamide phenyl group, 3,4-dichlorophenyl group).
【0042】[0042]
【化33】 [Chemical 33]
【0043】式中、XLはヒドロキシ基,ORL′基,N
(RL′)2基又は置換基を有してもよいアルキル基,ア
リール基若しくはアラルキル基を表し、YL,RLはハロ
ゲン原子,シアノ基,ニトロ基,CF3基,CORL′
基,COORL′基,OCORL′基,CONHRL′
基,SORL′基又はSO2RL′基を表し、RL′は置換
基を有してもよいアルキル基,アリール基又はアラルキ
ル基を表し、Dは複素環を形成するに必要な非金属原子
群を表す。l,m及びnは0又は正の整数を表し、m+
nは2以上の整数を表し、l+mは2から8の整数を表
す。又XL,YL,RLの各基はそれぞれ同じ基から成っ
てもよく、異なる基から成ってもよい。In the formula, X L is a hydroxy group, OR L' group, N
( RL ') 2 group or an optionally substituted alkyl group, aryl group or aralkyl group, wherein Y L and R L are a halogen atom, a cyano group, a nitro group, a CF 3 group and COR L '
Group, COOR L ′ group, OCOR L ′ group, CONHR L ′
Group, a SOR L 'groups or SO 2 R L' group, R L 'is an optionally substituted alkyl group, an aryl group or an aralkyl group, D a is necessary to form a heterocyclic non Represents a group of metal atoms. l, m and n represent 0 or a positive integer, m +
n represents an integer of 2 or more, and l + m represents an integer of 2 to 8. The groups X L , Y L , and R L may be the same or different.
【0044】又前記一般式〔L〕における置換基がアル
キル基であるか、又はアルキル基を含む時、特に規定の
ない限り、アルキル基は直鎖状、分岐鎖状又は架橋され
ていてもよい脂環式環であり、置換されていても、不飽
和結合を含んでいてもよいアルキル基(たとえば、メチ
ル基,エチル基,iso−プロピル基,t−ブチル基,
ペンチル基,2−エチルヘキシル基,ドデシル基,アリ
ル基,オレイル基,ベンジル基,ヒドロキシエチル基,
メトキシエチル基,フェノキシエチル基,シクロペンチ
ル基,シクロヘキシル基,ノルボルニル基)を意味す
る。When the substituent in the above formula [L] is an alkyl group or contains an alkyl group, the alkyl group may be linear, branched or crosslinked unless otherwise specified. An alkyl group which is an alicyclic ring and may be substituted or may contain an unsaturated bond (eg, methyl group, ethyl group, iso-propyl group, t-butyl group,
Pentyl group, 2-ethylhexyl group, dodecyl group, allyl group, oleyl group, benzyl group, hydroxyethyl group,
Methoxyethyl group, phenoxyethyl group, cyclopentyl group, cyclohexyl group, norbornyl group).
【0045】又前記一般式〔L〕における置換基がアリ
ール基であるか、又はアリール基を含む時、特に規定の
ない限り、アリール基は置換されていてもよく単環若し
くは縮合環のアリール基(たとえば、フェニル基,1−
ナフチル基,p−トリル基,p−クロロフェニル基,4
−メトキシフェニル基,ペンタフルオロフェニル基,p
−ヒドロキシフェニル基,p−シアノフェニル基,p−
メタンスルホンアミドフェニル基,3,4−ジクロロフ
ェニル基)を意味する。When the substituent in the above formula [L] is an aryl group or contains an aryl group, the aryl group may be substituted unless otherwise specified, and is a monocyclic or condensed ring aryl group. (For example, phenyl group, 1-
Naphthyl group, p-tolyl group, p-chlorophenyl group, 4
-Methoxyphenyl group, pentafluorophenyl group, p
-Hydroxyphenyl group, p-cyanophenyl group, p-
Methanesulfonamide phenyl group, 3,4-dichlorophenyl group).
【0046】また本発明の好ましい態様としては、前記
一般式〔A〕〜〔L〕に更に構造諸元に制限を加えた前
記一般式の夫々に対応する一般式〔a〕〜〔l〕で示さ
れる化合物が挙げられる。In a preferred embodiment of the present invention, there are provided general formulas [a] to [l] corresponding to the general formulas [A] to [L], respectively, which are structurally restricted. Included are the compounds shown.
【0047】本発明の感光体においては、P型CTMと
必要によりバインダー樹脂を含有するCTLを下層と
し、CGMと必要によりP型CTM及びバインダー樹脂
を含有するCGLを上層とする二層構成の感光層上に、
電子輸送機能が優れた本発明特有の電子受容性物質を均
一に含有する保護層が設けられる。In the photoconductor of the present invention, a two-layer photoconductor having P-type CTM and CTL optionally containing a binder resin as a lower layer, and CGM and optionally CGL containing P-type CTM and a binder resin as an upper layer. On a layer,
A protective layer is provided which uniformly contains an electron-accepting substance peculiar to the present invention having an excellent electron-transporting function.
【0048】又本発明の感光体では、CGMとP型CT
Mと必要によりバインダー樹脂を含有する単層構成の感
光層上に前記電子受容性物質を含有する保護層が設けら
れていてもよい。Further, in the photoreceptor of the present invention, CGM and P-type CT
A protective layer containing the electron-accepting substance may be provided on the photosensitive layer having a single-layer structure containing M and, if necessary, a binder resin.
【0049】前記のように構成された感光体は正帯電用
とされ、感光層上に光照射時ホール及び電子が発生する
と、ホールは感光層中のP型CTMを介して基体側へ速
やかに移動すると共に、電子は保護層内の前記電子受容
性物質の作用で表面層へと速やかに移動し、表面層の正
の電荷を打ち消すようになる。かくして保護層が設けら
れていても高感度で残留電位特性に優れた電子写真特性
が得られ、かつ高耐久性が発揮される。The photoconductor thus constructed is for positive charging, and when holes and electrons are generated on the photosensitive layer during light irradiation, the holes are promptly transferred to the substrate side through the P-type CTM in the photosensitive layer. As the electrons move, the electrons rapidly move to the surface layer by the action of the electron-accepting substance in the protective layer, and the positive charge of the surface layer is canceled. Thus, even if the protective layer is provided, high sensitivity, electrophotographic characteristics excellent in residual potential characteristics are obtained, and high durability is exhibited.
【0050】本発明の正帯電用感光体の保護層に含有さ
れる前記電子受容性物質の具体例及び合成例は以下のよ
うである。Specific examples and synthetic examples of the electron-accepting substance contained in the protective layer of the positive charging photoreceptor of the present invention are as follows.
【0051】[0051]
【作用】次に前記一般式〔A〕〜〔L〕で表される化合
物の具体例及びその合成例を示す。Next, specific examples of the compounds represented by the above general formulas [A] to [L] and synthetic examples thereof will be shown.
【0052】一般式〔A〕で表される例示化合物:Exemplary compounds represented by the general formula [A]:
【0053】[0053]
【化34】 [Chemical 34]
【0054】(上記一般式の1〜13の数字は置換基の位
置を示す。)(Numbers 1 to 13 in the above general formula indicate the positions of the substituents.)
【0055】[0055]
【化35】 [Chemical 35]
【0056】[0056]
【化36】 [Chemical 36]
【0057】合成例Synthesis example
【0058】[0058]
【化37】 [Chemical 37]
【0059】上記の合成経路に従い例示化合物A−16を
合成した。2,5-ビス(トリフルオロメチル)アニリン(ア
ルドリッチ社製)を出発原料として、既知の方法(J.Ch
em,Soc, 1071〜6(1954))に従い、化合物4を合成し
た。Exemplified Compound A-16 was synthesized according to the above synthetic route. Using 2,5-bis (trifluoromethyl) aniline (manufactured by Aldrich) as a starting material, a known method (J.Ch
Compound 4 was synthesized according to em, Soc, 1071-6 (1954)).
【0060】化合物4 10gを100mlの四頭フラスコに入
れ、塩化亜鉛20gと2,6-キシリジン5(和光純薬工業株
式会社製)5gとODB100mlを加え、エステル管と温度
計をつけて、50時間加熱還流した。放冷後固体を吸引濾
過で除き、酢酸エチルでよく洗い込む。母液の溶媒を減
圧下留去し、残渣をシリカゲルのカラムに付した。トル
エン:n-ヘキサン=1:1溶出部を、n-ヘキサンにて結
晶化して、例示化合物A−16の赤色粉末 9.5g(収率75
%)を得た。融点は日本薬局方融点測定法に従い測定し
た結果153〜155℃であった。元素分析値も計算値とよく
一致したことから例示化合物A−16の構造を確認した。10 g of compound 4 was placed in a 100 ml four-headed flask, 20 g of zinc chloride, 5 g of 2,6-xylidine 5 (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 ml of ODB were added, an ester tube and a thermometer were attached, and 50 Heated to reflux for hours. After allowing to cool, the solid is removed by suction filtration and washed well with ethyl acetate. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. Toluene: n-hexane = 1: 1 eluate was crystallized from n-hexane to give 9.5 g of red powder of Exemplified Compound A-16 (yield 75
%) Was obtained. The melting point was measured by the Japanese Pharmacopoeia melting point measurement method and was found to be 153-155 ° C. Since the elemental analysis values also agreed well with the calculated values, the structure of Exemplified Compound A-16 was confirmed.
【0061】 C H N 計算値 59.15% 2.90% 2.87% 実測値 58.51% 3.01% 2.73% 一般式〔B〕で表される例示化合物:置換基の位置表示
法は一般式〔A〕と同じ。C H N calculated value 59.15% 2.90% 2.87% Measured value 58.51% 3.01% 2.73% Exemplified compound represented by the general formula [B]: The method for indicating the position of the substituent is the same as the general formula [A].
【0062】[0062]
【化38】 [Chemical 38]
【0063】[0063]
【化39】 [Chemical Formula 39]
【0064】合成例Synthesis example
【0065】[0065]
【化40】 [Chemical 40]
【0066】上記の合成経路に従い例示化合物B−2を
合成した。2-ヨードベンゾトリフルオライド(アルドリ
ッチ社製)を出発原料として、既知の方法(J.Chem,So
c, 1071〜6(1954))に従い、化合物4を合成した。Exemplified Compound B-2 was synthesized according to the above synthetic route. Using 2-iodobenzotrifluoride (manufactured by Aldrich) as a starting material, a known method (J. Chem, So
c, 1071-6 (1954)), compound 4 was synthesized.
【0067】化合物4 10gを100mlの四頭フラスコに入
れ、塩化亜鉛20gと2,6-キシリジン5(和光純薬工業株
式会社製)5gとODB 100mlを加え、エステル管と温
度計をつけて、50時間加熱還流した。放冷後固体を吸引
濾過で除き、酢酸エチルとクロロホルムでよく洗い込
む。母液の溶媒を減圧下留去し、残渣をシリカゲルのカ
ラムに付した。トルエン:n-ヘキサン=1:1溶出部
を、n-ヘキサンにて結晶化して、例示化合物B−2の赤
色粉末 8.5g(収率64%)を得た。融点は日本薬局方融
点測定法に従い測定した結果189〜190℃であった。元素
分析値も計算値とよく一致したことから、例示化合物B
−2の構造を確認した。10 g of compound 4 was placed in a 100 ml four-headed flask, 20 g of zinc chloride, 5 g of 2,6-xylidine 5 (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 ml of ODB were added, and an ester tube and a thermometer were attached. The mixture was heated under reflux for 50 hours. After cooling, the solid is removed by suction filtration and washed well with ethyl acetate and chloroform. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. The eluate of toluene: n-hexane = 1: 1 was crystallized with n-hexane to obtain 8.5 g (yield 64%) of a red powder of Exemplified Compound B-2. The melting point was 189 to 190 ° C as measured by the Japanese Pharmacopoeia melting point measuring method. Since the elemental analysis values were in good agreement with the calculated values, Exemplified Compound B
-2 structure was confirmed.
【0068】 C H N 計算値 59.87% 3.20% 9.52% 実測値 59.71% 3.31% 9.40% 一般式〔C〕で表される例示化合物:置換基の位置表示
法は一般式〔A〕と同じ。C H N calculated value 59.87% 3.20% 9.52% measured value 59.71% 3.31% 9.40% Exemplified compound represented by the general formula [C]: The method for indicating the position of the substituent is the same as the general formula [A].
【0069】[0069]
【化41】 [Chemical 41]
【0070】[0070]
【化42】 [Chemical 42]
【0071】[0071]
【化43】 [Chemical 43]
【0072】合成例Synthesis example
【0073】[0073]
【化44】 [Chemical 44]
【0074】上記の合成経路に従い例示化合物C−1を
合成した。9-フルオレノン-4-カルボキシリックアミド
(アルドリッチ社製)を出発原料として、常法に従い、
化合物3を合成した。Exemplified Compound C-1 was synthesized according to the above synthetic route. Using 9-fluorenone-4-carboxylic amide (manufactured by Aldrich) as a starting material, according to a conventional method,
Compound 3 was synthesized.
【0075】化合物3 10gを100mlの四頭フラスコに入
れ、塩化亜鉛20gと2,6-キシリジン5(和光純薬工業株
式会社製)5gとODB 100mlを加え、エステル管と温
度計をつけて、50時間加熱還流した。放冷後固体を吸引
濾過で除き、酢酸エチルでよく洗い込む。母液の溶媒を
減圧下留去し、残渣をシリカゲルのカラムに付した。ト
ルエン:n-ヘキサン=1:1溶出部を、n-ヘキサンにて
結晶化して、例示化合物C−1赤色粉末 6.8g(収率56
%)を得た。融点は日本薬局方融点測定法に従い測定し
た結果193〜196℃であった。元素分析値も計算値とよく
一致したことから例示化合物C−1の構造を確認した。10 g of compound 3 was placed in a 100 ml four-headed flask, 20 g of zinc chloride, 5 g of 2,6-xylidine 5 (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 ml of ODB were added, and an ester tube and a thermometer were attached. The mixture was heated under reflux for 50 hours. After allowing to cool, the solid is removed by suction filtration and washed well with ethyl acetate. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. Toluene: n-hexane = 1: 1 eluate was crystallized from n-hexane to give 6.8 g of Exemplified Compound C-1 red powder (yield 56
%) Was obtained. The melting point was 193-196 ° C as measured by the Japanese Pharmacopoeia melting point measuring method. Since the elemental analysis values also agreed well with the calculated values, the structure of the exemplified compound C-1 was confirmed.
【0076】 C H N 計算値 68.04% 5.90% 7.93% 実測値 67.59% 6.05% 7.72% 一般式〔D〕で表される例示化合物:置換基の位置表示
法は一般式〔A〕と同じ。C H N calculated value 68.04% 5.90% 7.93% Actual value 67.59% 6.05% 7.72% Exemplified compound represented by the general formula [D]: The method for indicating the position of the substituent is the same as that of the general formula [A].
【0077】[0077]
【化45】 [Chemical formula 45]
【0078】[0078]
【化46】 [Chemical formula 46]
【0079】合成例Synthesis example
【0080】[0080]
【化47】 [Chemical 47]
【0081】上記の合成経路に従い例示化合物D−2を
合成した。化合物1を出発原料として、既知の方法(J.
Chem,Soc, 1071〜6(1954))に従い、化合物4を合成し
た。Exemplified Compound D-2 was synthesized according to the above synthetic route. Compound 1 as a starting material, the known methods (J.
Compound 4 was synthesized according to Chem, Soc, 1071-6 (1954)).
【0082】化合物4 10gを100mlの四頭フラスコに入
れ、塩化亜鉛20gと2-エチルアニリン5(アルドリッチ
社製)5gとODB 100mlを加え、エステル管と温度計
をつけて、120時間加熱還流した。放冷後固体を吸引濾
過で除き、DMSOでよく洗い込む。母液の溶媒を減圧
下留去し、残渣をシリカゲルのカラムに付した。トルエ
ン:n-ヘキサン=9:1溶出部を、トルエンにて結晶化
して、例示化合物D−2の暗赤色粉末 9.9g(収率78
%)を得た。融点は日本薬局方融点測定法に従い測定し
た結果193〜194℃であった。元素分析値も計算値とよく
一致したことから、例示化合物D−2の構造を確認し
た。10 g of Compound 4 was placed in a 100 ml four-headed flask, 20 g of zinc chloride, 5 g of 2-ethylaniline 5 (manufactured by Aldrich) and 100 ml of ODB were added, and the mixture was heated under reflux for 120 hours with an ester tube and a thermometer attached. . After allowing to cool, the solid is removed by suction filtration and washed well with DMSO. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. The toluene: n-hexane = 9: 1 eluate was crystallized from toluene to give 9.9 g of a dark red powder of Exemplified Compound D-2 (yield 78
%) Was obtained. The melting point was 193-194 ° C. as measured by the Japanese Pharmacopoeia melting point measuring method. Since the elemental analysis values were in good agreement with the calculated values, the structure of Exemplified Compound D-2 was confirmed.
【0083】 C H N 計算値 56.80% 3.97% 2.76% 実測値 56.62% 4.01% 2.51% 一般式〔E〕で表される例示化合物:置換基の表示法は
一般式〔A〕と同じ。C H N calculated value 56.80% 3.97% 2.76% Actual value 56.62% 4.01% 2.51% Exemplified compound represented by the general formula [E]: The method of displaying substituents is the same as that of the general formula [A].
【0084】[0084]
【化48】 [Chemical 48]
【0085】[0085]
【化49】 [Chemical 49]
【0086】合成例Synthesis example
【0087】[0087]
【化50】 [Chemical 50]
【0088】上記の合成経路に従い例示化合物E−1を
合成した。2,4,7-トリニトロフルオレノン(アルドリッ
チ社製)を出発原料として、既知の方法(特開平1-2906
54号)に従い、化合物2を合成した。Exemplified compound E-1 was synthesized according to the above synthetic route. A known method using 2,4,7-trinitrofluorenone (manufactured by Aldrich) as a starting material is disclosed in JP-A 1-2906.
No. 54), compound 2 was synthesized.
【0089】化合物2;10gを100mlの四頭フラスコに入
れ、塩化亜鉛20gと2-エチルアニリン3(アルドリッチ
社製)5gとODB 100mlを加え、エステル管と温度計
をつけて、60時間加熱還流した。放冷後固体を吸引濾過
で除き、酢酸エチルでよく洗い込む。母液の溶媒を減圧
下留去し、残渣をシリカゲルのカラムに付した。トルエ
ン:n-ヘキサン=1:1溶出部を、n-ヘキサンにて結晶
化して、例示化合物E−1の赤色粉末 6.8g(収率52
%)を得た。融点は日本薬局方融点測定法に従い測定し
た結果176〜178℃であった。元素分析値も計算値とよく
一致したことから例示化合物E−1の構造を確認した。10 g of compound 2 was placed in a 100 ml four-headed flask, 20 g of zinc chloride, 5 g of 2-ethylaniline 3 (manufactured by Aldrich) and 100 ml of ODB were added, and the mixture was heated under reflux for 60 hours with an ester tube and a thermometer attached. did. After allowing to cool, the solid is removed by suction filtration and washed well with ethyl acetate. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. Toluene: n-hexane = 1: 1 eluate was crystallized from n-hexane to give 6.8 g of red powder of Exemplified Compound E-1 (yield 52
%) Was obtained. The melting point was 176 to 178 ° C as measured by the Japanese Pharmacopoeia melting point measuring method. Since the elemental analysis values also agreed well with the calculated values, the structure of Exemplified Compound E-1 was confirmed.
【0090】 C H N 計算値 55.77% 3.12% 9.29% 実測値 55.72% 3.14% 9.10% 一般式〔F〕で表される例示化合物:C H N calculated value 55.77% 3.12% 9.29% measured value 55.72% 3.14% 9.10% Exemplary compound represented by general formula [F]:
【0091】[0091]
【化51】 [Chemical 51]
【0092】[0092]
【化52】 [Chemical 52]
【0093】[0093]
【化53】 [Chemical 53]
【0094】合成例Synthesis example
【0095】[0095]
【化54】 [Chemical 54]
【0096】上記の合成経路に従い例示化合物F−1を
合成した。3-メチル-4-アミノベンゾニトリルを出発原
料として、既知の方法(J.Chem,Soc, 1071〜6(1954))
に従い、化合物4を合成した。Exemplified compound F-1 was synthesized according to the above synthetic route. Known method using 3-methyl-4-aminobenzonitrile as a starting material (J. Chem, Soc, 1071-6 (1954))
According to the above, compound 4 was synthesized.
【0097】化合物4;10gを100mlの四頭フラスコに入
れ、塩化亜鉛20gと2,6-キシリジン5(和光純薬工業株
式会社製)5gとODB 100mlを加え、エステル管と温
度計をつけて、75時間加熱還流した。放冷後固体を吸引
濾過で除き、酢酸エチルでよく洗い込む。母液の溶媒を
減圧下留去し、残渣をシリカゲルのカラムに付した。ト
ルエン:n-ヘキサン=1:1溶出部を、n-ヘキサンにて
結晶化して、例示化合物F−1の褐色結晶 11.9g(収率
84%)を得た。融点は日本薬局方融点測定法に従い測定
した結果159〜160℃であった。元素分析値も計算値とよ
く一致したことから例示化合物F−1の構造を確認し
た。Compound 4 ; 10 g was placed in a 100 ml four-headed flask, 20 g of zinc chloride, 5 g of 2,6-xylidine 5 (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 ml of ODB were added, and an ester tube and a thermometer were attached. The mixture was heated under reflux for 75 hours. After allowing to cool, the solid is removed by suction filtration and washed well with ethyl acetate. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. The toluene: n-hexane = 1: 1 eluate was crystallized from n-hexane to give 11.9 g of brown crystals of the exemplified compound F-1 (yield
84%). The melting point was measured in accordance with the Japanese Pharmacopoeia melting point measurement method and was found to be 159 to 160 ° C. Since the elemental analysis values also agreed well with the calculated values, the structure of the exemplified compound F-1 was confirmed.
【0098】 C H N 計算値 82.97% 4.93% 12.09% 実測値 82.93% 4.95% 12.03% 一般式〔G〕で表される例示化合物:置換基の表示法は
一般式〔A〕と同じ。C H N calculated value 82.97% 4.93% 12.09% Measured value 82.93% 4.95% 12.03% Exemplified compound represented by general formula [G]: The method of displaying substituents is the same as in general formula [A].
【0099】[0099]
【化55】 [Chemical 55]
【0100】[0100]
【化56】 [Chemical 56]
【0101】合成例Synthesis example
【0102】[0102]
【化57】 [Chemical 57]
【0103】上記反応によって例示化合物G−1を合成
した。Exemplified Compound G-1 was synthesized by the above reaction.
【0104】即ち、2,4,7-トリフルオレノン1(東京化
成社製)10gを100mlの四頭フラスコに入れ、塩化亜鉛20
gと2-アミノビフェニル2(アルドリッチ社製)10gとO
DB100mlを加え、エステル管と温度計をつけて、80時
間加熱還流した。放冷後固体を吸引濾過で除き、酢酸エ
チルでよく洗い込む。母液の溶媒を減圧下留去し、残渣
をシリカゲルのカラムに付した。トルエン:n-ヘキサン
=1:1溶出部を、トルエンにて結晶化して、例示化合
物G−1の赤色結晶 12.1g(収率81%)を得た。融点は
日本薬局方融点測定法に従い測定した結果181〜183℃で
あった。元素分析値も計算値とよく一致したことから例
示化合物G−1の構造を確認した。That is, 10 g of 2,4,7-trifluorenone 1 (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a 100 ml four-headed flask, and zinc chloride 20
g and 2-aminobiphenyl 2 (made by Aldrich) 10 g and O
DB100 ml was added, and the mixture was heated under reflux for 80 hours with an ester tube and a thermometer attached. After allowing to cool, the solid is removed by suction filtration and washed well with ethyl acetate. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. The toluene: n-hexane = 1: 1 eluate was crystallized from toluene to obtain 12.1 g (yield 81%) of red crystals of Exemplified Compound G-1. The melting point was 181 to 183 ° C as measured by the Japanese Pharmacopoeia melting point measuring method. Since the elemental analysis values also agreed well with the calculated values, the structure of Exemplified Compound G-1 was confirmed.
【0105】 C H N 計算値 64.38% 3.03% 12.01% 実測値 64.21% 3.07% 11.92% 一般式〔H〕で表される例示化合物:C H N calculated value 64.38% 3.03% 12.01% measured value 64.21% 3.07% 11.92% exemplary compound represented by general formula [H]:
【0106】[0106]
【化58】 [Chemical 58]
【0107】[0107]
【化59】 [Chemical 59]
【0108】[0108]
【化60】 [Chemical 60]
【0109】[0109]
【化61】 [Chemical formula 61]
【0110】合成例Synthesis example
【0111】[0111]
【化62】 [Chemical formula 62]
【0112】上記の合成経路に従い例示化合物H−1を
合成した。2,4-ビス(トリフルオロメチル)ブロモベンゼ
ン1(アルドリッチ社製)を出発原料として、既知の方
法(J.Chem,Soc, 1071〜6(1954))に従い、化合物3を
合成した。Exemplified Compound H-1 was synthesized according to the above synthetic route. Compound 3 was synthesized according to a known method (J. Chem, Soc, 1071 to 6 (1954)) using 2,4-bis (trifluoromethyl) bromobenzene 1 (manufactured by Aldrich) as a starting material.
【0113】化合物3 10gを100mlの四頭フラスコに入
れ、塩化亜鉛20gとt-オクチルアミン4(アルドリッチ
社製)5gとo-ジクロルベンゼン(以下ODBと略す)
100mlを加え、エステル管と温度計をつけて、55時間加
熱還流した。放冷後固体を吸引濾過で除き、酢酸エチル
でよく洗い込む。母液の溶媒を減圧下留去し、残渣をシ
リカゲルのカラムに付した。トルエン:n-ヘキサン=
1:1溶出部を、n-ヘキサンにて結晶化して、例示化合
物I−1の赤色粉末 7.9g(収率61%)を得た。融点は
日本薬局方融点測定法に従い測定した結果171〜173℃で
あった。元素分析値も計算値とよく一致したことから例
示化合物H−1の構造を確認した。10 g of Compound 3 was placed in a 100 ml four-headed flask, and 20 g of zinc chloride, 5 g of t-octylamine 4 (manufactured by Aldrich) and o-dichlorobenzene (hereinafter abbreviated as ODB).
100 ml was added, and the mixture was heated under reflux for 55 hours with an ester tube and a thermometer attached. After allowing to cool, the solid is removed by suction filtration and washed well with ethyl acetate. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. Toluene: n-hexane =
The 1: 1 eluate was crystallized with n-hexane to obtain 7.9 g (yield 61%) of a red powder of Exemplified Compound I-1. The melting point was determined to be 171-173 ° C according to the Japanese Pharmacopoeia melting point measuring method. Since the elemental analysis values also agreed well with the calculated values, the structure of the exemplified compound H-1 was confirmed.
【0114】 C H N 計算値 58.18% 4.48% 2.83% 実測値 57.97% 4.55% 2.78% 一般式〔J〕で表される例示化合物:C H N calculated value 58.18% 4.48% 2.83% measured value 57.97% 4.55% 2.78% Exemplified compound represented by general formula [J]:
【0115】[0115]
【化63】 [Chemical formula 63]
【0116】[0116]
【化64】 [Chemical 64]
【0117】[0117]
【化65】 [Chemical 65]
【0118】[0118]
【化66】 [Chemical formula 66]
【0119】[0119]
【化67】 [Chemical formula 67]
【0120】[0120]
【化68】 [Chemical 68]
【0121】合成例Synthesis example
【0122】[0122]
【化69】 [Chemical 69]
【0123】上記の合成経路に従い例示化合物J−1を
合成した。2,4-ビス(トリフルオロメチル)ブロモベン
ゼン1(アルドリッチ社製)を出発原料として、常法に
従い、化合物3を合成した。Exemplified Compound J-1 was synthesized according to the above synthetic route. Compound 3 was synthesized according to a conventional method using 2,4-bis (trifluoromethyl) bromobenzene 1 (manufactured by Aldrich) as a starting material.
【0124】化合物3 10gを100mlの四頭フラスコに入
れ、塩化亜鉛20gと9-アミノフェナンスレン4(アルド
リーチ社製)5gとODB 100mlを加え、エステル管と
温度計をつけて、50時間加熱還流した。放冷後固体を吸
引濾過で除き、酢酸エチルでよく洗い込む。母液の溶媒
を減圧下留去し、残渣をシリカゲルのカラムに付した。
トルエン:n-ヘキサン=1:1溶出部を、n-ヘキサンに
て結晶化して、例示化合物II−1暗赤色結晶 9.3g(収
率64%)を得た。融点は日本薬局方融点測定法に従い測
定した結果193〜194℃であった。元素分析値も計算値と
よく一致したことから例示化合物J−1の構造を確認し
た。10 g of Compound 3 was placed in a 100 ml four-headed flask, 20 g of zinc chloride, 5 g of 9-aminophenanthrene 4 (manufactured by Aldrich Co.) and 100 ml of ODB were added, and an ester tube and a thermometer were attached and heated for 50 hours. Refluxed. After allowing to cool, the solid is removed by suction filtration and washed well with ethyl acetate. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column.
The toluene: n-hexane = 1: 1 eluate was crystallized from n-hexane to give 9.3 g (yield 64%) of Exemplified Compound II-1 dark red crystals. The melting point was 193-194 ° C. as measured by the Japanese Pharmacopoeia melting point measuring method. The structure of Exemplified Compound J-1 was confirmed because the elemental analysis values also agreed well with the calculated values.
【0125】 C H N 計算値 64.41% 2.52% 2.50% 実測値 64.32% 2.57% 2.45% 一般式〔K〕で表される例示化合物:C H N calculated value 64.41% 2.52% 2.50% Actual value 64.32% 2.57% 2.45% Exemplary compound represented by the general formula [K]:
【0126】[0126]
【化70】 [Chemical 70]
【0127】[0127]
【化71】 [Chemical 71]
【0128】[0128]
【化72】 [Chemical 72]
【0129】[0129]
【化73】 [Chemical formula 73]
【0130】合成例Synthesis example
【0131】[0131]
【化74】 [Chemical 74]
【0132】上記の合成経路に従い例示化合物K−1を
合成した。2,4-ビス(トリフルオロメチル)ブロモベン
ゼン1(アルドリッチ社製)を出発原料として、既知の
方法(J.Chem,Soc, 1071〜6(1954))に従い、化合物3
を合成した。Exemplified Compound K-1 was synthesized according to the above synthetic route. 2,4-bis (trifluoromethyl) bromobenzene 1 (manufactured by Aldrich) was used as a starting material, and compound 3 was used according to a known method (J. Chem, Soc, 1071-6 (1954)).
Was synthesized.
【0133】化合物3 10gを100mlの四頭フラスコに入
れ、塩化亜鉛20gと1-アミノ-5,6,7,8-テトラヒドロナ
フタレン4(アルドリッチ社製)5gとODB 100mlを
加え、エステル管と温度計をつけて、50時間加熱還流し
た。放冷後固体を吸引濾過で除き、酢酸エチルとクロロ
ホルムでよく洗い込む。母液の溶媒を減圧下留去し、残
渣をシリカゲルのカラムに付した。トルエン:n-ヘキサ
ン=1:1溶出部を、n-ヘキサンにて結晶化して、例示
化合物III−1の赤色粉末 7.5g(収率55%)を得た。
融点は日本薬局方融点測定法に従い測定した結果187〜1
88℃であった。10 g of Compound 3 was placed in a 100 ml four-headed flask, 20 g of zinc chloride, 5 g of 1-amino-5,6,7,8-tetrahydronaphthalene 4 (manufactured by Aldrich) and 100 ml of ODB were added, and the ester tube and the temperature were adjusted. A meter was turned on and the mixture was heated under reflux for 50 hours. After cooling, the solid is removed by suction filtration and washed well with ethyl acetate and chloroform. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. The toluene: n-hexane = 1: 1 eluate was crystallized from n-hexane to obtain 7.5 g (yield 55%) of a red powder of Exemplified Compound III-1.
Melting point was measured according to the Japanese Pharmacopoeia melting point measurement method 187-1
It was 88 ° C.
【0134】元素分析値も計算値とよく一致したことか
ら、例示化合物K−1の構造を確認した。Since the elemental analysis values were in good agreement with the calculated values, the structure of Exemplified Compound K-1 was confirmed.
【0135】 C H N 計算値 60.83% 3.14% 2.73% 実測値 60.68% 3.25% 2.70% 一般式〔L〕で表される例示化合物:例示化合物C H N calculated value 60.83% 3.14% 2.73% Actual value 60.68% 3.25% 2.70% Exemplified compound represented by the general formula [L]: Exemplified compound
【0136】[0136]
【化75】 [Chemical 75]
【0137】[0137]
【化76】 [Chemical 76]
【0138】[0138]
【化77】 [Chemical 77]
【0139】[0139]
【化78】 [Chemical 78]
【0140】[0140]
【化79】 [Chemical 79]
【0141】[0141]
【化80】 [Chemical 80]
【0142】[0142]
【化81】 [Chemical 81]
【0143】[0143]
【化82】 [Chemical formula 82]
【0144】[0144]
【化83】 [Chemical 83]
【0145】[0145]
【化84】 [Chemical 84]
【0146】[0146]
【化85】 [Chemical 85]
【0147】[0147]
【化86】 [Chemical 86]
【0148】[0148]
【化87】 [Chemical 87]
【0149】合成例Synthesis example
【0150】[0150]
【化88】 [Chemical 88]
【0151】上記の合成経路に従い例示化合物L−1を
合成した。2,4-ビス(トリフルオロメチル)ブロモベン
ゼン1を出発原料として、既知の方法(J.Chem,Soc, 10
71〜6(1954))に従い、化合物3を合成した。Exemplified Compound L-1 was synthesized according to the above synthetic route. Using 2,4-bis (trifluoromethyl) bromobenzene 1 as a starting material, a known method (J. Chem, Soc, 10
71 to 6 (1954)), compound 3 was synthesized.
【0152】化合物3 10gを100mlの四頭フラスコに入
れ、塩化亜鉛20gと5-アミノ-1-エチルピラゾール4
(アルドリッチ社製)5gとODB 100mlを加え、エス
テル管と温度計をつけて、40時間加熱還流した。放冷後
固体を吸引濾過で除き、DMSOでよく洗い込む。母液
の溶媒を減圧下留去し、残渣をシリカゲルのカラムに付
した。トルエン:n-ヘキサン=9:1溶出部を、トルエ
ンにて結晶化して、例示化合物IV−1の赤色結晶 9.3g
(収率75%)を得た。融点は日本薬局方融点測定法に従
い測定した結果168〜170℃であった。元素分析値も計算
値とよく一致したことから、例示化合物L−1の構造を
確認した。CompoundThree Put 10g into a 100ml four-headed flask
20 g of zinc chloride and 5-amino-1-ethylpyrazoleFour
Add 5g (made by Aldrich) and 100ml ODB,
A tellurium tube and a thermometer were attached, and the mixture was heated under reflux for 40 hours. After cooling
The solid is filtered off with suction and rinsed well with DMSO. Mother liquor
The solvent was distilled off under reduced pressure and the residue was applied to a silica gel column.
did. Toluene: n-hexane = 9: 1 eluate,
9.3 g of red crystal of Exemplified Compound IV-1
(Yield 75%) was obtained. Melting point is according to Japanese Pharmacopoeia Melting Point Measurement Method
The measurement result was 168 to 170 ° C. Calculate elemental analysis values
Since the values were in good agreement, the structure of Exemplified Compound L-1 was
confirmed.
【0153】 C H N 計算値 52.84% 2.53% 8.80% 実測値 52.81% 2.55% 8.77% 本発明の電子写真感光体において、導電性支持体として
は、例えば金属パイプ、金属板、金属シート、金属箔、
導電処理を施した高分子フィルム、Al等の金属の蒸着
層を設けた高分子フィルム、金属酸化物、第4級アンモ
ニウム塩等により被覆された高分子フィルム又は紙等が
用いられる。C H N calculated value 52.84% 2.53% 8.80% Actual value 52.81% 2.55% 8.77% In the electrophotographic photosensitive member of the present invention, examples of the conductive support include metal pipes, metal plates, metal sheets, and metal foils. ,
A conductive polymer film, a polymer film provided with a vapor deposition layer of a metal such as Al, a polymer film coated with a metal oxide, a quaternary ammonium salt, or the like, or paper is used.
【0154】本発明の電子写真感光体において、導電性
支持体上には感光層が設けられるが、感光層は単層構造
でもよく、電荷発生層と電荷輸送層とに機能分離された
積層構造のものでもよい。又、導電性支持体と感光層の
間に接着層を設けても良い。In the electrophotographic photosensitive member of the present invention, the photosensitive layer is provided on the conductive support, but the photosensitive layer may have a single layer structure, or a laminated structure in which the charge generation layer and the charge transport layer are functionally separated. It may be one. An adhesive layer may be provided between the conductive support and the photosensitive layer.
【0155】本発明の感光体は、図1(1)〜(4)に
示すように導電性支持体1上に、必要により接着層5を
設け、この上に感光層6を設け、さらにその上に本発明
に係る電子受容性物質を含有する保護層4が設けられ
る。図1(1)は導電性支持体1上にの直接P型CTM
を主成分とするCTL3、CGMを主成分とするCGL
2をこの順に積層して感光層6を形成し、この上に前記
電子受容性物質を含有する保護層4を設けた構成とされ
る。In the photoreceptor of the present invention, as shown in FIGS. 1 (1) to 1 (4), an adhesive layer 5 is optionally provided on a conductive support 1, a photosensitive layer 6 is provided thereon, and further, an adhesive layer 5 is provided thereon. A protective layer 4 containing the electron-accepting substance according to the present invention is provided on the top. FIG. 1 (1) shows a direct P-type CTM on the conductive support 1.
CTL3 whose main component is CGL and CGL whose main component is CGM
2 is laminated in this order to form a photosensitive layer 6, on which a protective layer 4 containing the electron-accepting substance is provided.
【0156】図1(2)は図1(1)の感光体の支持体
1とCTL3との間に接着層5を設けた構成とされる。
図1(3)は図1(2)の感光体のCGL2中にCGM
と共に適量のP型又はN型CTMを含有した構成とされ
る。図1(4)は図1(2)の二層構成の感光層6に代
えてCGMとP型CTMと共存させた単層構成の感光層
を設けた構成とされる。FIG. 1B shows a structure in which an adhesive layer 5 is provided between the support 1 and the CTL 3 of the photoconductor of FIG. 1A.
FIG. 1 (3) shows the CGM in the CGL2 of the photoconductor of FIG. 1 (2).
Together with an appropriate amount of P-type or N-type CTM. 1 (4) has a structure in which a single-layer photosensitive layer in which CGM and P-type CTM coexist is provided in place of the double-layer photosensitive layer 6 in FIG. 1 (2).
【0157】接着層は、樹脂単独で形成したもの、酸化
錫,酸化インジウム、酸化チタンなどの低抵抗化合物を
樹脂中に分散させたものを塗布したもの、又酸化アルミ
ニウム,酸化亜鉛,酸化珪素などの蒸着膜でもよい。接
着層に用いる樹脂としては、特に制限はないが、塩化ビ
ニリデン-塩化ビニル共重合体,水溶性ポリビニルブチ
ラール樹脂,アルコール可溶性ポリアミド樹脂,酢酸ビ
ニル系樹脂,ポリビニルアルコール,ニトロセルロー
ス,ポリイミド樹脂等が挙げられ、該接着層の膜厚は0.
01〜10μmとされ、好ましくは0.01〜1μmとされる。The adhesive layer is formed of resin alone, coated with a dispersion of a low resistance compound such as tin oxide, indium oxide and titanium oxide in resin, aluminum oxide, zinc oxide, silicon oxide, etc. The vapor deposition film of The resin used for the adhesive layer is not particularly limited, and examples thereof include vinylidene chloride-vinyl chloride copolymer, water-soluble polyvinyl butyral resin, alcohol-soluble polyamide resin, vinyl acetate resin, polyvinyl alcohol, nitrocellulose, and polyimide resin. The thickness of the adhesive layer is 0.
The thickness is from 01 to 10 μm, preferably from 0.01 to 1 μm.
【0158】前記感光層6を形成するCTM,CGMの
特性によって次の方法によって形成される。It is formed by the following method according to the characteristics of CTM and CGM forming the photosensitive layer 6.
【0159】(1)気相堆積法 (2)塗料塗布法 a)CGM,CTMを適当な溶剤に溶解した溶液塗料を
塗布する方法 b)CGM,CTMをボールミル,ホモミキサ等によっ
て分散媒中で微細粒子状とし、必要に応じて結着剤と混
合分散して得られる分散液塗料を塗布する方法 前記気相堆積法には真空蒸着法,スパッタリング法,イ
オンプレーテング法或はCVD法等が挙げられ、また塗
料塗布法にはディッピング法,スプレイ法,エアドクタ
法,ドクタブレイド法,リバースロール法,バーコート
法等塗料の物性に合せて適当な方法が選ばれる。(1) Vapor deposition method (2) Coating method a) Method of applying a solution coating in which CGM and CTM are dissolved in a suitable solvent b) CGM and CTM are finely dispersed in a dispersion medium by a ball mill, homomixer or the like. A method of applying a dispersion liquid coating obtained by making it into particles and optionally mixing and dispersing it with a binder. The vapor deposition method includes a vacuum deposition method, a sputtering method, an ion plating method, a CVD method and the like. Further, as a coating method, a suitable method is selected according to the physical properties of the coating such as a dipping method, a spray method, an air doctor method, a doctor blade method, a reverse roll method and a bar coat method.
【0160】前記図1(1)〜(3)の二層構成の感光
体において、CTL3を形成するには、通常P型CTM
をバインダー樹脂と共に1:100〜100〜1、好ましくは
1:20〜20:1の混合比で有機溶剤に溶解し、得られた
塗布液を乾燥膜厚2〜100μm、好ましくは5〜50μm
に塗布加工される。In the two-layered photoreceptor of FIGS. 1 (1) to 1 (3), a P-type CTM is usually used to form CTL3.
Is dissolved in an organic solvent at a mixing ratio of 1: 100 to 100 to 1, preferably 1:20 to 20: 1 together with a binder resin, and the obtained coating solution is dried to a film thickness of 2 to 100 μm, preferably 5 to 50 μm.
Is applied and processed.
【0161】前記P型CTMとしては、特に制限はない
が、例えばオキサゾール誘導体,オキサジアゾール誘導
体,チアゾール誘導体,チアジアゾール誘導体,トリア
ゾール誘導体,イミダゾール誘導体,イミダゾロン誘導
体,イミダゾリジン誘導体,ビスイミダゾリジン誘導
体,スチリル化合物,ヒドラゾン化合物,ピラゾリン誘
導体,オキサゾロン誘導体,ベンゾチアゾール誘導体、
ベンゾフラン誘導体,アクリジン誘導体,フエナジン誘
導体,アミノスチルベン誘導体,ポリ-N-ビニルカルバ
ゾール,ポリ-1-ビニルピレン、ポリ-9-ビニルアントラ
セン等であってよい。The P-type CTM is not particularly limited, and examples thereof include oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazolidine derivatives, bisimidazolidine derivatives, styryl. Compounds, hydrazone compounds, pyrazoline derivatives, oxazolone derivatives, benzothiazole derivatives,
It may be a benzofuran derivative, an acridine derivative, a phenazine derivative, an aminostilbene derivative, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene or the like.
【0162】中でも例えば特開昭62-157047号公報に記
載されるスチリル化合物,ヒドラゾン化合物,アミン誘
導体、さらには特願平4-55243号,同4-55244号,同4-55
245号等の各号明細書に記載されるジスチリル系化合物
等が好ましく用いられる。Among them, for example, styryl compounds, hydrazone compounds, amine derivatives described in JP-A-62-157047, and Japanese Patent Application Nos. 4-55243, 4-55244 and 4-55.
Distyryl compounds described in each specification such as No. 245 are preferably used.
【0163】前記CTL3に用いられるバインダー樹脂
としては、例えばアクリロニトリル-ブタジエン共重合
体,スチレン-ブタジエン共重合体,ビニルトルエン-ス
チレン共重合体,スチレン変性アルキッド樹脂,シリコ
ーン変性アルキッド樹脂,大豆油変性アルキッド樹脂,
塩化ビニリデン-塩化ビニル樹脂,ポリビニルブチラー
ル,ニトロ化ポリスチレン,ポリメチルスチレン,ポリ
イソプレン,ポリエステル,フェノール樹脂,ケトン樹
脂,ポリアミド,ポリカーボネート,ポリチオカーボネ
ート,ポリアミリレート,ポリハロアクリレート,酢酸
ビニル系樹脂,ポリスチレン,ポリアリルエーテル,ポ
リビニルアクリレート,ポリスルホン,ポリメタクリレ
ート等が挙げられる。なかでもビフェニルZ型ポリカー
ボネートは特に好ましい。Examples of the binder resin used in the CTL3 include acrylonitrile-butadiene copolymer, styrene-butadiene copolymer, vinyltoluene-styrene copolymer, styrene-modified alkyd resin, silicone-modified alkyd resin, soybean oil-modified alkyd. resin,
Vinylidene chloride-vinyl chloride resin, polyvinyl butyral, nitrated polystyrene, polymethylstyrene, polyisoprene, polyester, phenol resin, ketone resin, polyamide, polycarbonate, polythiocarbonate, polyamylate, polyhaloacrylate, vinyl acetate resin, Examples thereof include polystyrene, polyallyl ether, polyvinyl acrylate, polysulfone, polymethacrylate and the like. Among them, biphenyl Z type polycarbonate is particularly preferable.
【0164】次に図1(1)〜(3)の二層構成の感光
体において前記CTL3上にCGL2を形成するには、
バインダー樹脂を有機溶剤に溶解した溶液中にCGMバ
インダー樹脂/CGMの比率が0〜10、好ましくは0.1
〜2となるように混合・撹拌して平均粒径1μm以下の
微粒子状に分散し、得られた分散液から成る塗布液を乾
燥膜厚が0.01〜10μm、好ましくは0.05〜2μmとなるよ
う塗布加工して得られる。Next, in order to form the CGL2 on the CTL3 in the two-layered photoreceptor of FIGS. 1 (1) to (3),
The ratio of CGM binder resin / CGM in the solution in which the binder resin is dissolved in an organic solvent is 0 to 10, preferably 0.1.
~ 2 to mix and stir to disperse into fine particles with an average particle size of 1 μm or less, and apply a coating solution consisting of the resulting dispersion to a dry film thickness of 0.01 to 10 μm, preferably 0.05 to 2 μm Obtained by processing.
【0165】尚図1(3)の二層構成の感光体において
は、CGL2中にN型CTM又は前記P型CTMをバイ
ンダー樹脂に対して1〜200wt%、好ましくは5〜100wt
%含有される。ここでCGMと共にCGL2中に含有さ
れるN型CTMとしては、本発明に係る前記一般式
〔A〕〜一般式〔L〕で表わされる電子受容性物質が好
ましいがその他例えば特願平3-3841号明細書に記載され
るN型CTMであってもよい。In the two-layer photosensitive member of FIG. 1 (3), the N-type CTM or the P-type CTM is contained in CGL2 in an amount of 1 to 200 wt%, preferably 5 to 100 wt% with respect to the binder resin.
% Contained. Here, as the N-type CTM contained in CGL2 together with CGM, the electron-accepting substances represented by the above general formulas [A] to [L] according to the present invention are preferable, but other examples are Japanese Patent Application No. 3-3841. It may be an N-type CTM described in the specification.
【0166】次に感光層6が単層構成とされる図4の感
光体において該感光層6を形成するには、バインダー樹
脂と共に前記したP型CTMを有機溶剤に溶解して得ら
れる溶液中にCGMを分散して成る塗布液を乾燥膜厚5
〜50μm、好ましくは10〜30μmに塗布加工して得られ
る。Next, in order to form the photosensitive layer 6 in the photoreceptor of FIG. 4 in which the photosensitive layer 6 has a single layer structure, in the solution obtained by dissolving the above-mentioned P-type CTM together with the binder resin in the organic solvent. A coating solution of CGM dispersed in
˜50 μm, preferably 10 to 30 μm.
【0167】この場合、バインダー樹脂/CGMの比率
は0.05〜20、好ましくは0.1〜5とされ、又前記バイン
ダー樹脂に対してCTMは1〜200wt%、好ましくは5
〜100wt%とされる。In this case, the ratio of binder resin / CGM is 0.05 to 20, preferably 0.1 to 5, and CTM is 1 to 200 wt%, preferably 5 to the binder resin.
~ 100wt%
【0168】前記CGL2は蒸着により形成されてもよ
く、通常は前記のように塗布加工により形成される。The CGL2 may be formed by vapor deposition, and is usually formed by coating as described above.
【0169】前記図1(1)〜(3)のCGL2及び
(4)の感光層6に含有されるCGMとしては、Te-S
eなどの無機半導体,ポリビニルカルバゾール等の有機
半導体,ビスアゾ系化合物,トリスアゾ系化合物,無金
属フタロシアニン系化合物,金属フタロシアニン系化合
物,ピリリウム系化合物,スクエアリウム系化合物,シ
アニン系化合物,ペリレン系化合物,多環キノン系化合
物等の有機顔料が使用できる。なかでも好ましい電荷発
生物質としては、例えば特開昭64-17066号の27.2°
にX線回折ピークを有するY型チタニルフタロシアニン
顔料、特開昭62−67094号の26.3°にX線回折ピ
ークを有するA型チタニルフタロシアニン顔料、特開昭
61-239248号の28.7°にX線回折ピークを有するB型チ
タニルフタロシアニン顔料、特公昭49-4338号の無金属
フタロシアニン顔料、特開昭57-163239号の銅フタロシ
アニン顔料、特開昭57-148747号のバナジルフタロシア
ニン顔料、特開昭49-128734号のペリレン顔料、特開昭4
7-18544号の縮合多環顔料、特開平1-150145号のビスア
ゾ顔料などがある。又、結着樹脂としては、ポリスチレ
ン,シリコーン樹脂,ポリカーボネート樹脂,アクリル
樹脂,メタクリル樹脂,ポリエステル,ビニル系重合
体,セルロース系樹脂,ブチラール系樹脂,シリコーン
変性ブチラール樹脂,アルキッド樹脂等が使用できる。The CGM contained in the CGL 2 and the photosensitive layer 6 of (4) in FIGS. 1 (1) to 1 (3) is Te-S.
Inorganic semiconductors such as e, organic semiconductors such as polyvinylcarbazole, bisazo compounds, trisazo compounds, metal-free phthalocyanine compounds, metal phthalocyanine compounds, pyrylium compounds, squarylium compounds, cyanine compounds, perylene compounds, many Organic pigments such as ring quinone compounds can be used. Among them, a preferable charge generating substance is, for example, 27.2 ° in JP-A-64-17066.
Y-type titanyl phthalocyanine pigment having an X-ray diffraction peak at 2, and A-type titanyl phthalocyanine pigment having an X-ray diffraction peak at 26.3 ° in JP-A-62-67094,
61-239248, B-type titanyl phthalocyanine pigment having an X-ray diffraction peak at 28.7 °, metal-free phthalocyanine pigment of JP-B-49-4338, copper phthalocyanine pigment of JP-A-57-163239, JP-A-57-148747. Vanadyl phthalocyanine pigment, JP-A-49-128734, perylene pigment, JP-A-4
There are condensed polycyclic pigments of No. 7-18544 and bisazo pigments of JP-A No. 1-150145. As the binder resin, polystyrene, silicone resin, polycarbonate resin, acrylic resin, methacrylic resin, polyester, vinyl polymer, cellulose resin, butyral resin, silicone modified butyral resin, alkyd resin, etc. can be used.
【0170】次に前記図1(1)〜(3)のCGL2又
は(4)の感光層6上に設けられる保護層4は、バイン
ダー樹脂と該バインダー樹脂に対して0.1〜200wt%の本
発明特有の前記電子受容性物質を含有する塗布液を乾燥
膜厚0.1〜20μm、好ましくは1〜5μmとなるよう塗布
加工して形成される。Next, the protective layer 4 provided on the photosensitive layer 6 of CGL 2 or (4) shown in FIGS. 1 (1) to 1 (3) is a binder resin and 0.1 to 200 wt% of the present invention with respect to the binder resin. It is formed by applying a coating solution containing the above-mentioned electron-accepting substance to a dry film thickness of 0.1 to 20 μm, preferably 1 to 5 μm.
【0171】前記保護層中に含有されるバインダー樹脂
としては、例えばポリプロピレン,アクリル樹脂,メタ
クリル樹脂,塩化ビニル樹脂,酢酸ビニル樹脂,エポキ
シ樹脂,ブチラール樹脂,ポリカーボネート樹脂,シリ
コーン樹脂又はこれらの共重合樹脂、例えば塩化ビニル
-酢酸ビニル共重合体樹脂,塩化ビニル-酢酸ビニル-無
水マレイン酸共重合体樹脂,ポリ-N-ビニルカルバゾー
ル等の熱可塑性樹脂が用いられる。又熱可塑性樹脂と混
合して、又は独立に例えば熱硬化性アクリル樹脂,シリ
コーン樹脂,エポキシ樹脂,ウレタン樹脂,尿素樹脂,
フェノール樹脂,ポリエステル樹脂,アルキッド樹脂,
メラミン樹脂,光硬化性・桂皮酸樹脂等又はこれらの共
重合もしくは共縮合樹脂等の光又は熱硬化性樹脂も使用
可能である。The binder resin contained in the protective layer is, for example, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, butyral resin, polycarbonate resin, silicone resin or copolymer resin thereof. , For example vinyl chloride
-Vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin, thermoplastic resin such as poly-N-vinylcarbazole are used. Further, by mixing with a thermoplastic resin or independently, for example, thermosetting acrylic resin, silicone resin, epoxy resin, urethane resin, urea resin,
Phenolic resin, polyester resin, alkyd resin,
A light or thermosetting resin such as a melamine resin, a photocurable / cinnamic acid resin, or a copolymerization or cocondensation resin thereof can also be used.
【0172】又前記保護層は、電子受容性物質の外、必
要によりCGL中のCGMを保護する目的で紫外線吸収
剤又は酸化防止剤等を含有せしめてもよい。In addition to the electron-accepting substance, the protective layer may optionally contain an ultraviolet absorber or an antioxidant for the purpose of protecting CGM in CGL.
【0173】[0173]
【実施例】以下本発明の実施例及び比較例により具体的
に説明するが、本発明の実施の態様はこれにより限定さ
れるものではない。EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the embodiments of the present invention are not limited thereto.
【0174】〔感光体の作成〕アルミニウム製素管上に
必要によりアルコール可溶性ポリアミド樹脂の薄層から
成る中間層を設け、該中間層上に積層型及び単層型の各
種感光層を設け、該感光層上に本発明に係る電子受容性
物質及び比較用の電子受容性物質を含有する保護層を設
けて40種類の感光体(感光体1〜40)を得た。又前記40
種類の感光体の製法及びその要約(表1〜4)が下記に
示される。[Preparation of Photoreceptor] If necessary, an intermediate layer composed of a thin layer of an alcohol-soluble polyamide resin is provided on an aluminum tube, and various laminated and single-layer type photosensitive layers are provided on the intermediate layer. A protective layer containing an electron-accepting substance according to the present invention and an electron-accepting substance for comparison was provided on the photosensitive layer to obtain 40 kinds of photoreceptors (photoreceptors 1 to 40). Also above 40
A method of making various types of photoreceptors and a summary thereof (Tables 1 to 4) are shown below.
【0175】尚積層型には、仮称X型とZ型とがあり、
X型は基体上にCTL,CGL及び保護層をこの順に積
層した感光層であり、Z型はX型の感光層のCGL中に
CTMを含有する感光層である。なお前記X型感光層に
はさらにX型-1,X型-2,X型-3,X型-4及びX型
-5の互いに異なる基準処方に基づく5種類の感光層が
設定された。The laminated type includes a tentative name X type and a Z type.
The X type is a photosensitive layer in which CTL, CGL and a protective layer are laminated in this order on a substrate, and the Z type is a photosensitive layer containing CTM in the CGL of the X type photosensitive layer. The X-type photosensitive layer further includes X-type-1, X-type-2, X-type-3, X-type-4 and X-type.
Five photosensitive layers were set based on -5 different reference formulations.
【0176】又前記単層型はY型と仮称され、基体上に
CGMとCTMを共に含有する層から成る単層構成の感
光層である。The single layer type is tentatively called Y type, and is a photosensitive layer having a single layer structure composed of a layer containing both CGM and CTM on the substrate.
【0177】〈感光体1(X型-1)の作成〉共重合ナ
イロン樹脂「CM-8000」(東レ社製)のメタノール/1-
ブタノール溶液を用い、前記PETベース上に0.15μm
の中間層を設けた。次に、下記構造のCTM(CTM
1)75部、ポリカーボネート樹脂「パンライトTS205
0」(帝人化成社製)100部、酸化防止剤「IRGANO
X1010」(チバガイギー社製)8部及び微量のシリコン
オイル「KF-54」(信越化学社製)をジクロルメタン6
70部に溶解した液を用い、浸漬塗布方法によって塗布し
乾燥の後、膜厚25μmのCTLを形成した。<Preparation of Photoreceptor 1 (X-type-1)> Copolymer nylon resin "CM-8000" (manufactured by Toray Industries) in methanol / 1-
0.15 μm on the PET base using butanol solution
Was provided. Next, a CTM with the following structure (CTM
1) 75 parts, polycarbonate resin "Panlite TS205
0 "(manufactured by Teijin Kasei) 100 parts, antioxidant" IRGANO
8 parts of "X1010" (manufactured by Ciba Geigy) and a small amount of silicon oil "KF-54" (manufactured by Shin-Etsu Chemical Co., Ltd.)
A solution dissolved in 70 parts was applied by a dip coating method and dried to form a CTL having a film thickness of 25 μm.
【0178】次に、下記構造のCGM(CGM1)5
部、バインダー樹脂としてポリビニルブチラール樹脂
「エスレックBL-S」(積水化学社製)1部をMEK
(メチルエチルケトン)200部と共にサンドミルを用い
て分散し、円形スライドホッパー塗布機を用いて塗布
し、乾燥の後、膜厚0.3μmのCGLを形成した。さらに
該CGL上に例示化合物(A−1)15部とシリコーンハ
ードコート剤「KT-85」(信越化学社製)100部をTH
F100部に溶解し、得られた塗布液を円形スライドホッ
パーを用いて塗布、硬化させ3μmの表面保護層を形成
し、積層構成の感光体1を得た。Next, CGM (CGM1) 5 having the following structure
Part, 1 part of polyvinyl butyral resin "ESREC BL-S" (manufactured by Sekisui Chemical Co., Ltd.) as a binder resin is MEK
It was dispersed together with 200 parts of (methyl ethyl ketone) using a sand mill, coated using a circular slide hopper coating machine, and dried to form CGL having a film thickness of 0.3 μm. Further, on the CGL, 15 parts of the exemplified compound (A-1) and 100 parts of a silicone hard coating agent "KT-85" (manufactured by Shin-Etsu Chemical Co., Ltd.) were added.
The coating solution thus obtained was dissolved in 100 parts of F and was coated and cured using a circular slide hopper to form a surface protective layer of 3 μm, whereby a photoreceptor 1 having a laminated structure was obtained.
【0179】〈感光体2〜6(X型-1)の作成〉感光
体1の保護層中の例示化合物(A−1)に代えて例示化
合物(B−2),(C−2),(D−3),(E−1)
及び(F−5)を用いた他は感光体1と同様にして積層
構成の感光体2,感光体3,感光体4,感光体5及び感
光体6を得た。<Preparation of Photoreceptors 2 to 6 (X-type-1)> Exemplified compounds (B-2), (C-2), in place of the exemplified compound (A-1) in the protective layer of the photoreceptor 1. (D-3), (E-1)
And (F-5) were used in the same manner as in the photoconductor 1 to obtain a photoconductor 2, a photoconductor 3, a photoconductor 4, a photoconductor 5, and a photoconductor 6 having a laminated structure.
【0180】〈感光体7(X型-2)の作成〉下記構造
のCTM(CTM2)75部とポリカーボネート樹脂「ユ
ーピロンZ300」(粘度平均分子量30,000)(三菱瓦斯
化学社製)100部、ポリエステル樹脂「バイロン200」
(東洋紡社製)10部、酸化防止剤「サノールLS-262
6」(三共社製)7部及び微量のシリコンオイル「KF-
54」(信越化学社製)をジクロロメタン500部に溶解し
た液をアルミニウムドラム上に浸漬塗布法によって塗布
して、乾燥の後、膜厚25μmのCTLを形成した。<Preparation of Photoreceptor 7 (X-Type-2)> 75 parts of CTM (CTM2) having the following structure, 100 parts of polycarbonate resin "UPILON Z300" (viscosity average molecular weight 30,000) (manufactured by Mitsubishi Gas Chemical Co., Inc.), polyester resin "Byron 200"
(Toyobo Co., Ltd.) 10 parts, antioxidant "Sanol LS-262"
6 "(manufactured by Sankyosha) and a small amount of silicone oil" KF- "
A solution obtained by dissolving 54 "(manufactured by Shin-Etsu Chemical Co., Ltd.) in 500 parts of dichloromethane was applied onto an aluminum drum by a dip coating method, and after drying, a CTL having a film thickness of 25 μm was formed.
【0181】次に、下記構造のCGM(CGM2)2.5
部、バインダー樹脂としてポリビニルブチラール樹脂
「エスレックBX-1」(積水化学社製)1部をMIP
K(メチルイソプロピルケトン)143部と共にサンドミ
ルを用いて分散した後、円形スライドホッパー塗布機を
用いて塗布し、乾燥の後、膜厚0.5μmのCGLを形成し
た。更に該CGL上に例示化合物(G−1)15部とシリ
コーンハードコート剤「KP-85」(信越化学社製)100
部をTHF100部に溶解し、得られた塗布液を円形スラ
イドホッパーを用いて塗布,硬化させ3μmの表面保護
層を形成して、積層構成の感光体7を得た。Next, CGM (CGM2) 2.5 having the following structure
Parts, 1 part of polyvinyl butyral resin "ESREC BX-1" (manufactured by Sekisui Chemical Co., Ltd.) as a binder resin
After dispersing with a sand mill together with 143 parts of K (methyl isopropyl ketone), it was coated using a circular slide hopper coater and dried to form a CGL having a film thickness of 0.5 μm. Further, on the CGL, 15 parts of the exemplified compound (G-1) and a silicone hard coat agent "KP-85" (manufactured by Shin-Etsu Chemical Co., Ltd.) 100
Part was dissolved in 100 parts of THF, and the obtained coating solution was applied and cured using a circular slide hopper to form a surface protection layer of 3 μm, and a photoconductor 7 having a laminated structure was obtained.
【0182】〈感光体8〜12(X型-2)の作成〉感光
体7の保護層中の例示化合物(G−1)に代えて、例示
化合物(H−3),(J−4),(K−3),(L−
1)及び(A−3)を用いた他は感光体7と同様にして
積層構成の感光体8,感光体9,感光体10,感光体11及
び感光体12を得た。<Preparation of Photoreceptors 8 to 12 (X-Type-2)> In place of the exemplified compound (G-1) in the protective layer of the photoreceptor 7, exemplified compounds (H-3) and (J-4). , (K-3), (L-
Photoconductor 8, photoconductor 9, photoconductor 10, photoconductor 11, photoconductor 11 and photoconductor 12 having a laminated structure were obtained in the same manner as photoconductor 7 except that 1) and (A-3) were used.
【0183】〈感光体13(X型-3)の作成〉下記構造
のCTM(CTM3)13部とポリカーボネート樹脂「ユ
ーピロンZ200」(粘度平均分子量20,000)(三菱瓦斯
化学社製)20部、ポリエステル樹脂「バイロン200」
(東洋紡社製)2部を1,2-ジクロルエタン100部に溶解
した液をアルミニウムドラム上に浸漬塗布法によって塗
布,乾燥した後、膜厚25μmのCTLを形成した。次
に、下記構造のCGM(CGM3)2部、バインダー樹
脂としてポリビニルブチラール樹脂「エスレックBM-
S」(積水化学社製)1部をMEK/シクロヘキサノン
(=4/1)85部と共にサンドミルを用いて分散した
後、円形スライドホッパー塗布機を用いて塗布し乾燥の
後、膜厚0.7μmのCGLを形成した。更に該CGL上に
例示化合物(B−8)6部とポリカーボネート樹脂「ユ
ーピロンZ800」(粘度平均分子量80,000)(三菱瓦斯
化学社製)10部をジクロルメタン100部に溶解し、得ら
れた塗布液を円形スライドホッパーを用いて塗布,乾燥
の後、膜厚5μmの表面保護を形成して、積層構成の感
光体13を得た。<Preparation of Photoreceptor 13 (X-type-3)> 13 parts of CTM (CTM3) having the following structure and 20 parts of polycarbonate resin "UPILON Z200" (viscosity average molecular weight 20,000) (manufactured by Mitsubishi Gas Chemical Co., Inc.), polyester resin "Byron 200"
(Toyobo Co., Ltd.) A solution prepared by dissolving 2 parts in 100 parts of 1,2-dichloroethane was applied on an aluminum drum by a dip coating method and dried, and then a CTL having a film thickness of 25 μm was formed. Next, 2 parts of CGM (CGM3) having the following structure, and polyvinyl butyral resin "ESREC BM-" as a binder resin
S ”(manufactured by Sekisui Chemical Co., Ltd.) was dispersed with 85 parts of MEK / cyclohexanone (= 4/1) using a sand mill, and then coated using a circular slide hopper coater and dried to give a film thickness of 0.7 μm. CGL was formed. Furthermore, 6 parts of the exemplified compound (B-8) and 10 parts of a polycarbonate resin "Iupilon Z800" (viscosity average molecular weight 80,000) (manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 100 parts of dichloromethane on the CGL to obtain a coating solution. After coating and drying using a circular slide hopper, surface protection having a film thickness of 5 μm was formed to obtain a photoconductor 13 having a laminated structure.
【0184】〈感光体14〜16(X型-3)の作成〉感光
体13の保護層中の例示化合物(B−8)に代えて(C−
6),(D−7)及び(E−8)を用いた他は感光体13
と同様にして積層構成の感光体14,感光体15及び感光体
16を得た。<Preparation of Photoreceptors 14 to 16 (X-Type-3)> Instead of the exemplified compound (B-8) in the protective layer of the photoreceptor 13, (C-
6), (D-7) and (E-8) except that a photoconductor 13 is used.
Photoreceptor 14, photoreceptor 15 and photoreceptor having a laminated structure similar to
Got 16.
【0185】〈感光体17(X型-4)の作成〉アルミニ
ウム素管上にポリアミド樹脂「X-1874M」(ダイセル
ヒュルス社製)から成る膜厚0.3μmの中間層を設け、そ
の上に下記構造のCTM(CTM4)11部とポリカーボ
ネート樹脂「ユーピロンZ300」(粘度平均分子量30,00
0)(三菱瓦斯化学社製)15部をジクロルメタン100部に
溶解した液を用いて膜厚25μmのCTLを形成した。次
に、下記CGM(CGM3)2部、CGM2 0.2部、
バインダー樹脂としてポリビニルブチラール樹脂「エス
レックBH-S」(積水化学社製)1部をMEK85部と
共にサンドミルを用いて分散した後、スプレー塗布機を
用いて塗布し、膜厚0.5μmのCGLを形成した。更に該
CGL上に例示化合物(F−9)15部をシリコンハード
コート剤「KP-85」100部、MEK100部に溶解し、得
られた塗布液をスプレー塗布機を用いて塗布、硬化の
後、2μmの表面保護層を形成して、積層構成の感光体1
7を得た。<Preparation of Photoreceptor 17 (X-Type-4)> An intermediate layer made of polyamide resin "X-1874M" (manufactured by Daicel Hüls) having a thickness of 0.3 μm is provided on an aluminum tube, and an intermediate layer is provided thereon. 11 parts of CTM (CTM4) having the following structure and polycarbonate resin “UPILON Z300” (viscosity average molecular weight 30,00
0) 15 parts (manufactured by Mitsubishi Gas Chemical Co., Inc.) was dissolved in 100 parts of dichloromethane to form a CTL having a film thickness of 25 μm. Next, 2 parts of the following CGM (CGM3), 0.2 part of CGM2,
As a binder resin, 1 part of polyvinyl butyral resin "ESREC BH-S" (manufactured by Sekisui Chemical Co., Ltd.) was dispersed together with 85 parts of MEK using a sand mill and then applied using a spray applicator to form a CGL having a film thickness of 0.5 μm. . Further, 15 parts of the exemplified compound (F-9) was dissolved in 100 parts of silicon hard coating agent "KP-85" and 100 parts of MEK on the CGL, and the obtained coating solution was applied using a spray coater, and after curing. A 2 μm surface protective layer is formed to form a laminated photoreceptor 1.
Got 7.
【0186】〈感光体18及び19(X型-4)の作成〉感
光体17の保護層中の例示化合物(F−7)に代えて例示
化合物(G−5)及び(H−10)を用いた他は感光体17
と同様にして積層構成の感光体18及び感光体19を得た。<Preparation of Photoreceptors 18 and 19 (X-type-4)> Exemplified compounds (G-5) and (H-10) were used in place of the exemplified compound (F-7) in the protective layer of the photoreceptor 17. Photoconductor 17
In the same manner as described above, a photosensitive member 18 and a photosensitive member 19 having a laminated structure were obtained.
【0187】[0187]
【化89】 [Chemical 89]
【0188】[0188]
【化90】 [Chemical 90]
【0189】〈感光体20(X型-5)の作成〉共重合ナ
イロン樹脂「CM-8000」(東レ社製)のメタノール/1-
ブタノール溶液を用いてアルミドラム基体上に0.2μmの
中間層を設けた。次に、前記CTM(CTM2)13部と
ポリカーボネート樹脂「ユーピロンZ200」(粘度平均
分子量20,000)(三菱瓦斯化学社製)20部を1,2-ジクロ
ルエタン100部に溶解した液をアルミニウムドラム上に
浸漬塗布法によって塗布、乾燥した後、膜厚25μmのC
TLを形成した。次に、下記構造のCGM(CGM5)
2部、バインダー樹脂としてセルロース変性シリコン樹
脂「KR-5240」(信越化学社製)1部を酢酸t-ブチル1
00部と共にサンドミルを用いて分散した後、円形スライ
ドホッパーを用いて塗布、乾燥し膜厚0.2μmのCGLを
形成した。更に該CGL上に例示化合物(J−9)6部
とポリカーボネート樹脂「ユーピロンZ800」(粘度平
均分子量80,000)(三菱瓦斯化学社製)10部をジクロル
メタン100部に溶解し、得られた塗布液を円形スライド
ホッパーを用いて塗布、乾燥の後、膜厚5μmの表面保
護層を形成して、積層構成の感光体20を得た。<Preparation of Photoreceptor 20 (X-type-5)> Copolymer nylon resin "CM-8000" (manufactured by Toray Industries) in methanol / 1-
A 0.2 μm intermediate layer was provided on an aluminum drum substrate using butanol solution. Next, a solution prepared by dissolving 13 parts of the CTM (CTM2) and 20 parts of a polycarbonate resin "UPILON Z200" (viscosity average molecular weight 20,000) (manufactured by Mitsubishi Gas Chemical Co., Inc.) in 100 parts of 1,2-dichloroethane was immersed in an aluminum drum. After coating and drying by the coating method, C with a film thickness of 25 μm
TL was formed. Next, CGM (CGM5) having the following structure
2 parts, 1 part of cellulose-modified silicone resin "KR-5240" (manufactured by Shin-Etsu Chemical Co., Ltd.) as a binder resin, and 1 part of t-butyl acetate
After being dispersed together with 00 parts using a sand mill, it was coated using a circular slide hopper and dried to form a CGL having a film thickness of 0.2 μm. Further, 6 parts of the exemplified compound (J-9) and 10 parts of a polycarbonate resin "Iupilon Z800" (viscosity average molecular weight 80,000) (manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 100 parts of dichloromethane on the CGL to obtain a coating solution. After coating and drying using a circular slide hopper, a surface protective layer having a film thickness of 5 μm was formed to obtain a photoconductor 20 having a laminated structure.
【0190】[0190]
【化91】 [Chemical Formula 91]
【0191】〈感光体21及び22(X型-5)の作成〉感
光体20の保護層中の例示化合物(J−9)に代えて例示
化合物(K−12)及び(L−15)を用いた他は感光体20
と同様にして積層構成の感光体21及び22を得た。<Preparation of Photoreceptors 21 and 22 (X-type-5)> Exemplified compounds (K-12) and (L-15) were used in place of the exemplified compound (J-9) in the protective layer of the photoreceptor 20. Other than used, photoconductor 20
Photosensitive members 21 and 22 having a laminated structure were obtained in the same manner as in.
【0192】〈感光体23(Y型)の作成〉前記CGM
(CGM3)10部、前記CTM(CTM2)15部、ポリ
カーボネート樹脂「ユーピロンZ200」(粘度平均分子
量20,000)(三菱瓦斯化学社製)20部を1,2-ジクロルエ
タン45部と共にサンドミルを用いて分散した後、浸漬塗
布法にて塗布、乾燥の後、膜厚25μmの感光層を得た。
更に該感光層上に例示化合物(A−1)15部をシリコン
ハードコート剤「KP-85」100部、MEK100部に溶解
し、得られた塗布液をスプレー塗布機を用いて塗布、硬
化の後、2μmの表面保護層を形成して、単層構成の感
光体23を得た。<Preparation of Photoreceptor 23 (Y Type)> CGM
(CGM3) 10 parts, CTM (CTM2) 15 parts, polycarbonate resin "UPILON Z200" (viscosity average molecular weight 20,000) (manufactured by Mitsubishi Gas Chemical Co., Inc.) 20 parts were dispersed together with 45 parts of 1,2-dichloroethane using a sand mill. Then, after coating by a dip coating method and drying, a photosensitive layer having a film thickness of 25 μm was obtained.
Further, 15 parts of Exemplified Compound (A-1) was dissolved in 100 parts of silicon hard coating agent "KP-85" and 100 parts of MEK on the photosensitive layer, and the obtained coating solution was applied and cured using a spray coating machine. After that, a surface protective layer having a thickness of 2 μm was formed to obtain a single-layer photosensitive member 23.
【0193】〈感光体24(Y型)の作成〉感光体23の保
護層中の例示化合物(A−1)に代えて例示化合物(A
−3)を用いた他は感光体23と同様にして、単層構成の
感光体24を得た。<Preparation of Photoreceptor 24 (Y Type)> In place of the exemplified compound (A-1) in the protective layer of the photoreceptor 23, the exemplified compound (A
A single-layer photosensitive member 24 was obtained in the same manner as the photosensitive member 23 except that (3) was used.
【0194】〈感光体25及び26(Y型)の作成〉感光体
23の感光層中のCTM2に代えてCTM3を用い、保護
層中の例示化合物(A−1)に代えて例示化合物(E−
30)及び(H−4)を用いた他は感光体23と同様にして
単層構成の感光体25及び26を得た。<Production of Photoreceptors 25 and 26 (Y Type)> Photoreceptor
CTM3 in the photosensitive layer of 23 was used instead of CTM3, and the exemplary compound (E- was used instead of the exemplary compound (A-1) in the protective layer.
30) and (H-4) were used, and single-layer photosensitive members 25 and 26 were obtained in the same manner as the photosensitive member 23.
【0195】〈感光体27(Y型)の作成〉感光体23の感
光層中のCTM2に代えて例示化合物(A−1)を用
い、保護層中の例示化合物(A−1)に代えて例示化合
物(CT−17)を用いた他は感光体23と同様にして単層
構成の感光体27を得た。<Preparation of Photoreceptor 27 (Y Type)> Exemplified compound (A-1) was used in place of CTM2 in the photosensitive layer of photoreceptor 23, and replaced with Exemplified compound (A-1) in the protective layer. A single-layer photoreceptor 27 was obtained in the same manner as the photoreceptor 23 except that the exemplified compound (CT-17) was used.
【0196】〈感光体28(Z型)の作成〉前記CTM
(CTM4)7部、ポリカーボネート樹脂「パンライト
TS2050」(帝人化成社製)10部、および微量のシリコ
ンオイル「KF-54」(信越化学社製)をジクロルメタ
ン67部に溶解した液を用い、浸漬塗布方法によって塗布
し乾燥の後、膜厚25μmのCTLを形成した。次に前記
CGM(CGM3)10部、前記CTM(CTM3)15
部、ポリカーボネート樹脂「ユーピロンZ200」(粘度
平均分子量20,000)(三菱瓦斯化学社製)20部を1,2-ジ
クロルエタン35部と共にサンドミルを用いて分散した
後、円形スライドホッパーを用いて塗布、乾燥の後、膜
厚5μmのCGLを形成した。更に該CGL上に例示化
合物(A−1)6部とポリカーボネート樹脂「ユーピロ
ンZ800」(粘度平均分子量80,000)(三菱瓦斯化学社
製)10部を1,2-ジクロルエタン100部に溶解し、得られ
た塗布液を円形スライドホッパーを用いて塗布、乾燥の
後、膜厚5μmの表面保護層を形成して、複層構成の感
光体28を得た。<Production of Photoreceptor 28 (Z Type)> CTM
(CTM4) 7 parts, Polycarbonate resin "Panlite TS2050" (manufactured by Teijin Chemicals Co., Ltd.), and a small amount of silicon oil "KF-54" (manufactured by Shin-Etsu Chemical Co., Ltd.) dissolved in 67 parts dichloromethane. After coating by a coating method and drying, a CTL having a film thickness of 25 μm was formed. Next, 10 parts of the CGM (CGM3) and the CTM (CTM3) 15
Parts, 20 parts of polycarbonate resin "Iupilon Z200" (viscosity average molecular weight 20,000) (manufactured by Mitsubishi Gas Chemical Co., Inc.) and 35 parts of 1,2-dichloroethane were dispersed in a sand mill, and then coated using a circular slide hopper and dried. After that, a CGL having a film thickness of 5 μm was formed. Further, 6 parts of Exemplified Compound (A-1) and 10 parts of polycarbonate resin "Iupilon Z800" (viscosity average molecular weight 80,000) (manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 100 parts of 1,2-dichloroethane on the CGL to obtain the compound. The coating solution was applied using a circular slide hopper and dried, and then a surface protective layer having a film thickness of 5 μm was formed to obtain a photoreceptor 28 having a multilayer structure.
【0197】〈感光体29,30及び31(Z型)の作成〉感
光体28の保護層中の例示化合物(A−1)に代えて例示
化合物(C−14),(E−30)及び(H−2)を用いた
他は感光体28と同様にして複層構成の感光体29,30及び
31を得た。<Preparation of Photoreceptors 29, 30 and 31 (Z Type)> Exemplified compounds (C-14), (E-30) and (E-30) in place of the exemplified compound (A-1) in the protective layer of the photoreceptor 28. Photosensitive members 29, 30 having a multi-layer structure in the same manner as the photosensitive member 28 except that (H-2) is used, and
Got 31
【0198】〈比較用感光体32及び32(X型-1)の作
成〉感光体1の保護層中の例示化合物(A−1)に代え
て例示化合物(M−1)及び(M−2)を用いた他は感
光体1と同様にして積層構成の感光体32及び33を得た。<Preparation of Comparative Photoreceptors 32 and 32 (X-Type-1)> Exemplified Compounds (M-1) and (M-2) instead of Exemplified Compound (A-1) in the protective layer of Photoreceptor 1. ) Was used in the same manner as the photoconductor 1 to obtain photoconductors 32 and 33 having a laminated structure.
【0199】〈比較用感光体34及び35(X型-2)の作
成〉感光体7の保護層中の例示化合物(G−1)に代え
て例示化合物(M−1)を用いた他は感光体7と同様に
して積層構成の感光体35を得た。<Preparation of Comparative Photosensitive Members 34 and 35 (X-Type-2)> Except that the exemplified compound (M-1) in the protective layer of the photosensitive member 7 was used in place of the exemplified compound (M-1). A photoconductor 35 having a laminated structure was obtained in the same manner as the photoconductor 7.
【0200】〈比較用感光体36(X型−3)の作成〉感
光体13の保護層中の例示化合物(B−8)に代えて例示
化合物(M−1)を用いた他は感光体13と同様にして積
層構成の感光体36を得た。<Preparation of Comparative Photoreceptor 36 (X-Type-3)> Except that Exemplified Compound (M-1) was used instead of Exemplified Compound (B-8) in the protective layer of Photoreceptor 13 A photoconductor 36 having a laminated structure was obtained in the same manner as 13.
【0201】〈比較用感光体37(Y型)の作成〉感光体
23の保護層中の例示化合物(A−1)に代わって例示化
合物(M−1)を用いた他は感光体23と同様にして単層
構成の感光体37を得た。<Preparation of Comparative Photoreceptor 37 (Y Type)> Photoreceptor
A photoreceptor 37 having a single-layer structure was obtained in the same manner as the photoreceptor 23 except that the exemplified compound (M-1) was used in place of the exemplified compound (A-1) in the protective layer of 23.
【0202】〈比較用感光体38(Y型)の作成〉感光体
25の保護層中の例示化合物(E−30)に代えて例示化合
物(M−2)を用いた他は感光体25と同様にして単層構
成の感光体38を得た。<Preparation of Comparative Photosensitive Member 38 (Y Type)> Photosensitive Member
A photoreceptor 38 having a single layer structure was obtained in the same manner as the photoreceptor 25 except that the exemplified compound (M-2) was used in place of the exemplified compound (E-30) in the protective layer of No. 25.
【0203】〈比較用感光体39及び40(Z型)の作成〉
感光体28の保護層中の例示化合物(A−1)に代えて例
示化合物(M−1)及び(M−2)を用いた他は感光体
28と同様にして積層構成の感光体39及び40を得た。<Preparation of Comparative Photoreceptors 39 and 40 (Z Type)>
Photoreceptor except that Exemplified Compounds (M-1) and (M-2) are used instead of Exemplified Compound (A-1) in the protective layer of Photoreceptor 28.
Photoconductors 39 and 40 having a laminated structure were obtained in the same manner as in 28.
【0204】前記40種類の感光体は以下の表1〜4にま
とめられる。The 40 types of photoconductors are summarized in Tables 1 to 4 below.
【0205】[0205]
【表1】 [Table 1]
【0206】[0206]
【表2】 [Table 2]
【0207】[0207]
【表3】 [Table 3]
【0208】[0208]
【表4】 [Table 4]
【0209】〔画像テスト及び静電特性テスト〕コニカ
(株)社製U−BIX3035を正帯電方式に改造した改造機
に前記40種類の感光体を順次装着して、RH60%,20℃
の雰囲気下で1万回に亘る連続コピーテストを行ない、
初期及び1万回コピー時のかぶり濃度を中心とした画質
評価及び静電特性テストを行なった。ここで前記画像テ
スト及び静電特性テストを行なうには、まずコピー開始
前に複写機の現像器を取外し、代わりに電位測定用プロ
ーブを配置し、複写機を駆動して黒紙電位Vb、白紙電
位Vw及び残留電位Vrを測定する。次に前記プローブに
代えて現像器を装着して1万回に亘り連続して像形成を
行ない、コピー終了後初期と同様現像器の位置に電位測
定用プローブを配置して1万コピー後のVb,Vw及びV
rを測定し、その結果を表5に示した。又初期及び1万
回目コピーの画像のかぶり濃度を濃度計「マクベスRD
918」(イーストマンコダック社製)により測定し、こ
れを下記評価基準により「○」,「×」方式で評価し、
その結果を表5に示した。[Image Test and Electrostatic Property Test] Konica
U-BIX3035 manufactured by Co., Ltd. was modified into a positive charging system, and the above 40 kinds of photoconductors were sequentially mounted on the modified machine. RH 60%, 20 ° C
Performed a continuous copy test over 10,000 times in the atmosphere of
Image quality evaluation and electrostatic characteristic test centering on the fog density at the initial stage and at the time of copying 10,000 times were performed. In order to perform the image test and the electrostatic characteristic test, first, the developing device of the copying machine is removed before the start of copying, a potential measuring probe is arranged instead, and the copying machine is driven to drive the black paper potential V b , The blank sheet potential V w and the residual potential V r are measured. Then, instead of the probe, a developing device was attached and continuous image formation was carried out 10,000 times. After completion of copying, the potential measuring probe was placed at the developing device position in the same manner as in the initial stage. V b , V w and V
The r was measured and the results are shown in Table 5. Also, the fog density of the image of the initial copy and the 10,000th copy is measured by a densitometer "Macbeth RD".
918 "(manufactured by Eastman Kodak Company), and evaluated by the" ○ "and" × "methods according to the following evaluation criteria,
The results are shown in Table 5.
【0210】評価基準: かぶり濃度 0.005未満 ◎ 0.005〜0.008 ○ 0.009〜0.012 △ 0.013以上 × 但し上記かぶり濃度(A)は前記濃度計で測定して得た
測定濃度(B)から白紙反射濃度(C)を差引いた値で
ある。Evaluation criteria: Fogging density less than 0.005 ◎ 0.005 to 0.008 ○ 0.009 to 0.012 △ 0.013 or more × However, the above fog density (A) is obtained by measuring with the densitometer from the measured density (B) to the white paper reflection density (C). ) Is the value subtracted.
【0211】即ち求めるかぶり濃度A=B−Cにより求
められる。That is, the obtained fog density A = BC.
【0212】[0212]
【表5】 [Table 5]
【0213】表5より実施例の感光体はいずれも保護層
を設けたにもかかわらず正帯電時の黒紙電位Vbに対し
て白紙電位Vwが低く高感度であり、かつ特に初期及び
1万回の像形成後共に残留電位が少なく終始かぶりのな
い高画質が安定して得られ、これに対して比較例の感光
体は白紙電位Vwが大きく感度低下が目立ち、特に残留
電位の上昇が著しいためかぶりが多く画質が不鮮明とな
り実用性のないことがわかる。As shown in Table 5, the photoconductors of the examples have high sensitivity because the white paper potential V w is low with respect to the black paper potential V b at the time of positive charging, even though the protective layer is provided. After 10,000 times of image formation, the residual potential is small and the high image quality without fogging is stably obtained from the beginning. On the other hand, the photoconductor of the comparative example has a large blank sheet potential V w , and the decrease in sensitivity is noticeable. It can be seen that there is a lot of fog and the image quality is unclear due to the remarkable rise, which is not practical.
【0214】[0214]
【発明の効果】本発明の感光体によれば、正帯電用の感
光体表面に本発明特有の電子受容性物質を含有する保護
層を設けたことにより、帯電露光の繰り返しによる劣化
及び機械的摩耗による劣化が防止され、しかも高感度特
性を有し、かつ繰り返し像形成の過程で残留電位の上昇
がなく長期に亘りかぶりのない鮮明な画像を安定して得
ることができる等の効果が奏される。According to the photoreceptor of the present invention, a protective layer containing an electron-accepting substance peculiar to the present invention is provided on the surface of the photoreceptor for positive charging, so that deterioration due to repeated charging and exposure and mechanical Deterioration due to abrasion is prevented, high sensitivity characteristics are provided, and there is an effect such that a clear image can be stably obtained without fog over a long period of time without an increase in residual potential during repeated image formation. To be done.
【図面の簡単な説明】[Brief description of drawings]
【図1】本発明に含まれる各種感光体の層構成を表す断
面図。FIG. 1 is a cross-sectional view showing a layer structure of various photoconductors included in the present invention.
1 導電性支持体 2 電荷発生層(CGL) 3 電荷輸送層(CTL) 4 保護層 5 接着層 6 感光層 1 Conductive Support 2 Charge Generation Layer (CGL) 3 Charge Transport Layer (CTL) 4 Protective Layer 5 Adhesive Layer 6 Photosensitive Layer
───────────────────────────────────────────────────── フロントページの続き (72)発明者 廣瀬 尚弘 東京都日野市さくら町1番地コニカ株式会 社内 (72)発明者 大柴 知美 東京都日野市さくら町1番地コニカ株式会 社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Naohiro Hirose, Konica Stock Company, Sakura City, Hino City, Tokyo (72) Inventor Tomomi Oshiba, Konica Stock Company, Sakura City, Hino City, Tokyo
Claims (55)
荷輸送物質を含有する感光層を設け、該感光層上に一般
式〔A〕で表される電子受容性物質を含有する保護層を
設けたことを特徴とする電子写真感光体。 【化1】 〔式中、RAはハロゲン原子,ヒドロキシ基,ニトロ
基,CF3基,COORA′基,OCORA′基,CON
H2基,CONHRA′基,CON(RA′)2基,COR
A′基又は置換基を有してもよいアルキル基,アルコキ
シ基,アリール基,アラルキル基若しくはアルキルアミ
ノ基を表し、RA′は置換基を有してもよいアルキル
基,アリール基又はアラルキル基を表す。l,m及びn
はそれぞれ0又は正の整数を表し、lが0のときmは2
以上の整数を表し、lが1以上の整数のときmは0又は
正の整数を表す。又複数個あるRAで表す基は互いに同
じでも異なってもよい。〕1. A protective layer comprising a photosensitive layer containing a charge generating substance and a P-type charge transporting substance on a conductive support, and the photosensitive layer containing an electron accepting substance represented by the general formula [A]. An electrophotographic photoreceptor having a layer. [Chemical 1] [In the formula, R A is a halogen atom, a hydroxy group, a nitro group, a CF 3 group, a COOR A ′ group, an OCOR A ′ group, a CON
H 2 group, CONHR A ′ group, CON (R A ′) 2 group, COR
A 'group or an optionally substituted alkyl group, an alkoxy group, an aryl group, an aralkyl group or an alkylamino group, R A' is an optionally substituted alkyl group, an aryl group or an aralkyl group Represents l, m and n
Each represent 0 or a positive integer, and when 1 is 0, m is 2
The above integers are represented, and when l is an integer of 1 or more, m represents 0 or a positive integer. The plural groups represented by R A may be the same or different. ]
有する電荷輸送層を設け、該電荷輸送層上に電荷発生物
質を含有する電荷発生層を設け、該電荷発生層上に前記
保護層を設けたことを特徴とする請求項1に記載の電子
写真感光体。2. A charge transporting layer containing a P-type charge transporting substance is provided on a conductive support, a charge generating layer containing a charge generating substance is provided on the charge transporting layer, and the charge generating layer is provided on the charge generating layer. The electrophotographic photosensitive member according to claim 1, further comprising a protective layer.
有する電荷輸送層を設け、該電荷輸送層上に電荷発生物
質とP型又はN型電荷輸送物質を含有する電荷発生層を
設け、該電荷発生層上に前記保護層を設けたことを特徴
とする請求項1に記載の電子写真感光体。3. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member is provided, and the protective layer is provided on the charge generation layer.
荷輸送物質とを共に含有する層から成る感光層を設け、
該感光層上に前記保護層を設けたことを特徴とする請求
項1に記載の電子写真感光体。4. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support,
The electrophotographic photoreceptor according to claim 1, wherein the protective layer is provided on the photosensitive layer.
物質が下記一般式〔a〕で表される化合物であることを
特徴とする請求項1、請求項2、請求項3又は請求項4
のいづれかに記載の電子写真感光体。 【化2】 〔式中、R1A,R2Aはハロゲン原子,シアノ基又は置換
基を有してもよいアルキル基を表し、l及びmは一般式
〔A〕と同義であり、pは0又は正の整数を表す。〕5. The electron-accepting substance represented by the general formula [A] is a compound represented by the following general formula [a], claim 1, claim 2, claim 3 or Claim 4
The electrophotographic photosensitive member according to any one of 1. [Chemical 2] [In the formula, R 1A and R 2A represent a halogen atom, a cyano group or an alkyl group which may have a substituent, l and m have the same meanings as those in the general formula [A], and p is 0 or a positive integer. Represents ]
荷輸送物質を含有する感光層を設け、該感光層上に一般
式〔B〕で表される電子受容性物質を含有する保護層を
設けたことを特徴とする電子写真感光体。 【化3】 〔式中、YBはシアノ基又はCF3基を表し、RBはハロ
ゲン原子,ヒドロキシ基,ニトロ基,CF3基,COO
RB′基,OCORB′基,CONH2基,CONHRB′
基,CON(RB′)2基,CORB′基又は置換基を有
してもよいアルキル基,アルコキシ基,アリール基,ア
ラルキル基若しくはアルキルアミノ基を表し、RB′は
置換基を有してもよいアルキル基,アリール基又はアラ
ルキル基を表す。l,m及びnはそれぞれ1以上の整数
を表す。又複数個有るYB,RBの各基はそれぞれ同じ基
から成ってもよく、異なる基から成ってもよい。〕6. A protective layer comprising a photosensitive layer containing a charge generating substance and a P-type charge transporting substance on a conductive support, and the photosensitive layer containing an electron-accepting substance represented by the general formula [B]. An electrophotographic photoreceptor having a layer. [Chemical 3] [In the formula, Y B represents a cyano group or a CF 3 group, and R B represents a halogen atom, a hydroxy group, a nitro group, a CF 3 group, COO.
R B ′ group, OCOR B ′ group, CONH 2 group, CONHR B ′
Group, CON (R B ′) 2 group, COR B ′ group or an optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group or alkylamino group, and R B ′ has a substituent group. Represents an alkyl group, an aryl group or an aralkyl group which may be present. l, m and n each represent an integer of 1 or more. The plural groups of Y B and R B may be the same or different. ]
有する電荷輸送層を設け、該電荷輸送層上に電荷発生物
質を含有する電荷発生層を設け、該電荷発生層上に前記
保護層を設けたことを特徴とする請求項6に記載の電子
写真感光体。7. A charge transporting layer containing a P-type charge transporting substance is provided on a conductive support, a charge generating layer containing a charge generating substance is provided on the charge transporting layer, and the charge generating layer is provided on the charge generating layer. The electrophotographic photosensitive member according to claim 6, wherein a protective layer is provided.
有する電荷輸送層を設け、該電荷輸送層上に電荷発生物
質とP型又はN型電荷輸送物質を含有する電荷発生層を
設け、該電荷発生層上に前記保護層を設けたことを特徴
とする請求項6に記載の電子写真感光体。8. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. The electrophotographic photosensitive member according to claim 6, wherein the electrophotographic photosensitive member is provided, and the protective layer is provided on the charge generation layer.
荷輸送物質とを共に含有する層から成る感光層を設け、
該感光層上に前記保護層を設けたことを特徴とする請求
項1に記載の電子写真感光体。9. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support,
The electrophotographic photoreceptor according to claim 1, wherein the protective layer is provided on the photosensitive layer.
性物質が下記一般式〔b〕で表される化合物であること
を特徴とする請求項6、請求項7、請求項8又は請求項
9のいづれかに記載の電子写真感光体。 【化4】 〔式中R1B,R2Bはハロゲン原子,シアノ基又は置換基
を有してもよいアルキル基を表し、l及びmは一般式
〔B〕と同義であり、pは0又は正の整数を表す。〕10. The electron accepting substance represented by the general formula [B] is a compound represented by the following general formula [b], claim 6, claim 7, claim 8 or The electrophotographic photosensitive member according to claim 9. [Chemical 4] [Wherein R 1B and R 2B represent a halogen atom, a cyano group or an alkyl group which may have a substituent, l and m have the same meanings as those in the general formula [B], and p represents 0 or a positive integer. Represent ]
電荷輸送物質を含有する感光層を設け、該感光層上に一
般式〔C〕で表される電子受容性物質を含有する保護層
を設けたことを特徴とする電子写真感光体。 【化5】 〔式中、XCはCOORC′基,OCORC′基,CON
H2基,CONHRC′基,CON(RC′)2基,COR
C′基又はCHO基を表し、YCはハロゲン原子,シアノ
基,ニトロ基,CF3基,COOH基,SO2NH2基,
SO2RC′基又はSORC′基を表し、RCはハロゲン原
子,ヒドロキシ基,ニトロ基,CF3基,COORC′
基,OCORC′基,CONH2基,CONHRC′基,
CON(RC′)2基,CORC′基又は置換基を有して
もよいアルキル基,アルコキシ基,アリール基,アラル
キル基若しくはアルキルアミノ基を表し、RC′は置換
基を有してもよいアルキル基,アリール基又はアラルキ
ル基を表す。l及びnは1以上の整数を表し、mは0又
は正の整数を表し、l+mは2以上の整数を表す。又複
数個あるXC,YC,RCの各基はそれぞれ同じ基から成
ってもよく、異なる基から成ってもよい。〕11. A protective layer containing a charge generating substance and a P-type charge transporting substance on a conductive support, and the photosensitive layer containing an electron accepting substance represented by the general formula [C]. An electrophotographic photoreceptor having a layer. [Chemical 5] [Wherein X C is a COOR C ′ group, an OCOR C ′ group, a CON
H 2 group, CONHR C ′ group, CON (R C ′) 2 group, COR
Represents a C ′ group or a CHO group, and Y C represents a halogen atom, a cyano group, a nitro group, a CF 3 group, a COOH group, a SO 2 NH 2 group,
Represents a SO 2 R C ′ group or a SOR C ′ group, wherein R C is a halogen atom, a hydroxy group, a nitro group, a CF 3 group, a COOR C ′
Group, OCOR C ′ group, CONH 2 group, CONHR C ′ group,
A CON (R C ′) 2 group, a COR C ′ group or an optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group or alkylamino group, wherein R C ′ has a substituent Represents an alkyl group, an aryl group or an aralkyl group. l and n represent an integer of 1 or more, m represents 0 or a positive integer, and l + m represents an integer of 2 or more. The plural groups of X C , Y C and R C may be the same or different. ]
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質を含有する電荷発生層を設け、該電荷発生層上に前
記保護層を設けたことを特徴とする請求項11に記載の電
子写真感光体。12. A charge transporting layer containing a P-type charge transporting substance is provided on a conductive support, a charge generating layer containing a charge generating substance is provided on the charge transporting layer, and the charge generating layer is provided on the charge generating layer. 12. The electrophotographic photosensitive member according to claim 11, which is provided with a protective layer.
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質とP型又はN型電荷輸送物質を含有する電荷発生層
を設け、該電荷発生層上に前記保護層を設けたことを特
徴とする請求項11に記載の電子写真感光体。13. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 12. The electrophotographic photosensitive member according to claim 11, wherein the electrophotographic photosensitive member is provided, and the protective layer is provided on the charge generation layer.
電荷輸送物質とを共に含有する層から成る感光層を設
け、該感光層上に前記保護層を設けたことを特徴とする
請求項11に記載の電子写真感光体。14. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 11. The electrophotographic photosensitive member according to item 11.
性物質が下記一般式〔c〕で表される化合物であること
を特徴とする請求項11、請求項12、請求項13又は請求項
14のいづれかに記載の電子写真感光体。 【化6】 〔式中、XC及びYCは一般式〔C〕と同義であり、
R1C,R2Cはハロゲン原子,シアノ基又は置換基を有し
てもよいアルキル基を表す。l及びmは一般式〔C〕と
同義であり、pは0又は正の整数を表す。〕15. The electron accepting substance represented by the general formula [C] is a compound represented by the following general formula [c], 11, 12, 13 or Claim
The electrophotographic photosensitive member according to any one of 14. [Chemical 6] [In the formula, X C and Y C have the same meanings as those in the general formula [C],
R 1C and R 2C represent a halogen atom, a cyano group or an alkyl group which may have a substituent. l and m have the same meaning as in the general formula [C], and p represents 0 or a positive integer. ]
電荷輸送物質を含有する感光層を設け、該感光層上に一
般式〔D〕で表される電子受容性物質を含有する保護層
を設けたことを特徴とする電子写真感光体。 【化7】 〔式中、XDはCOOH基,SO2NH2基,SORD′基
又はSO2RD′基を表し、YDはハロゲン原子,シアノ
基,ニトロ基又はCF3基を表し、RDはハロゲン原子,
ヒドロキシ基,ニトロ基,CF3基,COORD′基、O
CORD′基,CONH2基,CONHRD′基,CON
(RD′)2基,CORD′基又は置換基を有してもよい
アルキル基,アルコキシ基,アリール基,アラルキル基
若しくはアルキルアミノ基を表し、RD′は置換基を有
してもよいアルキル基,アリール基又はアラルキル基を
表す。l及びnは1以上の整数を表し、mは0又は正の
整数を表し、l+mは2以上の整数を表す。又複数個あ
るXD,YD,RDの各基はそれぞれ同じ基から成っても
よく、異なる基から成ってもよい。〕16. A protective layer comprising, on a conductive support, a photosensitive layer containing a charge generating substance and a P-type charge transporting substance, and the photosensitive layer containing an electron accepting substance represented by the general formula [D]. An electrophotographic photoreceptor having a layer. [Chemical 7] [In the formula, X D represents a COOH group, SO 2 NH 2 group, SOR D ′ group or SO 2 R D ′ group, Y D represents a halogen atom, a cyano group, a nitro group or a CF 3 group, and R D Is a halogen atom,
Hydroxy group, nitro group, CF 3 group, COOR D ′ group, O
COR D ′ group, CONH 2 group, CONHR D ′ group, CON
(R D ′) 2 group, COR D ′ group or an optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group or alkylamino group, wherein R D ′ may have a substituent Represents a good alkyl group, aryl group or aralkyl group. l and n represent an integer of 1 or more, m represents 0 or a positive integer, and l + m represents an integer of 2 or more. The plural groups of X D , Y D and R D may be the same or different. ]
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質を含有する電荷発生層を設け、該電荷発生層上に前
記保護層を設けたことを特徴とする請求項16に記載の電
子写真感光体。17. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, a charge-generating layer containing a charge-generating substance is provided on the charge-transporting layer, and the charge-generating layer is provided on the charge-generating layer. 17. The electrophotographic photosensitive member according to claim 16, further comprising a protective layer.
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質とP型又はN型電荷輸送物質を含有する電荷発生層
を設け、該電荷発生層上に前記保護層を設けたことを特
徴とする請求項16に記載の電子写真感光体。18. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 17. The electrophotographic photosensitive member according to claim 16, wherein the electrophotographic photosensitive member is provided, and the protective layer is provided on the charge generation layer.
電荷輸送物質とを共に含有する層から成る感光層を設
け、該感光層上に前記保護層を設けたことを特徴とする
請求項16に記載の電子写真感光体。19. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 16. The electrophotographic photosensitive member according to item 16.
性物質が下記一般式〔d〕で表される化合物であること
を特徴とする請求項16、請求項17、請求項18又は請求項
19のいづれかに記載の電子写真感光体。 【化8】 〔式中、XD及びYDは一般式〔D〕と同義であり、
R1D,R2Dの各基はハロゲン原子,シアノ基又は置換基
を有してもよいアルキル基を表し、l及びmは一般式
〔D〕と同義であり、pは0又は正の整数を表す。〕20. The electron accepting substance represented by the general formula [D] is a compound represented by the following general formula [d], 16, 17, 18 or Claim
The electrophotographic photosensitive member according to any one of 19. [Chemical 8] [In the formula, X D and Y D have the same meanings as those in the general formula [D],
Each group of R 1D and R 2D represents a halogen atom, a cyano group or an alkyl group which may have a substituent, l and m have the same meaning as in the general formula [D], and p is 0 or a positive integer. Represent ]
電荷輸送物質を含有する感光層を設け、該感光層上に一
般式〔E〕で表される電子受容性物質を含有する保護層
を設けたことを特徴とする電子写真感光体。 【化9】 〔式中、XEはハロゲン原子を表し、YEはシアノ基,ニ
トロ基又はCF3基を表し、REはハロゲン原子,ヒドロ
キシ基,ニトロ基,CF3基,COORE′基,OCOR
E′基,CONH2基,CONHRE′基,CON
(RE′)2基,CORE′基又は置換基を有してもよい
アルキル基,アルコキシ基,アリール基,アラルキル基
若しくはアルキルアミノ基を表し、RE′は置換基を有
してもよいアルキル基,アリール基又はアラルキル基を
表す。l及びnは1以上の整数を表し、mは0又は正の
整数を表し、l+mは2以上の整数を表す。又複数個あ
るXE,YE,REの各基はそれぞれ同じ基から成っても
よく、異なる基から成ってもよい。〕21. A photosensitive layer containing a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer containing an electron accepting substance represented by the general formula [E] is provided on the photosensitive layer. An electrophotographic photoreceptor having a layer. [Chemical 9] [Wherein X E represents a halogen atom, Y E represents a cyano group, a nitro group or a CF 3 group, and R E represents a halogen atom, a hydroxy group, a nitro group, a CF 3 group, a COOR E ′ group, OCOR
E 'group, CONH 2 groups, CONHR E' group, CON
(R E ′) 2 group, COR E ′ group or an optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group or alkylamino group, wherein R E ′ may have a substituent Represents a good alkyl group, aryl group or aralkyl group. l and n represent an integer of 1 or more, m represents 0 or a positive integer, and l + m represents an integer of 2 or more. The plural groups of X E , Y E and R E may be the same or different. ]
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質を含有する電荷発生層を設け、該電荷発生層上に前
記保護層を設けたことを特徴とする請求項21に記載の電
子写真感光体。22. A charge transporting layer containing a P-type charge transporting substance is provided on a conductive support, a charge generating layer containing a charge generating substance is provided on the charge transporting layer, and the charge generating layer is provided on the charge generating layer. 22. The electrophotographic photosensitive member according to claim 21, further comprising a protective layer.
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質とP型又はN型電荷輸送物質を含有する電荷発生層
を設け、該電荷発生層上に前記保護層を設けたことを特
徴とする請求項22に記載の電子写真感光体。23. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 23. The electrophotographic photosensitive member according to claim 22, wherein the electrophotographic photosensitive member is provided, and the protective layer is provided on the charge generation layer.
電荷輸送物質とを共に含有する層から成る感光層を設
け、該感光層上に前記保護層を設けたことを特徴とする
請求項23に記載の電子写真感光体。24. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 23. The electrophotographic photoconductor of Item 23.
性物質が下記一般式〔e〕で表される化合物であること
を特徴とする請求項21、請求項22、請求項23又は請求項
24のいづれかに記載の電子写真感光体。 【化10】 〔式中、XE及びYEは一般式〔E〕と同義であり、
R1E,R2Eはハロゲン原子,シアノ基又は置換基を有し
てもよいアルキル基を表し、l及びmは一般式〔E〕と
同義であり、pは0又は正の整数を表す。〕25. The electron-accepting substance represented by the general formula [E] is a compound represented by the following general formula [e], 21, 21, 23, or Claim
The electrophotographic photosensitive member according to any one of 24. [Chemical 10] [In the formula, X E and Y E have the same meanings as those in the general formula [E],
R 1E and R 2E represent a halogen atom, a cyano group or an alkyl group which may have a substituent, l and m have the same meanings as in the general formula [E], and p represents 0 or a positive integer. ]
電荷輸送物質を含有する感光層を設け、該感光層上に一
般式〔F〕で表される電子受容性物質を含有する保護層
を設けたことを特徴とする電子写真感光体。 【化11】 〔式中、XFはハロゲン原子,シアノ基,ニトロ基,C
F3基,COOH基,COORF′基,OCORF′基,
CONH2基,CONHRF′基,CON(RF′)2基,
CORF′基,SO2NH2基,SORF′基,SO2RF′
基又はCHO基を表し、YFは置換基を有してもよいア
ルキル基,アリール基又はアラルキル基を表し、RFは
ハロゲン原子,ヒドロキシ基,ニトロ基,CF3基,C
OORF′基,OCORF′基,CONH2基,CONH
RF′基,CON(RF′)2基,CORF′基又は置換基
を有してもよいアルキル基,アルコキシ基,アリール
基,アラルキル基若しくはアルキルアミノ基を表し、R
F′は置換基を有してもよいアルキル基,アリール基又
はアラルキル基を表す。又複数個あるXF,YF,RFの
各基はそれぞれ同じ基から成ってもよく、異なる基から
成ってもよい。〕26. A photosensitive layer containing a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer containing an electron accepting substance represented by the general formula [F] is provided on the photosensitive layer. An electrophotographic photoreceptor having a layer. [Chemical 11] [In the formula, X F is a halogen atom, a cyano group, a nitro group, C
F 3 group, COOH group, COOR F ′ group, OCOR F ′ group,
CONH 2 group, CONHR F ′ group, CON (R F ′) 2 group,
COR F ′ group, SO 2 NH 2 group, SOR F ′ group, SO 2 R F ′
Group or CHO group, Y F represents an alkyl group which may have a substituent, an aryl group or an aralkyl group, and R F represents a halogen atom, a hydroxy group, a nitro group, a CF 3 group, C
OOR F 'group, OCOR F' group, CONH 2 groups, CONH
Represents an R F ′ group, a CON (R F ′) 2 group, a COR F ′ group or an optionally substituted alkyl group, an alkoxy group, an aryl group, an aralkyl group or an alkylamino group, and R
F'represents an alkyl group, an aryl group or an aralkyl group which may have a substituent. The plural groups of X F , Y F and R F may be the same or different. ]
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質を含有する電荷発生層を設け、該電荷発生層上に前
記保護層を設けたことを特徴とする請求項26に記載の電
子写真感光体。27. A charge transporting layer containing a P-type charge transporting substance is provided on a conductive support, a charge generating layer containing a charge generating substance is provided on the charge transporting layer, and the charge generating layer is provided on the charge generating layer. 27. The electrophotographic photosensitive member according to claim 26, which is provided with a protective layer.
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質とP型又はN型電荷輸送物質を含有する電荷発生層
を設け、該電荷発生層上に前記保護層を設けたことを特
徴とする請求項26に記載の電子写真感光体。28. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 27. The electrophotographic photosensitive member according to claim 26, wherein the protective layer is provided on the charge generation layer.
電荷輸送物質とを共に含有する層から成る感光層を設
け、該感光層上に前記保護層を設けたことを特徴とする
請求項26に記載の電子写真感光体。29. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 26. The electrophotographic photoreceptor according to Item 26.
性物質が下記一般式〔f〕で表される化合物であること
を特徴とする請求項26、請求項27、請求項28又は請求項
29のいづれかに記載の電子写真感光体。 【化12】 〔式中、XF及びYFは一般式〔F〕と同義であり、
R1F、R2Fの各基はハロゲン原子,シアノ基又は置換基
を有してもよいアルキル基を表し、l及びmは一般式
〔F〕と同義であり、pは0又は正の整数を表す。〕30. The electron accepting substance represented by the general formula [F] is a compound represented by the following general formula [f], 26, 27, 28 or Claim
The electrophotographic photosensitive member according to any one of 29. [Chemical 12] [In the formula, X F and Y F have the same meanings as those in the general formula [F],
Each group of R 1F and R 2F represents a halogen atom, a cyano group or an alkyl group which may have a substituent, l and m have the same meaning as in the general formula [F], and p is 0 or a positive integer. Represent ]
電荷輸送物質を含有する感光層を設け、該感光層上に一
般式〔G〕で表される電子受容性物質を含有する保護層
を設けたことを特徴とする電子写真感光体。 【化13】 〔式中、Y1Gは置換基を有してもよいアルキル基を表
し、R2Gはハロゲン原子,ヒドロキシ基,シアノ基,ニ
トロ基,N(RG′)2基,ORG′基,COORG′基,
OCORG′基,CORG′基,CONHRG′基,CO
N(RG′)2基,SORG′基,SO2RG′基又は置換
基を有してもよいアリール基若しくはアラルキル基を表
し、RG′は置換基を有してもよいアルキル基,アリー
ル基又はアラルキル基を表す。lは0又は正の整数を表
し、mは2以上の整数を表し、nは1以上の整数を表
す。又複数個あるY1G,R2Gの各基はそれぞれ同じ基か
ら成ってもよく、異なる基から成ってもよい。〕31. A photosensitive layer containing a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the photosensitive layer is protected by containing an electron accepting substance represented by the general formula [G]. An electrophotographic photoreceptor having a layer. [Chemical 13] [In the formula, Y 1G represents an alkyl group which may have a substituent, R 2G represents a halogen atom, a hydroxy group, a cyano group, a nitro group, an N (R G ′) 2 group, an OR G ′ group, COOR G'group ,
OCOR G ′ group, COR G ′ group, CONHR G ′ group, CO
N (R G ′) 2 group, SOR G ′ group, SO 2 R G ′ group or an optionally substituted aryl group or aralkyl group, and R G ′ is an optionally substituted alkyl group Represents a group, an aryl group or an aralkyl group. l represents 0 or a positive integer, m represents an integer of 2 or more, and n represents an integer of 1 or more. The plurality of Y 1G and R 2G groups may be the same or different. ]
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質を含有する電荷発生層を設け、該電荷発生層上に前
記保護層を設けたことを特徴とする請求項31に記載の電
子写真感光体。32. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, a charge-generating layer containing a charge-generating substance is provided on the charge-transporting layer, and the charge-generating layer is formed on the charge-generating layer. 32. The electrophotographic photosensitive member according to claim 31, which is provided with a protective layer.
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質とP型又はN型電荷輸送物質を含有する電荷発生層
を設け、該電荷発生層上に前記保護層を設けたことを特
徴とする請求項32に記載の電子写真感光体。33. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 33. The electrophotographic photosensitive member according to claim 32, wherein the protective layer is provided on the charge generation layer.
電荷輸送物質とを共に含有する層から成る感光層を設
け、該感光層上に前記保護層を設けたことを特徴とする
請求項33に記載の電子写真感光体。34. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 33. The electrophotographic photoconductor of Item 33.
性物質が下記一般式〔g〕で表される化合物であること
を特徴とする請求項31、請求項32、請求項33又は請求項
34のいづれかに記載の電子写真感光体。 【化14】 〔式中、Y1Gは一般式〔G〕と同義であり、R′2Gはハ
ロゲン原子,シアノ基,ニトロ基,COORG′基,O
CORG′基,CORG′基又はCONHRG′基を表
す。又l′は0を表し、m′は3以上の整数を表し、n
及びRG′は一般式〔G〕と同義である。〕35. The electron-accepting substance represented by the general formula [G] is a compound represented by the following general formula [g], 31, 32, 33 or Claim
The electrophotographic photosensitive member according to any one of 34. [Chemical 14] [Wherein Y 1G has the same meaning as in the general formula [G], and R ′ 2G represents a halogen atom, a cyano group, a nitro group, a COOR G ′ group, O
Represents a COR G ′ group, a COR G ′ group or a CONHR G ′ group. L'represents 0, m'represents an integer of 3 or more, n
And R G ′ have the same meaning as in general formula [G]. ]
電荷輸送物質を含有する感光層を設け、該感光層上に一
般式〔H〕で表される電子受容性物質を含有する保護層
を設けたことを特徴とする電子写真感光体。 【化15】 〔式中、XHはヒドロキシ基,ORH′基,N(RH′)2
基又は置換基を有してもよいアルキル基,アリール基若
しくはアラルキル基を表し、YHはハロゲン原子,シア
ノ基,ニトロ基,CF3基,CORH′基,COORH′
基,OCORH′基,CONHRH′基,CON
(RH′)2基,SORH′基又はSO2RH′基を表し、
RHは置換基を有してもよいアルキル基又はアラルキル
基を表し、RH′は置換基を有してもよいアルキル基又
はアリール基を表す。lは0又は正の整数を表し、mは
2以上の整数を表し、l+mは2から8の整数を表す。
又複数個あるXH,YH,RH′の各基はそれぞれ同じ基
から成ってもよく、異なる基から成ってもよい。又前記
一般式〔H〕における置換基がアルキル基であるか、又
はアルキル基を含む時、特に規定のない限り、アルキル
基は直鎖状、分岐鎖状又は環状の置換されていても、不
飽和結合を含んでいても良いアルキル基(たとえば、メ
チルエチル基,iso−プロピル基,t−ブチル基,ペ
ンチル基,2−エチルヘキシル基,ドデシル基,アリル
基,オレイル基,ベンジル基,ヒドロキシエチル基,メ
トキシエチル基,フェノキシエチル基)を意味する。又
前記一般式〔H〕における置換基がアリール基である
か、又はアリール基を含む時、特に規定のない限り、ア
リール基は置換されていてもよく単環若しくは縮合環の
アリール基(たとえば、フェニル基,1−ナフチル基,
p−トリル基,p−クロロフェニル基,4−メトキシフ
ェニル基,ペンタフルオロフェニル基,p−ヒドロキシ
フェニル基,p−シアノフェニル基,p−メタンスルホ
ンアミドフェニル基,3,4−ジクロロフェニル基)を
意味する。〕36. A photosensitive layer containing a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer containing an electron accepting substance represented by the general formula [H] is provided on the photosensitive layer. An electrophotographic photoreceptor having a layer. [Chemical 15] [Wherein, X H is a hydroxy group, OR H ′ group, N (R H ′) 2
Represents a group or an alkyl group which may have a substituent, an aryl group or an aralkyl group, and Y H represents a halogen atom, a cyano group, a nitro group, a CF 3 group, a COR H ′ group, a COOR H ′.
Group, OCOR H ′ group, CONHR H ′ group, CON
Represents a (R H ′) 2 group, a SOR H ′ group or a SO 2 R H ′ group,
R H represents an alkyl group or an aralkyl group which may have a substituent, and R H ′ represents an alkyl group or an aryl group which may have a substituent. l represents 0 or a positive integer, m represents an integer of 2 or more, and l + m represents an integer of 2 to 8.
The plural groups of X H , Y H and R H ′ may be the same or different. Further, when the substituent in the general formula [H] is an alkyl group or contains an alkyl group, unless otherwise specified, the alkyl group may be linear, branched or cyclic and may be substituted. An alkyl group which may contain a saturated bond (eg, methylethyl group, iso-propyl group, t-butyl group, pentyl group, 2-ethylhexyl group, dodecyl group, allyl group, oleyl group, benzyl group, hydroxyethyl group). , Methoxyethyl group, phenoxyethyl group). When the substituent in the general formula [H] is an aryl group or includes an aryl group, the aryl group may be substituted unless otherwise specified, and may be a monocyclic or condensed ring aryl group (for example, Phenyl group, 1-naphthyl group,
p-tolyl group, p-chlorophenyl group, 4-methoxyphenyl group, pentafluorophenyl group, p-hydroxyphenyl group, p-cyanophenyl group, p-methanesulfonamidophenyl group, 3,4-dichlorophenyl group) To do. ]
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質を含有する電荷発生層を設け、該電荷発生層上に前
記保護層を設けたことを特徴とする請求項36に記載の電
子写真感光体。37. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, a charge-generating layer containing a charge-generating substance is provided on the charge-transporting layer, and the charge-generating layer is provided on the charge-generating layer. 37. The electrophotographic photosensitive member according to claim 36, which is provided with a protective layer.
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質とP型又はN型電荷輸送物質を含有する電荷発生層
を設け、該電荷発生層上に前記保護層を設けたことを特
徴とする請求項36に記載の電子写真感光体。38. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 37. The electrophotographic photosensitive member according to claim 36, wherein the protective layer is provided on the charge generation layer.
電荷輸送物質とを共に含有する層から成る感光層を設
け、該感光層上に前記保護層を設けたことを特徴とする
請求項36に記載の電子写真感光体。39. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 36. The electrophotographic photoconductor of Item 36.
性物質が下記一般式〔h〕で表される化合物であること
を特徴とする請求項36、請求項37、請求項38又は請求項
39のいづれかに記載の電子写真感光体。 【化16】 〔式中、X′Hは炭素原子数5以下の低級アルキル基を
表し、Y′Hはシアノ基,CF3基,COR′H′基又は
COOR′H′基を表し、R′H基及びR′H′基は炭素
原子数5以上のアルキル基を表す。またm′は、3から
5の整数を表し、lは一般式〔H〕と同義である。〕40. The electron-accepting substance represented by the general formula [H] is a compound represented by the following general formula [h], 36, 37, 38 or Claim
The electrophotographic photosensitive member according to any one of 39. [Chemical 16] Wherein, X 'H denotes the following lower alkyl group 5 carbon atoms, Y' H represents a cyano group, CF 3 group, COR 'H' group or COOR 'H' group, R 'H groups and R 'H' group represents a 5 or greater alkyl group carbon atoms. Further, m ′ represents an integer of 3 to 5, and l has the same meaning as in the general formula [H]. ]
電荷輸送物質を含有する感光層を設け、該感光層上に一
般式〔J〕で表される電子受容性物質を含有する保護層
を設けたことを特徴とする電子写真感光体。 【化17】 〔式中、XJはヒドロキシ基、ORJ′基,N(RJ′)2
基又は置換基を有してもよいアルキル基,アリール基若
しくはアラルキル基を表し、YJ,RFはハロゲン原子,
シアノ基,ニトロ基,CF3基,COORJ′基,OCO
RJ′基,CONHRJ′基,SORJ′基又はSO
2RJ′基を表し、RJ′は置換基を有してもよいアルキ
ル基,アリール基又はアラルキル基を表し、Aは縮合多
環式芳香族炭素環を形成するに必要な原子群を表す。
l,m及びnは0又は正の整数を表し、n+mは2以上
の整数を表し、l+mは2から8の整数を表す。又複数
個あるXJ,YJ,RFの各基はそれぞれ同じ基から成っ
てもよく、異なる基から成ってもよい。又前記一般式
〔J〕における置換基がアルキル基であるか、又はアル
キル基を含む時、特に規定のない限り、アルキル基は直
鎖状、分岐鎖状又は架橋されていてもよい脂環式環であ
り、置換されていても不飽和結合を含んでいてもよいア
ルキル基(たとえば、メチル基,エチル基,iso−プ
ロピル基,t−ブチル基,ペンチル基,2−エチルヘキ
シル基,ドデシル基,アリル基,オレイル基,ベンジル
基,ヒドロキシエチル基,メトキシエチル基,フェノキ
シエチル基,シクロペンチル基,シクロヘキシル基,ノ
ルボルニル基)を意味する。又前記一般式〔J〕におけ
る置換基がアリール基であるか、又はアリール基を含む
時、特に規定のない限り、アリール基は置換されていて
も良く単環若しくは縮合環のアリール基(たとえば、フ
ェニル基,1−ナフチル基,p−トリル基,p−クロロ
フェニル基,4−メトキシフェニル基,ペンタフルオロ
フェニル基,p−ヒドロキシフェニル基,p−シアノフ
ェニル基,p−メタンスルホンアミドフェニル基,3,
4−ジクロロフェニル基)を意味する。〕41. A protective layer comprising, on a conductive support, a photosensitive layer containing a charge generating substance and a P-type charge transporting substance, and the photosensitive layer containing an electron accepting substance represented by the general formula [J]. An electrophotographic photoreceptor having a layer. [Chemical 17] [Wherein, X J is a hydroxy group, OR J ′ group, N (R J ′) 2
A group or an alkyl group which may have a substituent, an aryl group or an aralkyl group, wherein Y J and R F are halogen atoms,
Cyano group, nitro group, CF 3 group, COOR J ′ group, OCO
R J ′ group, CONHR J ′ group, SOR J ′ group or SO
2 represents an R J ′ group, R J ′ represents an optionally substituted alkyl group, an aryl group or an aralkyl group, and A represents an atomic group necessary for forming a condensed polycyclic aromatic carbocycle. Represent
l, m and n represent 0 or a positive integer, n + m represents an integer of 2 or more, and l + m represents an integer of 2 to 8. The plural groups of X J , Y J and R F may be the same or different. When the substituent in the general formula [J] is an alkyl group or contains an alkyl group, the alkyl group may be linear, branched or cross-linked alicyclic unless otherwise specified. An alkyl group which is a ring and may be substituted or may contain an unsaturated bond (eg, methyl group, ethyl group, iso-propyl group, t-butyl group, pentyl group, 2-ethylhexyl group, dodecyl group, Allyl group, oleyl group, benzyl group, hydroxyethyl group, methoxyethyl group, phenoxyethyl group, cyclopentyl group, cyclohexyl group, norbornyl group). When the substituent in the general formula [J] is an aryl group or contains an aryl group, the aryl group may be substituted unless otherwise specified, and a monocyclic or condensed ring aryl group (for example, Phenyl group, 1-naphthyl group, p-tolyl group, p-chlorophenyl group, 4-methoxyphenyl group, pentafluorophenyl group, p-hydroxyphenyl group, p-cyanophenyl group, p-methanesulfonamidophenyl group, 3 ,
4-dichlorophenyl group) is meant. ]
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質を含有する電荷発生層を設け、該電荷発生層上に前
記保護層を設けたことを特徴とする請求項41に記載の電
子写真感光体。42. A charge transporting layer containing a P-type charge transporting substance is provided on a conductive support, a charge generating layer containing a charge generating substance is provided on the charge transporting layer, and the charge generating layer is provided on the charge generating layer. 42. The electrophotographic photosensitive member according to claim 41, which is provided with a protective layer.
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質とP型又はN型電荷輸送物質を含有する電荷発生層
を設け、該電荷発生層上に前記保護層を設けたことを特
徴とする請求項42に記載の電子写真感光体。43. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 43. The electrophotographic photosensitive member according to claim 42, wherein the electrophotographic photosensitive member is provided, and the protective layer is provided on the charge generation layer.
電荷輸送物質とを共に含有する層から成る感光層を設
け、該感光層上に前記保護層を設けたことを特徴とする
請求項43に記載の電子写真感光体。44. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 43. The electrophotographic photosensitive member according to Item 43.
性物質が下記一般式〔j〕で表される化合物であること
を特徴とする請求項41、請求項42、請求項43又は請求
項44のいづれかに記載の電子写真感光体。 【化18】 〔式中、X′Jは炭素原子数5以下の低級アルキル基を
表し、Y′J,R′Jの各基はシアノ基,CF3基,CO
R′J′基又はCOOR′J′基を表し、R′J′は炭素
原子数5以上のアルキル基を表し、A′はナフタレン,
アントラセン,フェナンスレン又はピレン環を形成する
に必要な炭化水素原子群を表す。l′及びn′は0又は
正の整数を表し、m′は3から5の整数を表す。〕45. The electron-accepting substance represented by the general formula [J] is a compound represented by the following general formula [j], 41, 42, 43 or The electrophotographic photosensitive member according to claim 44. [Chemical 18] Wherein, X 'J represents a lower alkyl group having not more than 5 carbon atoms, Y' J, each group R 'J represents a cyano group, CF 3 group, CO
Represents R 'J' group or COOR 'J' group, R 'J' represents an 5 or greater alkyl group carbon atoms, A 'is a naphthalene,
It represents a hydrocarbon atom group necessary for forming an anthracene, phenanthrene or pyrene ring. l'and n'represent 0 or a positive integer, and m'represent an integer of 3 to 5. ]
電荷輸送物質を含有する感光層を設け、該感光層上に一
般式〔K〕で表される電子受容性物質を含有する保護層
を設けたことを特徴とする電子写真感光体。 【化19】 〔式中、XKはヒドロキシ基,ORK′基,N(RK′)2
基又は置換基を有してもよいアルキル基,アリール基若
しくはアラルキル基を表し、YK,RKはハロゲン原子,
シアノ基,ニトロ基,CF3基,CORK′基,COOR
K′基,OCORK′基,CONHRK′基,SORK′基
又はSO2RK′基を表し、RK′は置換基を有してもよ
いアルキル基,アリール基又はアラルキル基を表し、B
はベンゼン環の炭素原子とともに脂肪族環を形成するに
必要な炭化水素原子群を表す。l,m及びnは0又は正
の整数を表し、n+mは2以上の整数を表し、l+mは
2から8の整数を表す。又複数個あるRK,YK,RKの
各基はそれぞれ同じ基から成ってもよく、異なる基から
成ってもよい。又前記一般式〔K〕における置換基がア
ルキル基であるか、又はアルキル基を含む時、特に規定
のない限り、アルキル基は直鎖状、分岐鎖状又は架橋さ
れていてもよい脂環式環であり、置換されていても不飽
和結合を含んでいてもよいアルキル基(たとえば、メチ
ル基,エチル基,iso−プロピル基,t−ブチル基,
ペンチル基,2−エチルヘキシル基,ドデシル基,アリ
ル基,オレイル基,ベンジル基,ヒドロキシエチル基,
メトキシエチル基,フェノキシエチル基,シクロペンチ
ル基,シクロヘキシル基,ノルボルニル基)を意味す
る。又前記一般式〔K〕における置換基がアリール基で
あるか、又はアリール基を含む時、特に規定のない限
り、アリール基は置換されていてもよく単環若しくは縮
合環のアリール基(たとえば、フェニル基,1−ナフチ
ル基,p−トリル基,p−クロロフェニル基,4−メト
キシフェニル基,ペンタフルオロフェニル基,p−ヒド
ロキシフェニル基,p−シアノフェニル基,p−メタン
スルホンアミドフェニル基,3,4−ジクロロフェニル
基)を意味する。〕46. A protective layer comprising, on a conductive support, a photosensitive layer containing a charge generating substance and a P-type charge transporting substance, and the photosensitive layer containing an electron accepting substance represented by the general formula [K]. An electrophotographic photoreceptor having a layer. [Chemical 19] [Wherein X K is a hydroxy group, OR K ′ group, N (R K ′) 2
Represents a group or an alkyl group which may have a substituent, an aryl group or an aralkyl group, wherein Y K and R K are halogen atoms,
Cyano group, nitro group, CF 3 group, COR K ′ group, COOR
'I represent a group, R K' K 'groups, OCOR K' groups, CONHR K 'groups, SOR K' groups or SO 2 R K represents an optionally substituted alkyl group, an aryl group or an aralkyl group , B
Represents a hydrocarbon atom group necessary for forming an aliphatic ring together with the carbon atom of the benzene ring. l, m and n represent 0 or a positive integer, n + m represents an integer of 2 or more, and l + m represents an integer of 2 to 8. The plurality of R K , Y K , and R K groups may be the same or different. When the substituent in the general formula [K] is an alkyl group or contains an alkyl group, the alkyl group may be linear, branched or cross-linked alicyclic unless otherwise specified. A ring, which may be substituted or may contain an unsaturated bond (eg, methyl group, ethyl group, iso-propyl group, t-butyl group,
Pentyl group, 2-ethylhexyl group, dodecyl group, allyl group, oleyl group, benzyl group, hydroxyethyl group,
Methoxyethyl group, phenoxyethyl group, cyclopentyl group, cyclohexyl group, norbornyl group). When the substituent in the general formula [K] is an aryl group or contains an aryl group, the aryl group may be substituted unless otherwise specified, and the monocyclic or condensed ring aryl group (for example, Phenyl group, 1-naphthyl group, p-tolyl group, p-chlorophenyl group, 4-methoxyphenyl group, pentafluorophenyl group, p-hydroxyphenyl group, p-cyanophenyl group, p-methanesulfonamidophenyl group, 3 , 4-dichlorophenyl group). ]
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質を含有する電荷発生層を設け、該電荷発生層上に前
記保護層を設けたことを特徴とする請求項46に記載の電
子写真感光体。47. A charge transporting layer containing a P-type charge transporting substance is provided on a conductive support, a charge generating layer containing a charge generating substance is provided on the charge transporting layer, and the charge generating layer is provided on the charge generating layer. 47. The electrophotographic photosensitive member according to claim 46, which is provided with a protective layer.
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質とP型又はN型電荷輸送物質を含有する電荷発生層
を設け、該電荷発生層上に前記保護層を設けたことを特
徴とする請求項46に記載の電子写真感光体。48. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 47. The electrophotographic photosensitive member according to claim 46, wherein the electrophotographic photosensitive member is provided, and the protective layer is provided on the charge generation layer.
電荷輸送物質とを共に含有する層から成る感光層を設
け、該感光層上に前記保護層を設けたことを特徴とする
請求項46に記載の電子写真感光体。49. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 46. The electrophotographic photoreceptor according to Item 46.
性物質が下記一般式〔k〕で表される化合物であること
を特徴とする請求項46、請求項47、請求項48又は請求項
49のいづれかに記載の電子写真感光体。 【化20】 〔式中、X′Kは炭素原子数5以下の低級アルキル基、
Y′K,R′Kの各基はシアノ基,CF3基,COR′K′
基又はCOOR′K′基を表し、R′K′基は炭素原子数
5以上のアルキル基を表し、B′は5又は6員の脂肪族
環を形成するに必要な炭化水素原子群を表す。l′及び
n′は0又は1を表し、m′は3から5の整数を表し、
n′+m′は3以上の整数を表す。〕50. The electron-accepting substance represented by the general formula [K] is a compound represented by the following general formula [k], 46, 47, 48 or Claim
The electrophotographic photosensitive member according to any one of 49. [Chemical 20] [Wherein X'K is a lower alkyl group having 5 or less carbon atoms,
Y 'K, R' each group a cyano group K, CF 3 group, COR 'K'
It represents a group or COOR 'K' group, R 'K' groups represents an alkyl group having at least 5 carbon atoms, B 'represents a hydrocarbon atomic group necessary to form an aliphatic ring of 5 or 6-membered . l'and n'represent 0 or 1, m'represents an integer from 3 to 5,
n '+ m' represents an integer of 3 or more. ]
電荷輸送物質を含有する感光層を設け、該感光層上に下
記一般式〔L〕で表される電子受容性物質を含有する保
護層を設けたことを特徴とする電子写真感光体。 【化21】 〔式中、XLはヒドロキシ基,ORL′基,N(RL′)2
基又は置換基を有してもよいアルキル基,アリール基若
しくはアラルキル基を表し、YL,RLはハロゲン原子,
シアノ基,ニトロ基,CF3基,CORL′基,COOR
L′基,OCORL′基,CONHRL′基,SORL′基
又はSO2RL′基を表し、RL′は置換基を有してもよ
いアルキル基,アリール基又はアラルキル基を表し、D
は複素環を形成するに必要な非金属原子群を表す。l,
m及びnは0又は正の整数を表し、m+nは2以上の整
数を表し、l+mは2から8の整数を表す。又XL,
YL,RLの各基はそれぞれ同じ基から成ってもよく、異
なる基から成ってもよい。又前記一般式〔L〕における
置換基がアルキル基であるか、又はアルキル基を含む
時、特に規定のない限り、アルキル基は直鎖状、分岐鎖
状又は架橋されていてもよい脂環式環であり、置換され
ていても、不飽和結合を含んでいてもよいアルキル基
(たとえば、メチル基,エチル基,iso−プロピル
基,t−ブチル基,ペンチル基,2−エチルヘキシル
基,ドデシル基,アリル基,オレイル基,ベンジル基,
ヒドロキシエチル基,メトキシエチル基,フェノキシエ
チル基,シクロペンチル基,シクロヘキシル基,ノルボ
ルニル基)を意味する。又前記一般式〔L〕における置
換基がアリール基であるか、又はアリール基を含む時、
特に規定のない限り、アリール基は置換されていてもよ
く単環若しくは縮合環のアリール基(たとえば、フェニ
ル基,1−ナフチル基,p−トリル基,p−クロロフェ
ニル基,4−メトキシフェニル基,ペンタフルオロフェ
ニル基,p−ヒドロキシフェニル基,p−シアノフェニ
ル基,p−メタンスルホンアミドフェニル基,3,4−
ジクロロフェニル基)を意味する。〕51. A photosensitive layer containing a charge-generating substance and a P-type charge-transporting substance is provided on a conductive support, and the electron-accepting substance represented by the following general formula [L] is contained on the photosensitive layer. An electrophotographic photoreceptor comprising a protective layer. [Chemical 21] [Wherein X L is a hydroxy group, OR L ′ group, N (R L ′) 2
Represents a group or an alkyl group which may have a substituent, an aryl group or an aralkyl group, Y L and R L are halogen atoms,
Cyano group, nitro group, CF 3 group, COR L ′ group, COOR
L 'represents a group, R L' 'group, OCOR L' groups, CONHR L 'group, SOR L' groups or SO 2 R L represents an optionally substituted alkyl group, an aryl group or an aralkyl group , D
Represents a group of non-metal atoms necessary for forming a heterocycle. l,
m and n represent 0 or a positive integer, m + n represents an integer of 2 or more, and l + m represents an integer of 2 to 8. The X L,
The groups Y L and R L may be the same or different. When the substituent in the general formula [L] is an alkyl group or contains an alkyl group, the alkyl group may be linear, branched or cross-linked alicyclic unless otherwise specified. A ring, which may be substituted or may contain an unsaturated bond (eg, methyl group, ethyl group, iso-propyl group, t-butyl group, pentyl group, 2-ethylhexyl group, dodecyl group) , Allyl group, oleyl group, benzyl group,
Hydroxyethyl group, methoxyethyl group, phenoxyethyl group, cyclopentyl group, cyclohexyl group, norbornyl group). When the substituent in the general formula [L] is an aryl group or contains an aryl group,
Unless otherwise specified, the aryl group may be substituted and has a monocyclic or condensed ring aryl group (eg, phenyl group, 1-naphthyl group, p-tolyl group, p-chlorophenyl group, 4-methoxyphenyl group, Pentafluorophenyl group, p-hydroxyphenyl group, p-cyanophenyl group, p-methanesulfonamidophenyl group, 3,4-
Dichlorophenyl group). ]
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質を含有する電荷発生層を設け、該電荷発生層上に前
記保護層を設けたことを特徴とする請求項51に記載の電
子写真感光体。52. A charge transporting layer containing a P-type charge transporting substance is provided on a conductive support, a charge generating layer containing a charge generating substance is provided on the charge transporting layer, and the charge generating layer is provided on the charge generating layer. 52. The electrophotographic photosensitive member according to claim 51, wherein a protective layer is provided.
含有する電荷輸送層を設け、該電荷輸送層上に電荷発生
物質とP型又はN型電荷輸送物質を含有する電荷発生層
を設け、該電荷発生層上に前記保護層を設けたことを特
徴とする請求項51に記載の電子写真感光体。53. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 52. The electrophotographic photosensitive member according to claim 51, wherein the electrophotographic photosensitive member is provided, and the protective layer is provided on the charge generation layer.
電荷輸送物質とを共に含有する層から成る感光層を設
け、該感光層上に前記保護層を設けたことを特徴とする
請求項51に記載の電子写真感光体。54. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 51. The electrophotographic photosensitive member according to item 51.
性物質が下記一般式〔l〕で表される化合物であること
を特徴とする請求項51、請求項52、請求項53又は請求項
54のいづれかに記載の電子写真感光体。 【化22】 〔式中、X′Lは炭素原子数5以下の低級アルキル基を
表し、Y′L,R′Lの各基はシアノ基,CF3基,CO
R′L′基又はCOOR′L′基を表し、R′L′基は炭
素原子数5以上のアルキル基を表し、D′はO,N,
S,P,Se,Teから選ばれる少なくとも1ヶのヘテ
ロ原子を環内に含む3から8員の置換されてもよい単環
若しくは縮合環から成る複素環を形成するに必要な非金
属原子群を表し、前記複素環としてはスクシンイミド,
マレイミド,フタルイミド,ピロール,ピラゾール,イ
ミダゾール,セレナゾール,トリアゾール,テトラゾー
ル,インドール,ピリジン,ピリミジン,モルホリン,
トリアジン,ホスフェザン,ベンズイミダゾール,ベン
ズチアゾール,ベンズチアジアゾール,イミダゾロピリ
ミジン等の各複素環が挙げられる。又好ましくは、D′
はO,N,Sから選ばれる少なくとも1ヶのヘテロ原子
を環内に含む5又は6員の置換されてもよい単環若しく
は縮合環から成る複素環を形成するに必要な原子群を表
す。l′及びn′は0又は1を表し、m′は3から5の
整数を表し、n′+m′は3以上の整数を表す。〕55. The electron-accepting substance represented by the general formula [L] is a compound represented by the following general formula [l], 51, 52, 53 or Claim
The electrophotographic photosensitive member according to any one of 54. [Chemical formula 22] Wherein, X 'L represents a lower alkyl group having not more than 5 carbon atoms, Y' L, each group R 'L is a cyano group, CF 3 group, CO
Represents R 'L' group or COOR 'L' group, R 'L' groups represents an alkyl group having at least 5 carbon atoms, D 'is O, N,
Non-metallic atomic group necessary for forming a 3- to 8-membered optionally substituted monocyclic or heterocyclic ring consisting of a condensed ring containing at least one heteroatom selected from S, P, Se and Te in the ring And the heterocycle is succinimide,
Maleimide, phthalimide, pyrrole, pyrazole, imidazole, selenazole, triazole, tetrazole, indole, pyridine, pyrimidine, morpholine,
Heterocycles such as triazine, phosphazene, benzimidazole, benzthiazole, benzthiadiazole, and imidazolopyrimidine are mentioned. Also preferably, D '
Represents an atomic group necessary for forming a heterocycle consisting of a 5- or 6-membered optionally substituted monocyclic or condensed ring containing at least one heteroatom selected from O, N and S in the ring. l'and n'represent 0 or 1, m'represents an integer of 3 to 5, and n '+ m' represents an integer of 3 or more. ]
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12148893A JPH06332220A (en) | 1993-05-24 | 1993-05-24 | Electrophotographic sensitive body |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12148893A JPH06332220A (en) | 1993-05-24 | 1993-05-24 | Electrophotographic sensitive body |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH06332220A true JPH06332220A (en) | 1994-12-02 |
Family
ID=14812408
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12148893A Pending JPH06332220A (en) | 1993-05-24 | 1993-05-24 | Electrophotographic sensitive body |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH06332220A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000330315A (en) * | 1999-03-18 | 2000-11-30 | Nec Niigata Ltd | Positively charged type electrophotographic photoreceptor and its production |
KR100510135B1 (en) * | 2002-04-12 | 2005-08-26 | 삼성전자주식회사 | Organophotoreceptor with an electron transport layer |
-
1993
- 1993-05-24 JP JP12148893A patent/JPH06332220A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000330315A (en) * | 1999-03-18 | 2000-11-30 | Nec Niigata Ltd | Positively charged type electrophotographic photoreceptor and its production |
KR100510135B1 (en) * | 2002-04-12 | 2005-08-26 | 삼성전자주식회사 | Organophotoreceptor with an electron transport layer |
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