CN101386621A

CN101386621A - Naphthalenetetracarboxylic acid diimide derivative and electrophotographic photoconductor having the same

Info

Publication number: CN101386621A
Application number: CNA2008102127800A
Authority: CN
Inventors: 太田正文; 岛田知幸; 田中裕二; 栗本锐司; 下山启介
Original assignee: Ricoh Co Ltd
Current assignee: Ricoh Co Ltd
Priority date: 2007-09-10
Filing date: 2008-09-08
Publication date: 2009-03-18

Abstract

The invention relates to naphthalenetetracarboxylic acid diimide derivative and electrophotographic photoconductor having the same. The present invention provides a naphthalenetetracarboxylic acid diimide derivative represented by the following general formula (1): wherein R1 and R2, which are identical or different, each represent a substituted or non-substituted alkyl group or a substituted or non-substituted aromatic hydrocarbon group; R 3 represents an alkyl group having 1 to 8 carbon atoms or an aromatic hydrocarbon group; R4, R5, R6 and R7, which are identical or different, each represent a hydrogen atom, a substituted or non-substituted alkyl group, or a substituted or non-substituted aromatic hydrocarbon group; and R 1 and R 2 may be linked to form a substituted or non-substituted heterocyclic group including a nitrogen atom; with compounds where all of R1, R2 and R3 are a methyl group, and compounds where both of R1 and R2 are a methyl group and R3 is a 1-octyl group being excluded.

Description

Naphthalenetetracarbacidic acidic diimide derivatives and have the photoelectric conductor for electronic photography of naphthalenetetracarbacidic acidic diimide

Technical field

[0001] the present invention relates to new naphthalenetetracarbacidic acidic diimide derivatives, it can be used for organic electronic material, is used in particular for the organic photoconductor material.

[0002] the present invention also relates to comprise the photoelectric conductor for electronic photography of the photoconductive layer that contains at least a naphthalenetetracarbacidic acidic diimide derivatives.

Background technology

[0003] the electrophotographic photo-conductor that has extensively been come into operation comprises organic photoelectric conductor material.The organic photoconductor material has been required to satisfy stricter needs, for example for the production method of environment sensitive or the more high sensitivity and the practicality of process.

[0004] the electrophotographic photo-conductor is formed by charge generating material and charge transport material.The charge transport material is required to have higher susceptibility, promptly shows high charge transport capability (current carrier transfer ability).At present, the hole conveying material that shows actual practicality is used in many cases.

[0005] yet, the further raising of organic electronic material (for example organic photoconductor material) depends on the exploitation that the height with hole and electronics (being current carrier) transports the charge transport material of performance.In view of this, demand has been proposed the electron transport material that shows high charge transport capability (current carrier transfer ability).

[0006], significantly developed based on the message handler (information processing devices) of electrophotography in recent years.Particularly, information is converted into numerary signal and uses light beam record its laser printer and digital copier, be greatly improved aspect reliability and the print image quality.In addition, high speed technology (high-speed technologies) makes some printers and duplicating machine realize multicolor printing.Therefore, the special requirement photo-conductor is to obtain high image quality and high-durability.

[0007] from reducing cost, improve productive rate and avoiding the viewpoint of environmental pollution to consider, the photo-conductor that uses in electrofax laser printer, digital copier etc. is generally formed by organic photoconductor (OPC) material.Generally speaking, the photo-conductor that contains the OPC material has the multilayered structure of single layer structure or functional separation.PVK-TNF charge transfer composite photoelectric conductor---it is the OPC-photo-conductor of at first using, and has single layer structure.

[0008] in nineteen sixty-eight, Hayashi and Regensburger invent PVK/a-Se Heterolamellar photovoltaic conductor independently.Melz etc. (1977) and Schlosser (1978) report have the Heterolamellar photovoltaic conductor of pigment dyestuff dispersion layer and organic low molecular quantification compound dispersed polymeres layer, promptly only have the organic photoelectric conducting shell.These Heterolamellar photovoltaic conductors are called as the Heterolamellar photovoltaic conductor of functional separation, and this is because they contain charge generation layer (CGL), wherein charge generation after absorb light; And charge-transport layer (CTL), by charge-transport layer, the electric charge of generation transported with in and surface charge.

[0009] compare with inorganic photoconductor, cause owing to reuse, organic photoconductor suffers bigger film come off (film ablation).The minimizing and the photosensitivity variation that come off and cause charge potential (chargepotential) of forming the photoconductive layer of photo-conductor.In addition, because the no regularity of photoconductor surface is easy to generate background spot (background smear), and formed image density or quality tendency variation.Therefore, by convention, organic photoconductor need have enough resistance to abrasions.And, because along with the size of high speed performance increase or electronic photographing device reduces, photo-conductor diminishes, therefore the more important thing is to be to provide highly competent organic photoconductor.

[0010] as widely understood, by the curing photoconductive layer, by giving its oilness, replacing lower molecular weight charge transport material (CTM) dispersed polymeres layer, increase the resistance to abrasion of photo-conductor by mixing filler therein or passing through use charge transport polymkeric substance.Yet, new problem appears owing to use aforesaid method to prevent that photoconductive layer from coming off.Particularly, absorption responds ozone, NOx and the oxidizing substance that produces owing to repeated use or to surrounding environment on the surface of photoconductive layer.Behind repeated use or responsive operation environment, the resistance on surface can reduce, and this causes problematic image blurring.This is image blurring can to come off with photoconductive layer and improves to a certain extent traditionally by causing these image blurring materials.

[0011] yet, must adopt new countermeasure to satisfy recent needs; Promptly higher resolving power and the weather resistance of Geng Gao.A kind of proposition reduce cause that photo-conductor is provided with well heater in the method for side effect of image blurring material.Yet it is the serious hindrance that reduces the electronic photographing device size or reduce energy consumption that well heater is provided.Equally, it is favourable using additive (for example antioxidant).Yet, because common additive does not have photoconductivity, therefore contain the electrofax performance of the photoconductive layer performance variation of heavy addition agent, as the residual electric potential of susceptibility that reduces and increase.

[0012] as mentioned above, provide high-wearing feature owing to the technological design around having changed or to it, what photoelectric conductor for electronic photography performance degree reduced comes off, but these unavoidably produce detrimentally affect to picture quality; For example, image blurring and resolving power reduces.Therefore, in having the photoelectric conductor for electronic photography of high-durability and high image quality, manufacturing meets difficulty.In other words, image blurring in order to prevent, they preferably have higher resistance, on the contrary, increase in order to prevent residual electric potential, and they preferably have lower resistance, and this causes the trade-off relation between them.

[0013] photoelectric conductor for electronic photography of great majority application has the multilayered structure of functional separation, the charge-transport layer that it comprises conductive carrier (conductive support), charge generation layer and contains the hole conveying material, and these layers are provided on the carrier.These photoelectric conductor for electronic photography are normally used for negatron photographic means (negative

Electrophotographic processes) in.

[0014] in electrophotographic method, corona tube charging (corona charging) is used for charging reliably.Most of duplicating machine and printer use this chargingmethod.Yet, as knowing, to compare with the charging of positive corona pipe, the charging of negative corona pipe is unsettled.Therefore use grid electrode charger (scorotron charger), this causes cost to raise.In addition, the charging of negative corona pipe produces a large amount of ozone, may cause chemical damage to photo-conductor.Therefore, when the equipment that uses the charging of negative corona pipe was used for a long time, the ozone that produces between charge period made binder resin and charge transport material variation by oxidation.And ionic compound (for example nitrogen oxide ion, sulfur oxide ion and ammonium ion) also produces in process of charging, and this gathering of class ionic compound on photo-conductor causes the problem of picture quality variation.Simultaneously, ozone also is environmental pollutant, and therefore, its a large amount of generation is problematic.In view of this, be discharged into the outside in order to prevent ozone, ozone filter is normally used for negative charging duplicating machine or printer, and this cost that also causes these equipment raises.

[0015] in order to address the above problem, the exploitation of positive charge type photoelectric conductor for electronic photography continues to carry out.Using is just charging has reduced the generation of ozone, nitrogen oxide ion etc.And when using widely used two component developers, the photoelectric conductor for electronic photography that just charging can and can provide desired images consistently less by such environmental effects.Therefore, consider, preferably the photoelectric conductor for electronic photography that is just charging from above-described viewpoint.

[0016] in individual layer photo-conductor that is just charging or reverse Heterolamellar photovoltaic conductor (CGL/CTL), charge generating material is present near the photoconductor surface.Charge generating material is subject to oxidizing substance such as ozone and the influence of nitrogen oxide ionic very much, so the photo-conductor of the type has problem: the gases affect that they highly are subject to comprise in the Working environment tail gas of fan heater or transportation means (for example from).

[0017] in high speed duplicating process, the photo-conductor of negative charging than the photo-conductor that is just charging more preferably.This is because in existing organic materials, only hole conveying material (promptly only shifting the material in hole) shows this high electric charge movability that can be used for the process of duplicating at a high speed, and common multiple layer electronic photographic photo-conductor (CTL/CGL) is unique negative charging.

[0018] as mentioned above, can just charge and bear the photoelectric conductor for electronic photography that charges and can be used for range of application widely.In addition, by reducing the quantity of photo-conductor product, can realize that cost reduces.And they can advantageously be applied in the high speed processes.

[0019] under these circumstances, Japanese Patent (JP-B) openly can just charge and bear the photoelectric conductor for electronic photography of charging for No. 2732697.This photoelectric conductor for electronic photography comprises the diphenoquinone derivative as electron transport material.The diphenoquinone derivative has quite low electric charge movability, and therefore, photoelectric conductor for electronic photography can not show susceptibility like this: it is enough to be used at a high speed, size reduces duplicating machine or printer.And it causes problematic image blurring as a result as reusable.

[0020] Japanese Patent Application Publication (JP-A) openly contains the aromatic compound of dialkyl amido for 2000-231204 number, and it is impregnated in photo-conductor as acid neutralizing agent.Even when reusing, the photo-conductor that contains this compound keeps gratifying picture quality.Yet this compound has low charge transport capability, so photo-conductor is difficult to reach high sensitivity, high-speed requirement, and this has applied restriction to compounds content.

[0021] No. the 2884353rd, JP-A 60-196768 number, JP-B and other document openly contain the stilbene compounds of dialkyl amido.From document " Itami et al., KONICA Technical Report, Vol.13, p.37,2000 ", these stilbene compounds produce anti-oxidant gas and prevent image blurring.

[0022] these compounds have dialkyl amido as substituting group, and it is being used for the strong mesomeric effect (mesomeric effect) (+M effect) of triarylamine response of structure position performance of charge transport position.Therefore, the extremely low ionization potential of this compound performance.Only contain this compound as the photoconductive layer of hole conveying material from bringing into use or reusing the electric charge hold facility (charge retention capability) that the back performance is on duty mutually.Photoelectric conductor for electronic photography with such photoconductive layer has serious problem, because they are difficult to actual the use.In many cases, even when using with other charge transport combination of materials, stilbene compounds also has the much lower ionization potential of ionization potential of material that is used for the hole trap position of charge transfer than manufacturing.Therefore, the susceptibility that obviously reduces of formed photoelectric conductor for electronic photography performance and high residual electric potential.

[0023] JP-A openly contains the photo-conductor of stilbene compounds and specific diamine compound for 2004-258253 number.This photo-conductor can be repeated to use, and does not reduce its susceptibility, and the environmental stability of performance raising, for example to oxidizing gas.

[0024] yet, this photo-conductor is not also realized flying print and is not reduced the size of electronic photographing device.

[0025] naphthalenetetracarbacidic acidic diimide derivatives is reported as the acceptor that forms charge-transfer complex (referring to, for example, German Patent 1230031 (AUSLEGESCHRIFT 1230031)); Perhaps be used as the performance active compound of anti-helicobacter (medicine) (referring to international publication number 02/040479) by report.Yet, in above-mentioned document, do not hint they are used for photoelectric conductor for electronic photography.Independently, U.S. Patent number 5468583 is described and is had and the application as electron transport material of two-N-alkyl-naphthalenetetracarbacidic acidic diimide derivatives of naphthalenetetracarbacidic acidic diimide derivatives different structure of the present invention.The photoelectric conductor for electronic photography that contains two-N-alkyl-naphthalenetetracarbacidic acidic diimide derivatives has problem, and is image blurring because they cause after repeated use.

[0026] aforementioned JP-B number 2732697 suggestions use the diphenoquinone derivative as the electron transport material that uses in the photoelectric conductor for electronic photography.JP-A 2005-154409 and U.S. Patent number 6794102 open naphthalenetetracarbacidic acidic diimide derivatives.Document " Chemistry letters (2003), 32 (6), 508-509 " is described the semiconductor material that is formed by the naphthalenetetracarbacidic acidic diimide derivatives with following structural (1).International publication number 00/040657 is described the electron transport material that is formed by the naphthalenetetracarbacidic acidic diimide derivatives with following structural (2) and (3).

Naphthalenetetracarbacidic acidic diimide naphthalenetetracarbacidic acidic diimide naphthalenetetracarbacidic acidic diimide

Derivative (1) derivative (2) derivative (3)

[0027] as top disclosed, the diphenoquinone derivative of describing in JP-B numbers 2732697 has quite low electric charge movability, therefore, the photo-conductor that contains it can not show susceptibility like this: it is enough to be used at a high speed, reduces the duplicating machine or the printer of size.And as reusable result, this derivative causes problematic image blurring.The binder resin of the diphenoquinone derivative of describing in JP-B the 2732697th, the naphthalenetetracarbacidic acidic diimide derivatives of describing in international publication number 00/040657 (2) or (3) and diphenoquinone derivative of describing in JP-A 01-206349 and formation photo-conductor has poor consistency, can not show their characteristic fully.The naphthalenetetracarbacidic acidic diimide derivatives of describing in JP-A 2005-154409 and U.S. Patent number 6794102 has complicated structure, and this is causing problem aspect its production.The naphthalenetetracarbacidic acidic diimide derivatives of describing in the document " Chemistryletters (2003), 32 (6), 508-509 " (1) has low electron transfer capacity, is not useable for practical application.

Summary of the invention

[0028] the invention provides following so that address the above problem.Particularly, a target of the present invention provides new naphthalenetetracarbacidic acidic diimide derivatives, it is as electron transport material, and it is an advantageously used organic electronic material in plurality of devices, described equipment such as photoelectric conductor for electronic photography, photoelectric transducer, thin-layer transistor (thin-layer transistors) and luminaire.

[0029] another target of the present invention provides the photoelectric conductor for electronic photography to long-term repeated use performance high-durability; It prevents the image variation, and described image variation may be reduced or image blurring generation causes in addition by image density; And it can provide high quality graphic consistently.Another target of the present invention provides electronic photographing device, electrophotographic method and electrophotographic printing print cartridge (process cartridge), the photo-conductor that they use size to reduce, and it can just be charged and be born charging; The size that it is realized flying print and reduces electronic photographing device; With in addition it can provide high quality graphic consistently when reusing, and do not need to replace photo-conductor.

[0030] therefore, the invention provides following.

＜1〉naphthalenetetracarbacidic acidic diimide derivatives, it is represented by following general formula (1):

General formula (1)

R wherein ¹And R ², it is identical or different, each expression that replace or unsubstituted alkyl or replacement or unsubstituted aromatic hydrocarbon group; R ³Expression has the alkyl or the aromatic hydrocarbon group of 1 to 8 carbon atom; R ⁴, R ⁵, R ⁶And R ⁷, it is identical or different, each expression hydrogen atom, replacement or unsubstituted alkyl or that replace or unsubstituted aromatic hydrocarbon group; And R ¹And R ²Can be connected with formation contain nitrogen-atoms replacement or unsubstituted heterocyclic group; And, do not comprise wherein R ¹, R ²And R ³All be the compound of methyl and R wherein ¹And R ²All be methyl, R ³It is the compound of 1-octyl group.

＜2〉naphthalenetetracarbacidic acidic diimide derivatives, it is represented by following general formula (I):

General formula (I)

R wherein _aExpression contains the essential divalent group of azo-cycle together with nitrogen-atoms and carbon atom formation; The nitrogenous loop section of following general formula (II) expression is represented that replace or unsubstituted, saturated or unsaturated ring, and it can further contain nitrogen-atoms or Sauerstoffatom; When described nitrogenous loop section is that described substituting group can form condensed ring together with a described part that contains azo-cycle when having a plurality of substituent ring; And R _bRepresent amino-replacement or unsubstituted branched-chain alkyl or amino-replacement or unsubstituted branched alkoxy alkyl.

General formula (II)

＜3〉according to above-mentioned＜2〉described naphthalenetetracarbacidic acidic diimide derivatives, the part of wherein said general formula (II) expression is that replace or unsubstituted piperidines, replacement or unsubstituted tetramethyleneimine, replacement or unsubstituted high piperidines, replacement or unsubstituted piperazine or replacement or unsubstituted morpholine.

＜4〉be used for the charge transport material of photoelectric conductor for electronic photography, it comprises according to above-mentioned＜1〉to＜3〉each described naphthalenetetracarbacidic acidic diimide derivatives.

＜5〉photoelectric conductor for electronic photography, comprise conductive carrier and be provided at photoconductive layer on the described conductive carrier, wherein said photoconductive layer contains and comprises according to above-mentioned＜1〉the first charge transport material to＜3〉each described naphthalenetetracarbacidic acidic diimide derivatives.

＜6〉according to above-mentioned＜5〉described photoelectric conductor for electronic photography, wherein said photoconductive layer further comprises the second charge transport material.

＜7〉according to above-mentioned＜6〉described photoelectric conductor for electronic photography, the wherein said second charge transport material is the derivative of following general formula (2) expression:

General formula (2)

Wherein X represents singly-bound or vinylene; R ⁸Expression hydrogen atom, replacement or unsubstituted alkyl or that replace or unsubstituted aromatic hydrocarbon group; Ar ¹Replace or the unsubstituted aromatic hydrocarbon group of expression; R ⁹Expression hydrogen atom, replacement or unsubstituted alkyl or that replace or unsubstituted aromatic hydrocarbon group; Ar ¹And R ⁹Can be connected to form ring; Represent group, 9-anthryl or that replace or the unsubstituted carbazyl of following general formula (3) or (4) expression with A;

General formula (3)

R wherein ¹⁰The group of expression hydrogen atom, alkyl, alkoxyl group, halogen atom or following general formula (5) expression; M is 1 to 3 integer; And when m is 2 or more for a long time, R ¹⁰Can be identical or different;

General formula (4)

R wherein ¹¹The group of expression hydrogen atom, alkyl, alkoxyl group, halogen atom or following general formula (5) expression; M1 is 1 to 3 integer; And when m1 is 2 or more for a long time, R ¹¹Can be identical or different; With

General formula (5)

R wherein ¹²And R ¹³, it can be identical or different, that each expression replaces or unsubstituted alkyl or that replace or unsubstituted aromatic hydrocarbon group; And R ¹²And R ¹³Can be connected to form ring.

＜8〉according to above-mentioned＜6〉described photoelectric conductor for electronic photography, the wherein said second charge transport material is the derivative of following general formula (6) expression:

General formula (6)

R wherein ¹⁴, R ¹⁶And R ¹⁷Each expression hydrogen atom, amino, alkoxyl group, thioalkoxy group, aryloxy, methylene-dioxy, replacement or unsubstituted alkyl, halogen atom or that replace or unsubstituted aromatic hydrocarbon group; R ¹⁵Expression hydrogen atom, alkoxyl group, replacement or unsubstituted alkyl or halogen atom; K, l, m2 or n are 1,2,3 or 4 integers; When k is 2,3 or 4 integer, R ¹⁴Can be identical or different; When 1 when being 2,3 or 4 integer, R15 can be identical or different; When m2 is 2,3 or 4 integer, R ¹⁶Can be identical or different; During with the integer that as n is 2,3 or 4, R ¹⁷Can be identical or different.

＜9〉according to above-mentioned＜6〉described photoelectric conductor for electronic photography, the wherein said second charge transport material is the derivative of following general formula (7) expression:

General formula (7)

X wherein ¹Expression singly-bound or vinylene; R ¹⁸Expression hydrogen atom, replacement or unsubstituted alkyl or that replace or unsubstituted aromatic hydrocarbon group; Ar ²Replace or the unsubstituted aromatic hydrocarbon group of expression; R ¹⁹Expression hydrogen atom, replacement or unsubstituted alkyl or that replace or unsubstituted aromatic hydrocarbon group; Ar ²And R ¹⁹Can be connected to form ring; Ar ³The divalent group of representing following general formula (8) or (9) expression; And R ²⁰That expression replaces or unsubstituted alkyl or that replace or unsubstituted aromatic hydrocarbon group;

General formula (8)

R wherein ²¹Expression hydrogen atom, alkyl, alkoxy or halogen atom; M3 is 1 to 3 integer; And when m3 is 2 or more for a long time, R ²¹Can be identical or different; With

General formula (9)

R wherein ²²Expression hydrogen atom, alkyl, alkoxy or halogen atom; M4 is 1 to 3 integer; And when m4 is 2 or more for a long time, R ²²Can be identical or different.

＜10〉according to above-mentioned＜6〉described photoelectric conductor for electronic photography, the wherein said second charge transport material is the derivative of following general formula (10) expression:

General formula (10)

X wherein ²Expression singly-bound or vinylene; R ²³Expression hydrogen atom, replacement or unsubstituted alkyl or that replace or unsubstituted aromatic hydrocarbon group; Ar ⁴Replace or the unsubstituted bivalent aromatic hydrocarbon group of expression; R ²⁴Expression hydrogen atom, replacement or unsubstituted alkyl or that replace or unsubstituted aromatic hydrocarbon group; And A ¹Group, 9-anthryl or that replace or the unsubstituted carbazyl of representing following general formula (3) or (4) expression;

General formula (3)

R wherein ¹⁰Represent hydrogen atom, alkyl, alkoxyl group, halogen atom or represent the group that following general formula (5) is represented; M is 1 to 3 integer; And when m is 2 or more for a long time, R ¹⁰Can be identical or different;

General formula (4)

R wherein ¹¹The group of expression hydrogen atom, alkyl, alkoxyl group, halogen atom, following general formula (5) expression; M1 is 1 to 3 integer; And when m1 is 2 or more for a long time, R ¹¹Can be identical or different; With

General formula (5)

R wherein ¹²And R ¹³---it can be identical or different, that each expression replaces or unsubstituted alkyl or that replace or unsubstituted aromatic hydrocarbon group; And R ¹²And R ¹³Can be connected to form ring.

＜11〉according to＜5〉to＜10〉each described photoelectric conductor for electronic photography, wherein said photoconductive layer comprises conductive carrier, charge generation layer and charge-transport layer in order.

＜12〉according to＜5〉to＜10〉each described photoelectric conductor for electronic photography, wherein said photoconductive layer comprises conductive carrier, charge-transport layer and charge generation layer in order.

＜13〉according to＜5〉to＜10〉each described photoelectric conductor for electronic photography, wherein said photoconductive layer has single layer structure.

＜14〉electrophotographic method is wherein according to＜5〉to＜13〉each described photoelectric conductor for electronic photography experiences repeatedly and comprises the expose circulation of (imagewise light exposure), development and transfer printing of charging, imaging.

＜15〉digital and electronic photographic means, wherein according to＜5〉to＜13〉each described photoelectric conductor for electronic photography experiences the circulation that comprises charging, imaging exposure, development and transfer printing repeatedly, wherein between described imaging exposure period, use LD or LED that electrostatic latent image is write on the described photoelectric conductor for electronic photography.

＜16〉electronic photographing device, it comprise charge member, imaging exposure element, developing element, transferring member and according to above-mentioned＜5 to＜13〉each described photoelectric conductor for electronic photography.

＜17〉digital and electronic camera installation, it comprise charge member, imaging exposure element, developing element, transferring member and according to above-mentioned＜5 to＜13〉each described photoelectric conductor for electronic photography, wherein in described imaging exposure element, use LD or LED that electrostatic latent image is write on the described photoelectric conductor for electronic photography.

＜18〉electrophotographic printing print cartridge, it comprises according to above-mentioned＜5〉to＜13〉each described photoelectric conductor for electronic photography.

[0031] the good electron transfer capacity of this new naphthalenetetracarbacidic acidic diimide derivatives performance, and in high sensitive electronic photograph photo-conductor, be advantageously used for the organic photoconductor material.

[0032] the present invention can address the above problem, and realizes above-mentioned target.The naphthalenetetracarbacidic acidic diimide derivatives of general formula (1) expression allows photo-conductor to keep their susceptibility, with performance to reusable high-durability, to show obvious enhanced environmental stability for example to oxidizing gas with high-definition picture is provided over a long time.The invention provides photoelectric conductor for electronic photography, it realizes high-durability and high image quality, and it consistently provides high quality graphic over a long time, and it is just to charge and is negative the charging.Equally, the invention provides electrophotographic method, equipment and process cartridge with this photoelectric conductor for electronic photography.

Description of drawings

[0033] Fig. 1 is the cross-sectional view of first photoelectric conductor for electronic photography of the present invention.

[0034] Fig. 2 is the cross-sectional view of second photoelectric conductor for electronic photography of the present invention.

[0035] Fig. 3 is the cross-sectional view of the 3rd photoelectric conductor for electronic photography of the present invention.

[0036] Fig. 4 is the cross-sectional view of the 4th photoelectric conductor for electronic photography of the present invention.

[0037] Fig. 5 is the cross-sectional view of the 5th photoelectric conductor for electronic photography of the present invention.

[0038] Fig. 6 is the cross-sectional view of the 6th photoelectric conductor for electronic photography of the present invention.

[0039] Fig. 7 is the synoptic diagram that is used to describe electrophotographic method of the present invention and electronic photographing device.

[0040] Fig. 8 illustrates another embodiment of electrophotographic method of the present invention.

[0041] Fig. 9 is the synoptic diagram that is used to describe electrophotographic printing print cartridge of the present invention.

[0042] Figure 10 is the powder X-ray D spectrogram of TiOPc.

Embodiment

[0043] with reference to the accompanying drawings, various details naphthalenetetracarbacidic acidic diimide derivatives and the photoelectric conductor for electronic photography that contains naphthalenetetracarbacidic acidic diimide derivatives.

(naphthalenetetracarbacidic acidic diimide derivatives)

[0044] inventor has carried out a large amount of research, and the photoconductive layer that has been found that the naphthalenetetracarbacidic acidic diimide derivatives that contains at least a following general formula (1) expression is not only just charging but also bear charging photo-conductor, and solved the problems referred to above, for example oxidizing gas (causing image blurring material) cause image blurring.

General formula (1)

R wherein ¹And R ², it is identical or different, each expression that replace or unsubstituted alkyl or replacement or unsubstituted aromatic hydrocarbon group; R ³Expression has the alkyl or the aromatic hydrocarbon group of 1 to 8 carbon atom; R ⁴, R ⁵, R ⁶And R ⁷, it is identical or different, each expression hydrogen atom, replacement or unsubstituted alkyl or that replace or unsubstituted aromatic hydrocarbon group; And R ¹And R ²Can be connected with formation contain nitrogen-atoms replacement or unsubstituted heterocyclic group; And do not comprise wherein R ¹, R ²And R ³All be the compound of methyl and R wherein ¹And R ²All be methyl, R ³It is the compound of 1-octyl group.

[0045] as mentioned above, naphthalenetetracarbacidic acidic diimide derivatives of the present invention can make photo-conductor effectively even when being repeated to use, keep gratifying picture quality.This reason is not also illustrated, but inventor imagination, the amino part charge neutrality of the strong basicity that comprises in the chemical structure oxidizing gas, described oxidizing gas is considered to cause image blurring material.When using with another kind of charge transport combination of materials, this naphthalenetetracarbacidic acidic diimide derivatives is to reusing the higher stability of performance, higher susceptibility etc.Especially, preferably use following specific charge transport material.

[0046] this naphthalenetetracarbacidic acidic diimide derivatives performance electron transfer capacity.The individual layer photo-conductor---it not only can just be charged but also can be charged by negative, can be by suitably determining layer structure or forming from this naphthalenetetracarbacidic acidic diimide derivatives by being used in combination the hole conveying material.

[0047] for above-mentioned reasons, can provide the photoelectric conductor for electronic photography that obtains high-durability and high image quality, even it can consistently provide high quality graphic when reusing, and it not only can just be charged but also can be by negative charging; With electrophotographic method, equipment and process cartridge, even they can consistently provide high quality graphic when reusing.

[0048] independently, the inventor has carried out a large amount of research, and has been found that the naphthalenetetracarbacidic acidic diimide derivatives of following general formula (I) expression is the good electron transport material that is used for the organic electronic system.

General formula (I)

General formula (II)

[0049] below, will describe in detail above-mentioned general formula (1) or (I) expression new naphthalenetetracarbacidic acidic diimide derivatives, contain the photoelectric conductor for electronic photography of this derivative and have electrophotographic method, equipment and the process cartridge of this photo-conductor.

The new naphthalenetetracarbacidic acidic diimide derivatives of＜general formula (1) expression 〉

[0050] general formula (1) new naphthalenetetracarbacidic acidic diimide derivatives expression, that be included in the photoconductive layer of the present invention will be described in detail.

General formula (1)

[0051] naphthalenetetracarbacidic acidic diimide derivatives of general formula (1) expression is abideed by at for example JP-A2001-265031 or J.Am.Chem.Soc., and the reaction scheme of describing in 120,3231 (1998) 1 or 2 (below provide) are come synthetic.Particularly, with 1, the sulfonamide derivatives that 1-two replaces hydrazine and replacement reacts under the situation that has or do not exist solvent, thereby produces the naphthalenetetracarbacidic acidic diimide derivatives of general formula (1) expression by simultaneously or sequentially for naphthalene-1,4,5,8-tetracarboxylic dianhydride derivative.

[0052] solvent is not specially limited, and can suitably select according to purpose.The example comprises benzene,toluene,xylene, chloronaphthalene, chlorobenzene, acetate, pyridine, picoline (methylpyridine), picoline (picoline), N, dinethylformamide, N,N-dimethylacetamide, dimethyl ethylidene-urea and dimethyl sulfoxide (DMSO).Temperature of reaction is preferably room temperature to 250 ℃.The pH of reaction mixture can be by for example being used to promote the damping fluid that reacts to regulate.Damping fluid can prepare by the aqueous solution of mixing acid (for example phosphoric acid) and alkali (for example lithium hydroxide, potassium hydroxide or sodium hydroxide).

[0053] more specifically, as as shown in the scheme 1, the naphthalenetetracarbacidic acidic diimide derivatives of general formula (1) expression can produce by following method, described method comprises first step, wherein naphthalene-1,4,5,8-tetracarboxylic dianhydride derivative and 1,1-two replaces hydrazine reaction, thereby produces an imide compound; With second step, the wherein sulfonamide derivatives of an imide compound and replacement reaction.

[0054] alternatively, as as shown in the scheme 2, the naphthalenetetracarbacidic acidic diimide derivatives of general formula (1) expression can produce by following method, described method comprises first step, naphthalene-1,4 wherein, 5, the sulfonamide derivatives reaction of 8-tetracarboxylic dianhydride derivative and replacement, thus an imide compound produced; With second step, an imide compound and 1 wherein, 1-two replaces hydrazine reactions.

Scheme 2

[0055] R in the general formula (1) ¹Or R ²The alkyl of expression is not specially limited, and can suitably select according to purpose.Example comprises the straight or branched alkyl with 1 to 15 carbon atom, and preferable methyl, ethyl, propyl group, sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl, 2-amyl group, 3-amyl group, 2-heptyl, 3-heptyl, 4-heptyl and the second month in a season-octyl group.R ¹Or R ²The aromatic hydrocarbon group of expression is not specially limited, and can suitably select according to purpose.Example comprises aromatic ring group such as benzene, biphenyl, naphthalene, anthracene, fluorenes and pyrene; With aromatic heterocycle group such as pyridine, quinoline, thiophene, furans, oxazole, oxadiazole and carbazole.R ³The alkyl with 1 to 8 carbon atom of expression is not specially limited, and can suitably select according to purpose.Example comprises ethyl, propyl group, sec.-propyl, 1,2-dimethyl propyl, isobutyl-, sec-butyl, the tertiary butyl, 2-amyl group, 3-amyl group, hexyl, 2-heptyl, 3-heptyl, 4-heptyl and undecyl.R ³The aromatic hydrocarbon group of expression is not specially limited, and can suitably select according to purpose.Example comprises aromatic ring group such as benzene, biphenyl, naphthalene, anthracene, fluorenes and pyrene; With aromatic heterocycle group such as pyridine, quinoline, thiophene, furans, oxazole, oxadiazole and carbazole.

[0056] R ¹Or R ²The substituting group that the group of expression can have is not specially limited, and can suitably select according to purpose.Example comprises above-mentioned alkyl; Alkoxyl group such as methoxyl group, oxyethyl group, propoxy-and butoxy; Halogen atom such as fluorine atom, chlorine atom, bromine atoms and iodine atom; Dialkyl amido; Diphenylamino; Above-mentioned aromatic hydrocarbon group; With heterocyclic group such as tetramethyleneimine, piperidines and piperazine.

[0057] R ¹And R ²Can be connected the heterocyclic group that comprises nitrogen-atoms with formation.Heterocyclic group is not specially limited, and can suitably select according to purpose.Example comprises the annelated heterocycles group, and it forms by aromatic hydrocarbon group and pyrrolidino (pyrrolidino group), piperidino-(1-position only), Piperazino condensations such as (piperazino group).

[0058] compound (compound (derivative) 1-48 that uses among the embodiment 23-82 given below) of preferred general formula (1) expression will be listed below, and it should not be understood that the present invention is defined in this.

The naphthalenetetracarbacidic acidic diimide derivatives of＜general formula (I) expression 〉

[0059] naphthalenetetracarbacidic acidic diimide derivatives of the preferred general formula of the present invention (I) expression will be listed below, and it should not be understood that the present invention is defined in this.

General formula (I)

Table 1

Table 2

Table 3

Table 4

Table 5

[0060] compound of general formula (I) expression is abideed by at for example JP-A2001-265031 or J.Am.Chem.Soc., and the reactions steps of describing in 120,3231 (1998) 3 or 4 (below provide) are come synthetic.Particularly, this compound can produce by the following method: wherein naphthalene tetracarboxylic acid or its acid anhydride and replacement or unsubstituted branched-chain alkyl amine reaction, thereby produce an imide compound, then with this imide compound and hydrazine derivative reaction with ring structure; Perhaps produce by the following method: wherein naphthalene tetracarboxylic acid or its acid anhydride react with the hydrazine derivative with ring structure, then with the compound and replacement or the unsubstituted branched-chain alkyl amine reaction that obtain.

Scheme 4

[0061] existing or not existing under the situation of solvent, carries out in the reaction shown in scheme 3 and the scheme 4.Solvent is not specially limited, and can suitably select according to purpose.Example comprises N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), pyridine, picoline, acetate, chloronaphthalene, chlorobenzene, dimethylbenzene and toluene.If desired, can in reaction, use catalyzer.Catalyzer is not specially limited, and can suitably select according to purpose.Example comprises Phenylsulfonic acid, right-toluenesulphonic acids and acetate.

[0062] hydrazine derivative with ring structure is not specially limited, and can suitably select according to purpose.That preferably replace or unsubstituted 1-amino-pyrrolidine, replacement or unsubstituted 1-amino piperidine, replacement or the amino high piperidines of unsubstituted 1-, the amino morpholine of N-replacement or unsubstituted 1-aminopiperazine and replacement or unsubstituted.The substituting group that above-mentioned substituted radical has is not specially limited, and can suitably select according to purpose.Example comprises alkyl with 1 to 5 carbon atom, has hydroxyl as substituent alkyl and halogen atom such as chlorine.

[0063] replace or unsubstituted branched-chain alkyl amine is not specially limited, and can suitably select according to purpose.Alkylamine preferably has the alkyl of 4 to 15 carbon atoms, example comprises dimethyl propyl, ethyl propyl, diethyl propyl group, methyl butyl, dimethylbutyl, methyl amyl, dimethyl amyl group, methyl hexyl, dimethyl hexyl, alkoxyalkyl and dialkyl aminoalkyl.

[0064] this naphthalenetetracarbacidic acidic diimide derivatives is used as electron transport material especially as the organic photoconductor material, and is used to the photoelectric conductor for electronic photography of multiple following form:

1) individual layer photo-conductor, wherein the mixture of charge generating material, naphthalenetetracarbacidic acidic diimide derivatives and binder resin is coated on the conductive carrier;

2) individual layer photo-conductor, wherein the mixture of charge generating material, hole conveying material, naphthalenetetracarbacidic acidic diimide derivatives and binder resin is coated on the conductive carrier;

3) Heterolamellar photovoltaic conductor, it has conductive carrier, charge generation layer and charge-transport layer---mainly comprise naphthalene tetracarboxylic acid derivative and binder resin, wherein charge generation layer is provided on the conductive carrier, and charge-transport layer is provided on the charge generation layer; With

4) Heterolamellar photovoltaic conductor, it has conductive carrier, charge generation layer and charge-transport layer---mainly comprise naphthalene tetracarboxylic acid derivative and binder resin, wherein charge-transport layer is provided on the conductive carrier, and charge generation layer is provided on the charge-transport layer.

[0065] in addition, this naphthalenetetracarbacidic acidic diimide derivatives performance good electron transfer ability, so it is advantageously used for the material that is used for organic electronic system such as photoelectric transducer, thin-layer transistor or luminaire.

(photoelectric conductor for electronic photography)

[0066] next the layer structure of this photoelectric conductor for electronic photography will be described.

[0067] Fig. 1 is the cross-sectional view of first photoelectric conductor for electronic photography of the present invention.Photoelectric conductor for electronic photography shown in Figure 1 has conductive carrier 31 and photoconductive layer 33---and mainly contain charge generating material and charge transport material, wherein photoconductive layer 33 is provided on the conductive carrier 31.

[0068] Fig. 2 is the cross-sectional view of second photoelectric conductor for electronic photography of the present invention.Photoelectric conductor for electronic photography has conductive carrier 31, charge generation layer 35 shown in figure 2, and---mainly containing charge generating material and charge-transport layer 37---mainly contains the charge transport material, wherein charge-transport layer 37 is provided on the conductive carrier 31, and charge generation layer 35 is provided on the charge-transport layer 37.

[0069] Fig. 3 is the cross-sectional view of the 3rd photoelectric conductor for electronic photography of the present invention.Photoelectric conductor for electronic photography shown in Figure 3 has conductive carrier 31, photoconductive layer 33---mainly contain charge generating material and charge transport material and protective layer 39; wherein photoconductive layer 33 is provided on the conductive carrier 31, and protective layer 39 is provided on the surface of photoconductive layer 33.In this photoelectric conductor for electronic photography, protective layer 39 can comprise naphthalenetetracarbacidic acidic diimide derivatives of the present invention.

[0070] Fig. 4 is the cross-sectional view of the 4th photoelectric conductor for electronic photography of the present invention.Photoelectric conductor for electronic photography shown in Figure 4 has conductive carrier 31, charge generation layer 35, and---mainly containing charge generating material, charge-transport layer 37---mainly contains charge transport material and protective layer 39; wherein charge generation layer 35 is provided on the conductive carrier 31; charge-transport layer 37 is provided on the charge generation layer 35, and protective layer 39 is provided on the charge-transport layer 37.In this photoelectric conductor for electronic photography, protective layer 39 can contain naphthalenetetracarbacidic acidic diimide derivatives of the present invention.

[0071] Fig. 5 is the cross-sectional view of the 5th photoelectric conductor for electronic photography of the present invention.Photoelectric conductor for electronic photography shown in Figure 5 has conductive carrier 31, charge-transport layer 37, and---mainly containing charge transport material and charge generation layer 35---mainly contains charge generating material, wherein charge-transport layer 37 is provided on the conductive carrier 31, and charge generation layer 35 is provided on the charge-transport layer 37.

[0072] Fig. 6 is the cross-sectional view of the 6th photoelectric conductor for electronic photography of the present invention.Photoelectric conductor for electronic photography shown in Figure 6 has conductive carrier 31, charge-transport layer 37, and---mainly containing charge transport material, charge generation layer 35---mainly contains charge generating material and protective layer 39; wherein charge-transport layer 37 is provided on the conductive carrier 31; charge generation layer 35 is provided on the charge-transport layer 37, and protective layer 39 is provided on the charge generation layer 35.In this photoelectric conductor for electronic photography, protective layer 39 can contain naphthalenetetracarbacidic acidic diimide derivatives of the present invention.

＜conductive carrier 〉

[0073] as long as conductive carrier 31 performance 10 ¹⁰Ω/cm or following volume resistance, it is not particularly limited, and can suitably select according to purpose.The example comprises by vapour deposition or sputters at film shape or cylindric plastics or paper, metal (for example aluminium, nickel, chromium, nichrome, copper, gold and silver or platinum) or metal oxide (for example, stannic oxide or Indium sesquioxide) are gone up deposition and the sedimentation products that forms; Also comprise aluminium sheet, aluminium alloy plate, nickel plate and stainless steel plate.And, can be following the pipe that uses of manufacturing: by extruding, pultrusion etc., above-mentioned metal sheet is formed former pipe (raw tube); With the former pipe of cutting, and make it through surface treatment such as super finishing (superfinishing) and polishing.Equally, annular nickel strap or the ring stainless steel band described in JP-A52-36016 also can be used as conductive carrier 31.

[0074] and, can be coated on by the dispersed mixture that will be fit to the conductive powder in the binder resin on the carrier and to form conductive carrier 31.Conductive powder is not specially limited, and can suitably select according to purpose.The example comprises carbon black, acetylene black (acethylene black); The powder of metal such as aluminium, nickel, iron, nichrome, copper, zinc or silver; The powder of metal oxide such as conductive tin oxide or ITO.The binder resin that is used in combination with conductive powder is not specially limited, and can suitably select according to purpose.The example comprises thermoplastic resin, thermosetting resin and light curable resin are (as polystyrene, styrene-acrylonitrile copolymer, the styrene-butadiene copolymer styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, polyvinyl acetate, poly(vinylidene chloride), the polyarylate resin, phenoxy resin, polycarbonate, the rhodia resin, ethyl cellulose resin, polyvinyl butyral acetal, polyvinyl formal, polyvinyltoluene, poly--the N-vinyl carbazole, acrylic resin, silicone resin, Resins, epoxy, melamine resin, urethane resin, resol and Synolac).Conductive layer can forming by the mixture of conductive powder in the coating appropriate solvent (as tetrahydrofuran (THF), methylene dichloride, methyl ethyl ketone or toluene) and binder resin.

[0075] in addition, by providing thermal contraction tubulose thing as conductive layer for suitable cylindric carrier, can form conductive carrier 31, this thermal contraction tubulose thing contains conductive powder and material (as polyvinyl chloride, polypropylene, polyester, polystyrene, poly(vinylidene chloride), polyethylene, chlorinated rubber or teflon (Teflon) (registered trademark)).

＜photoconductive layer 〉

[0076] photoconductive layer will be described.Photoconductive layer can have the single or multiple lift structure.For for simplicity, the photoconductive layer (being the Heterolamellar photovoltaic conducting shell) that is made of charge generation layer 35 and charge-transport layer 37 will be described at first.

＜＜charge generation layer〉〉

[0077] charge generation layer 35 is the layers that mainly formed by charge generating material.Charge generation layer 35 can produce the material manufacturing by known charge.Its typical example comprises azo pigment such as C.I. Pigment blue 25 (C.I.21180), C.I. pigment red 41 (C.I.21200), C.I. sour red 52 (C.I.45100), C.I. red 3 (C.I.45210) of alkali have the pigment (describing) of carbazole skeleton in JP-A 53-95033 number, pigment (in JP-A 53-133445 number, describing) with distyryl benzene skeleton, pigment (in JP-A 53-132347 number, describing) with triphenylamine skeleton, pigment (in JP-A 54-12742 number, describing) with pigment (in JP-A 54-21728 number, describing) Ju You oxadiazole skeleton of dibenzothiophene skeleton, pigment (in JP-A 54-22834 number, describing) with Fluorenone skeleton, pigment (in JP-A 54-17733 number, describing) with two Stilbene skeletons, pigment (in JP-A 54-2129 number, describing) with Lian Ben Yi Xi oxadiazole skeleton, pigment (as described in) with distyryl carbazole skeleton JP-A 54-14967 number, with pigment with benzanthrone skeleton; Phthalocyanine pigment such as C.I. pigment blue 16 (C.I.74100), Y-type TiOPc (JP-A 64-17066 number), A (β)-type TiOPc, B (α)-type TiOPc, I-type TiOPc (JP-A describes for 11-21466 number), II-type phthalocyanine chlorine gallium (chlorogallium phthalocyanine) (Iijima etc., the 67th Japanese Chemical Society annual meeting (spring), 1B4,04 (1994)), V-type phthalocyanine hydroxyl gallium (hydroxygallium phthalocyanine) (Daimon etc., the 67th Japanese Chemical Society annual meeting (spring), 1B4,05 (1994)) and the metal-free phthalocyanine pigment of X-type (U.S. Patent number 3,816,118); Indigo-blue pigment such as C.I. Vat Brown 5 (C.I.73410) and C.I. vat dyes (C.I.73030); He perylene dye such as Argoscarlet B (product of Bayer AG) and Intansrencescarlet R (product of Bayer AG).These materials can separately or be united use.

[0078] following formation charge generation layer 35: use ball mill, device for grinding, sand mill or supersound process with charge generating material---if desired, together with binder resin---in appropriate solvent, disperse; Formed dispersed mixture (coating liquid) is coated on the conductive carrier; And drying coated carrier.

[0079] binder resin that can randomly be included in the charge generation layer 35 is not specially limited, and can suitably select according to purpose.The example comprises polymeric amide, urethane resin, Resins, epoxy, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral acetal, polyvinyl formal, polyethylene ketone, polystyrene, polysulfones, the poly-N-vinyl carbazole, polyacrylamide, the polyethyleneimine: benzyl, polyester, phenoxy resin, vinyl chloride vinyl acetate copolymer, polyvinyl acetate, polyphenylene oxide, polymeric amide, polyvinyl pyridine, celluosic resin, casein, polyvinyl alcohol and polyvinylpyrrolidone.By the quality of per 100 parts of charge generating materials, the amount of binder resin is 0 part to 500 parts by mass, preferably by mass 10 parts to 300 parts.The adding of binder resin can be carried out before or after the dispersion charge generating material.

[0080] solvent is not specially limited, and can suitably select according to purpose.The example comprises Virahol, acetone, methyl ethyl ketone, pimelinketone, tetrahydrofuran (THF), diox, ethyl cellosolve, ethyl acetate, methyl acetate, methylene dichloride, ethylene dichloride, mono chloro benzene, hexanaphthene, toluene, dimethylbenzene and petroleum naphtha (ligroin), preferred especially ketone solvent, ester solvent and ether solvents.These solvents can separately or be united use.

[0081] charge generation layer 35 mainly contains charge generating material, solvent and binder resin.In addition, this layer can comprise any additives such as sensitizing agent, dispersion agent, tensio-active agent and silicone oil.

[0082] method of coating coating liquid is not specially limited, and can suitably select according to purpose.The example comprises that dip-coating, spraying, drop coating (beat co ating), nozzle coating (nozzle coating), rotary coating (spinner coating) and ring are coated with.

[0083] thickness of charge generation layer 35 is not specially limited, and can suitably select according to purpose.This thickness preferably approximately 0.01 μ m is to about 5 μ m, and more preferably 0.1 μ m is to 2 μ m.

＜＜charge-transport layer〉〉

[0084] charge-transport layer 37 is the layers that mainly are made of the charge transport material.The charge transport material is an any kind of in hole conveying material, electron transport material and the charge transport polymkeric substance.These materials are described respectively below.

[0085] the hole conveying material is not specially limited, and can suitably select according to purpose.The example comprises, and poly--N-carbazole arrives the compound of (34) expression with its derivative, poly--γ-carbazyl ethyl glutamate and its derivative, pyrene-formaldehyde condensation products and its derivative, polyethylene pyrene, polyethylene Fei, oxazole derivative, imdazole derivatives, triphenylamine derivative and following general formula (11):

General formula (11)

R wherein ²⁵Expression methyl, ethyl, 2-hydroxyethyl or 2-chloroethyl; R ²⁶Expression methyl, ethyl, benzyl or phenyl; And R ²⁷Expression hydrogen atom, chlorine atom, bromine atoms, have 1 to 4 carbon atom alkyl, have alkoxyl group, dialkyl amido or the nitro of 1 to 4 carbon atom.

[0086] examples for compounds of general formula (11) expression comprises 9-ethyl carbazole-3-formaldehyde-1-methyl isophthalic acid-phenylhydrazone, 9-ethyl carbazole-3-formaldehyde-1-benzyl-1-phenylhydrazone and 9-ethyl carbazole-3-formaldehyde-1,1-diphenyl hydrazone.

General formula (12)

Ar wherein ⁵Expression naphthalene nucleus, anthracene nucleus, pyrene ring, the naphthalene nucleus of replacement, the anthracene nucleus of replacement, pyrene ring, pyridine ring, furan nucleus or the thiphene ring of replacement; And R ²⁸Expression alkyl, phenyl or benzyl.

[0087] examples for compounds of general formula (12) expression comprises 4-diethylamino styryl-β-formaldehyde-1-methyl isophthalic acid-phenylhydrazone and 4-methoxynaphthalene-1-formaldehyde-1-benzyl-1-phenylhydrazone.

General formula (13)

R wherein ²⁹Expression alkyl, benzyl, phenyl or naphthyl; R ³⁰Expression hydrogen atom, alkyl, alkoxyl group, dialkyl amido, two aryl alkyl aminos or ammonia diaryl base with 1 to 3 carbon atom with 1 to 3 carbon atom; n ¹It is 1 to 4 integer; Work as n ¹Be 2 or when bigger, R ³⁰Can be identical or different; And R ³¹Expression hydrogen atom or methoxyl group.

[0088] examples for compounds of general formula (13) expression comprises 4-methoxybenzaldehyde-1-methyl isophthalic acid-phenylhydrazone, 2,4-dimethoxy benzaldehyde-1-benzyl-1-phenylhydrazone, 4-diethyl amino benzaldehyde-1,1-diphenyl hydrazone, 4-methoxybenzaldehyde-1-(4-methoxyl group) phenylhydrazone, 4-diphenylamino phenyl aldehyde-1-benzyl-1-phenylhydrazone and 4-dibenzyl amino phenyl aldehyde-1, the 1-diphenyl hydrazone.

General formula (14)

R wherein ³²Expression has the alkyl of 1 to 11 carbon atom, replacement or unsubstituted phenyl or replacement or unsubstituted heterocyclic group; R ³³And R ³⁴---it can be identical or different, each expression hydrogen atom, the alkyl with 1 to 4 carbon atom, hydroxyalkyl, chlorine alkyl or replacement or unsubstituted aralkyl; R ³³And R ³⁴Can connect the heterocycle that comprises nitrogen-atoms with formation; And R ³⁵---it can be identical or different, each expression hydrogen atom, the alkyl with 1 to 4 carbon atom, alkoxy or halogen atom.

[0089] examples for compounds of general formula (14) expression comprises 1,1-two (4-dibenzyl amino phenyl) propane, three (4-diethylamino phenyl) methane, 1,1-two (4-dibenzyl amino phenyl) propane and 2,2 '-dimethyl-4,4 '-two (diethylamino)-triphenyl methanes.

General formula (15)

R wherein ³⁶Expression hydrogen atom or halogen atom; Ar ⁶That expression replaces or unsubstituted phenyl, replacement or unsubstituted naphthyl, replacement or unsubstituted anthryl or that replace or unsubstituted carbazyl.

[0090] examples for compounds of general formula (15) expression comprises 9-(4-diethylamino styryl) anthracene and 9-bromo-10-(4-diethylamino styryl) anthracene.

General formula (16)

R wherein ³⁷Expression hydrogen atom, halogen atom, cyano group, have the alkoxyl group of 1 to 4 carbon atom or have the alkyl of 1 to 4 carbon atom; And Ar ⁷The group of representing following general formula (17) or (18) expression.

General formula (17)

R wherein ³⁸Expression has the alkyl of 1 to 4 carbon atom.

General formula (18)

R wherein ³⁹Expression hydrogen atom, halogen atom, have 1 to 4 carbon atom alkyl, have the alkoxyl group or the dialkyl amido of 1 to 4 carbon atom; n ²Be 1 or 2; Work as n ²Be 2 o'clock, R ³⁹Can be identical or different; R ⁴⁰Or R ⁴¹The expression hydrogen atom, have 1 to 4 carbon atom replacement or unsubstituted alkyl or that replace or unsubstituted benzyl.

[0091] examples for compounds of general formula (16) expression comprises 9-(4-dimethylamino benzylidene) fluorenes and 3-(9-fluorenylidene)-9-ethyl carbazole.

General formula (19)

R wherein ⁴²Expression carbazyl, pyridyl, thienyl, indyl, furyl, replacement or unsubstituted phenyl, replacement or unsubstituted styryl, replacement or unsubstituted naphthyl or that replace or unsubstituted anthryl, wherein the group of each replacement has the substituting group that is selected from dialkyl amido, alkyl, alkoxyl group, carboxyl, esterifying carboxyl group, halogen atom, cyano group, aryl alkyl amino, N-alkyl-N-aryl alkyl amino, amino, nitro and acetylamino (acethylamino group).

[0092] examples for compounds of general formula (19) expression comprises 1,2-two (4-diethylamino styryl) benzene and 1,2-two (2, the 4-dimethoxy-styryl) benzene.

General formula (20)

R wherein ⁴³Expression low-carbon alkyl, replacement or unsubstituted phenyl or that replace or unsubstituted benzyl; R ⁴⁴And R ⁴⁵Each the expression hydrogen atom, low-carbon alkyl, low-carbon alkoxy, halogen atom, nitro, amino have low-carbon alkyl or benzyl as substituent amino; And n ³It is 1 or 2 integer.

[0093] examples for compounds of general formula (20) expression comprises 3-styryl-9-ethyl carbazole, 3-(4-methoxyl-styrene)-9-ethyl carbazole.

General formula (21)

R wherein ⁴⁶Expression hydrogen atom, alkyl, alkoxy or halogen atom; R ⁴⁷And R ⁴⁸Replace or the unsubstituted aryl of each expression; R ⁴⁹Expression hydrogen atom, low-carbon alkyl or that replace or unsubstituted phenyl; And Ar ⁸That expression replaces or unsubstituted phenyl or that replace or unsubstituted naphthyl.

[0094] examples for compounds of general formula (21) expression comprises 4-diphenylamino Stilbene, 4-dibenzyl amino Stilbene, the amino Stilbene of 4-dimethylbenzene, 1-(4-diphenylamino styryl) naphthalene and 1-(4-diphenylamino styryl) naphthalene.

General formula (22)

N wherein ⁴It is 0 or 1 integer; R ⁵⁰Expression hydrogen atom, alkyl or that replace or unsubstituted phenyl; Ar ⁹Replace or the unsubstituted aryl of expression; R ⁵¹Expression that replace or unsubstituted alkyl or replacement or unsubstituted aryl; A ²Group expression 9-anthryl, replacement or unsubstituted carbazyl or following general formula (23) or (24) expression; And work as n ⁴Be 0 o'clock, A ²And R ⁵⁰Can be connected to form ring.

General formula (23)

General formula (24)

In general formula (23) and (24), R ⁵²The group of expression alkyl, alkoxyl group, halogen atom or following general formula (25) expression; m ⁵It is 0 to 3 integer; And work as m ⁵Be 2 or when bigger, R ⁵²Can be identical or different.

General formula (25)

R wherein ⁵³And R ⁵⁴---it can be identical or different, replace or the unsubstituted aryl of each expression; And R ⁵³And R ⁵⁴Can be connected to form ring.

[0095] examples for compounds of general formula (22) expression comprises 4 '-diphenylamino-α-phenyl Stilbene and 4 '-two (4-aminomethyl phenyl) amino-α-phenyl Stilbene.

General formula (26)

R wherein ⁵⁵, R ⁵⁶And R ⁵⁷Each expression hydrogen atom, low-carbon alkyl, low-carbon alkoxy, halogen atom or dialkyl amido; And n ⁵Be 0 or 1.

[0096] examples for compounds of general formula (26) expression comprises 1-phenyl-3-(4-diethylamino styryl)-5-(4-diethylamino phenyl) pyrazoline.

General formula (27)

R wherein ⁵⁸And R ⁵⁹Each expression that replace or unsubstituted alkyl or replacement or unsubstituted aryl; A ³The amino that expression replaces, replacement or unsubstituted aryl or allyl group.

[0097] examples for compounds of general formula (27) expression comprises 2,5-two (4-diethylamino phenyl)-1,3,4-oxadiazole, 2-N, N-diphenylamino-5-(4-diethylamino phenyl)-1,3,4-oxadiazole and 2-(4-dimethylaminophenyl)-5-(4-diethylamino phenyl)-1,3, the 4-oxadiazole.

General formula (28)

X wherein ³Expression hydrogen atom, low-carbon alkyl or halogen atom; R ⁶⁰Expression that replace or unsubstituted alkyl or replacement or unsubstituted aryl; And A ⁴Amino or that replace or unsubstituted aryl that expression replaces.

[0098] examples for compounds of general formula (28) expression comprises 2-N, N-diphenylamino-5-(N-ethyl carbazole-3-yl)-1,3,4-oxadiazole and 2-(4-diethylamino phenyl)-5-(N-ethyl carbazole-3-yl)-1,3,4-oxadiazole.

General formula (29)

R wherein ⁶¹Expression low-carbon alkyl, low-carbon alkoxy or halogen atom; R ⁶²And R ⁶³---it can be identical or different, each expression hydrogen atom, low-carbon alkyl, low-carbon alkoxy or halogen atom; And l ¹, m ⁶Or n ⁶It is 0 to 4 integer.

[0099] example of the benzidine compound of general formula (29) expression comprises N, N '-phenylbenzene-N, N '-two (3-aminomethyl phenyl)-[1,1 '-xenyl]-4,4 '-diamines and 3,3 '-dimethyl-N, N, N ', N '-four (4-aminomethyl phenyl)-[1,1 '-xenyl]-4,4 '-diamines.

General formula (30)

R wherein ⁶⁴, R ⁶⁶And R ⁶⁷Each expression hydrogen atom, amino, alkoxyl group, thioalkoxy group, aryloxy, methylene-dioxy, replacement or unsubstituted alkyl, halogen atom or that replace or unsubstituted aryl; R ⁶⁵Expression hydrogen atom, alkoxyl group, replacement or unsubstituted alkyl or halogen atom; k ¹, l ², m ⁷Or n ⁷It is 1,2,3 or 4 integer; And work as k ¹, l ², m ⁷Or n ⁷When being 2,3 or 4 integer, R ⁶⁴, R ⁶⁵, R ⁶⁶Or R ⁶⁷Can be identical or different; And do not comprise wherein R ⁶⁴, R ⁶⁵, R ⁶⁶And R ⁶⁷It all is the compound of hydrogen atom.

[0100] example of the benzidine compound of general formula (30) expression comprises 4 '-methoxyl group-N, N-phenylbenzene-[1,1 '-xenyl]-4-amine, 4 '-methyl-N, N-two (4-aminomethyl phenyl)-[1,1 '-xenyl]-4-amine, 4 '-methoxyl group-N, N-two (4-aminomethyl phenyl)-[1,1 '-xenyl]-4-amine and N, N-two (3, the 4-3,5-dimethylphenyl)-[1,1 '-xenyl]-4-amine.

General formula (31)

Ar wherein ¹⁰Expression fused polycycle hydrocarbyl group, it can have substituting group, and it has and is equal to or less than 18 carbon atom; R ⁶⁸And R ⁶⁹---it can be identical or different, each expression hydrogen atom, halogen atom, replacement or unsubstituted alkyl, alkoxyl group or replacement or unsubstituted phenyl; And n ⁸It is 1 or 2 integer.

[0101] example of the triarylamine compound of general formula (31) expression comprises N, N-phenylbenzene-pyrene-1-amine, N, N-two-right-tolyl-pyrene-1-amine, N, N-two-right-tolyl-naphthalidine, N, the luxuriant and rich with fragrance amine, 9 of N-two (right-tolyl)-1-, 9-dimethyl-2-(two-right-tolyl amino) fluorenes, N, N, N ', N '-four (4-aminomethyl phenyl)-Fei-9,10-diamines and N, N, N ', N '-four (3-aminomethyl phenyl)--phenylenediamine.

A ⁵—CH＝CH—Ar ¹¹—CH＝CH—A ⁵

General formula (32)

Ar wherein ¹¹Replace or the unsubstituted aromatic hydrocarbon group of expression; And A ⁵The group of expression general formula (33) expression.

General formula (33)

Ar wherein ¹²Replace or the unsubstituted aromatic hydrocarbon group of expression; R ⁷⁰And R ⁷¹Each expression that replace or unsubstituted alkyl or replacement or unsubstituted aryl.

[0102] example of the diene aromatic compound of general formula (32) expression comprises 1,4-two (4-diphenylamino styryl) benzene and 1,4-two [4-two (right-tolyl) amino-benzene vinyl] benzene.

General formula (34)

Ar wherein ¹³Replace or the unsubstituted aromatic hydrocarbon group of expression; R ⁷²Expression hydrogen atom, replacement or unsubstituted alkyl or that replace or unsubstituted aryl; n ⁹Be 0 or 1; m ⁸Be 1 or 2; And work as n ⁹Be 0 and m ⁸Be 1 o'clock, Ar ¹³And R ⁷²Can be connected to form ring.

[0103] example of the styryl pyrene compound of general formula (34) expression comprises 1-(4-diphenylamino styryl) pyrene and 1-(N, N-two-right-tolyl-4-amino-benzene vinyl) pyrene.

[0104] electron transport material is not specially limited, and can suitably select according to purpose.The example comprises tetrachlorobenzoquinone (chloranil), tetrabromo-quinone (bromanil), tetracyanoethylene (tetracyanoethylene), four cyanide quinoline bismethanes (tetracyanoquinodimethane), 2,4,7-trinitro--9-Fluorenone, 2,4,5,7-tetranitro-9-Fluorenone, 2,4,5,7-tetranitro xanthone (2,4,5,7-tetranitroxanthone), 2,4,8-trinitro-thioxanthone, 2,6,8-trinitro--indenes-4H-indeno [1,2-b] thiophene-4-ketone and 1,3,7-trinitro-dibenzothiophene-5,5-dioxide.The electron transport material of preferably following general formula (35), (36), (37) or (38) expression.These electron transport materials can separately or be united use.

General formula (35)

R wherein ⁷³, R ⁷⁴And R ⁷⁵---it can be identical or different, each expression hydrogen atom, halogen atom, replacement or unsubstituted alkyl, alkoxyl group or that replace or unsubstituted phenyl.

General formula (36)

R wherein ⁷⁶And R ⁷⁷---it can be identical or different, each expression hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted phenyl.

General formula (37)

R wherein ⁷⁸, R ⁷⁹And R ⁸⁰---it can be identical or different, each expression hydrogen atom, halogen atom, replacement or unsubstituted alkyl, alkoxyl group or that replace or unsubstituted phenyl.

General formula (38)

Its

Middle R ⁸¹Expression can have substituent alkyl maybe can have substituent aryl; And R ⁸²Expression can have substituent alkyl, can have the group of substituent aryl or following general formula (39) expression.

-O-R ⁸³General formula (39)

R wherein ⁸³Expression can have substituent alkyl maybe can have substituent aryl.

[0105] if desired, charge-transport layer 37 comprises binder resin.Described binder resin is not specially limited, and can suitably select according to purpose.The example comprises thermoplastic resin and thermosetting resin, as polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, polyvinyl acetate, poly(vinylidene chloride), the polyarylate resin, phenoxy resin, polycarbonate, the rhodia resin, ethyl cellulose resin, polyvinyl butyral acetal, polyvinyl formal, polyvinyltoluene, the poly-N-vinyl carbazole, acrylic resin, silicone resin, Resins, epoxy, melamine resin, urethane resin, resol and Synolac.

[0106] when charge-transport layer contains charge transport material and naphthalenetetracarbacidic acidic diimide derivatives of the present invention, quality by per 100 parts of binder resins, its total content is preferably 20 parts to 300 parts by mass, more preferably by mass 40 parts to 150 parts.From improving the viewpoint of resolving power and response, the thickness of charge-transport layer is preferably 25 μ m or littler.The lower limit of thickness---it changes (the particularly charge potential of system) along with the system that uses---is preferably 5 μ m.

[0107] amount that is included in this naphthalenetetracarbacidic acidic diimide derivatives in the charge-transport layer is preferably the 0.01wt.% of amount of charge transport material to 150wt.%.When this measured less than 0.01wt.%, the charge-transport layer performance reduced the resistance of oxidizing gas, and on the contrary, when this measured greater than 150wt.%, owing to reuse, charge-transport layer shows residual electric potential to be increased.

[0108] forming the employed solvent of charge-transport layer can be for example tetrahydrofuran (THF), diox, toluene, methylene dichloride, mono chloro benzene, ethylene dichloride, pimelinketone, methyl ethyl ketone or acetone.The charge transport material can be used alone or be used in combination.

[0109] antioxidant can be used for preventing the variation of this naphthalenetetracarbacidic acidic diimide derivatives.Antioxidant can be normally used those antioxidants (below list).In this tabulation, (c) quinhydrones is with (f) hindered amines is preferred especially.

[0110] preferably, before adding this naphthalenetetracarbacidic acidic diimide derivatives, antioxidant is mixed in the coating liquid.When antioxidant with the 0.1wt.% of naphthalenetetracarbacidic acidic diimide derivatives amount when 200wt.% mixes, it shows enough effects.

[0111] charge-transport layer can contain the charge transport polymkeric substance with charge transport material and two kinds of functions of binder resin.The use of this charge transport polymkeric substance provides the charge-transport layer of the good resistance to abrasion of performance.This charge transport polymkeric substance can be known polymkeric substance.In them, the preferred polycarbonate that has the triarylamine structure at its main chain and/or side chain (one or more), more preferably below structural formula (I-2) to the charge transport polymkeric substance of (XIII-2) expression.

Structural formula (I-2)

[0112] R wherein ¹⁰¹, R ¹⁰²And R ¹⁰³That each expression replaces or unsubstituted alkyl or halogen atom; R ¹⁰⁴Expression hydrogen atom or replacement or unsubstituted alkyl; R ¹⁰⁵And R ¹⁰⁶Replace or the unsubstituted aryl of each expression; O, p or q are 0 to 4 integers; k ¹⁰¹Satisfy relation of plane: 0.1≤k down respectively with j ¹⁰¹≤ 1 and 0≤j≤0.9; n ¹⁰¹Be number of repeating units, and be 5 to 5,000 integer; And X ¹⁰¹The divalent group of expression aliphatic divalent group, divalence alicyclic group or following structural (II-2) expression.

Structural formula (II-2)

R wherein ¹⁰⁷And R ¹⁰⁸That each expression replaces or unsubstituted alkyl, aryl or halogen atom; And R ¹⁰⁷And R ¹⁰⁸Can be identical or different; l ¹⁰¹Or m ¹⁰¹It is 0 to 4 integer; Y represents singly-bound, has straight chain, side chain or the cyclic alkylidene of 1 to 12 carbon atom ,-O-,-S-,-SO-,-SO ₂-,-CO-,-group of CO-O-Z-O-CO-(wherein Z represents aliphatic divalent group) or following structural (III-2) expression.

Structural formula (III-2)

[0114] wherein a is 1 to 20 integer; B is 1 to 2,000 integer; R ¹⁰⁹And R ¹¹⁰That each expression replaces or unsubstituted alkyl or aryl; And R ¹⁰⁹And R ¹¹⁰Can be identical or different.

Structural formula (IV-2)

[0115] R wherein ¹¹¹And R ¹¹²Replace or the unsubstituted aryl of each expression; Ar ¹⁰¹, Ar ¹⁰²And Ar ¹⁰³---it is identical or different, and each represents arylidene; And X ¹⁰¹, k ¹⁰¹, j and n ¹⁰¹Meaning and the described same meaning of said structure formula (I-2).

Structural formula (V-2)

[0115b] be R wherein ¹¹³And R ¹¹⁴Replace or the unsubstituted aryl of each expression; Ar ¹⁰⁴, Ar ¹⁰⁵And Ar ¹⁰⁶---it is identical or different, and each represents arylidene; And ¹⁰¹, k ¹⁰¹, j and n ¹⁰¹Meaning and the described same meaning of said structure formula (I-2).

Structural formula (VI-2)

[0116] R wherein ¹¹⁵And R ¹¹⁶Replace or the unsubstituted aryl of each expression; Ar ¹⁰⁷, Ar ¹⁰⁸And Ar ¹⁰⁹---it is identical or different, and each represents arylidene; And ¹⁰¹, k ¹⁰¹, j and n ¹⁰¹Meaning and the described same meaning of said structure formula (I-2).

Structural formula (VII-2)

[0117] R wherein ¹¹⁷And R ¹¹⁸Replace or the unsubstituted aryl of each expression; Ar ¹¹⁰, Ar ¹¹¹And Ar ¹¹²---it is identical or different, and each represents arylidene; X ¹⁰²And X ¹⁰³That each expression replaces or unsubstituted ethylene or that replace or unsubstituted vinylene; And ¹⁰¹, k ¹⁰¹, j and n ¹⁰¹Meaning and the described same meaning of said structure formula (I-2).

Structural formula (VIII-2)

[0118] R wherein ¹¹⁹, R ¹²⁰, R ¹²¹And R ¹²²Replace or the unsubstituted aryl of each expression; Ar ¹¹³, Ar ¹¹⁴, Ar ¹¹⁵And Ar ¹¹⁶---it is identical or different, and each represents arylidene; Y ₁, Y ₂And Y ₃---it can be identical or different, each expression singly-bound, replacement or unsubstituted alkylidene group, replacement or unsubstituted ring alkylidene group, replacement or unsubstituted inferior hydrocarbyl ether base, Sauerstoffatom, sulphur atom or vinylene; And ¹⁰¹, k ¹⁰¹, j and n ¹⁰¹Meaning and the described same meaning of said structure formula (I-2).

Structural formula (IX-2)

[0119] R wherein ¹²³And R ¹²⁴Each expression hydrogen atom, replacement or unsubstituted aryl; R ¹²³And R ¹²⁴Can be connected to form ring; Ar ¹¹⁷, Ar ¹¹⁸And Ar ¹¹⁹---it is identical or different, and each represents arylidene; And X ¹⁰¹, k ¹⁰¹, j and n ¹⁰¹Meaning and the described same meaning of said structure formula (I-2).

Structural formula (X-2)

[0120] R wherein ¹²⁵Replace or the unsubstituted aryl of expression; Ar ¹²⁰, Ar ¹²¹, Ar ¹²²And Ar ¹²³---it is identical or different, and each represents arylidene; And X ¹⁰¹, k ¹⁰¹, j and n ¹⁰¹Meaning and the described same meaning of said structure formula (I-2).

Structural formula (XI-2)

[0121] R wherein ¹²⁶, R ¹²⁷, R ¹²⁸And R ¹²⁹Replace or the unsubstituted aryl of each expression; Ar ¹²⁴, Ar ¹²⁵, Ar ¹²⁶, Ar ¹²⁷And Ar ¹²⁸---it is identical or different, and each represents arylidene; And X ¹⁰¹, k ¹⁰¹, j and n ¹⁰¹Meaning and the described same meaning of said structure formula (I-2).

Structural formula (XII-2)

[0122] R wherein ¹³⁰And R ¹³¹Replace or the unsubstituted aryl of each expression; Ar ¹²⁹, Ar ¹³⁰And Ar ¹³¹---it is identical or different, and each represents arylidene; And X ¹⁰¹, k ¹⁰¹, j and n ¹⁰¹Meaning and the described same meaning of said structure formula (I-2).

Structural formula (XIII-2)

[0123] Ar wherein ¹³², Ar ¹³³, Ar ¹³⁴, Ar ¹³⁵And Ar ¹³⁶Replace or the unsubstituted aromatic ring group of each expression; Z represent the aromatic ring group or-Ar ¹³⁷-Za-Ar ¹³⁷-, Ar wherein ¹³⁷Replace or the unsubstituted aromatic ring group of expression; Za represents O, S or alkylidene group; R ¹³²And R ¹³³Each expression straight or branched alkylidene group; m ¹⁰²Be 0 or 1; And X ¹⁰¹, k ¹⁰¹, j and n ¹⁰¹Meaning and the described same meaning of said structure formula (I-2).

[0124] will by combine separately or with binder resin, the charge transport material be dispersed or dissolved in that coating liquid prepared in the appropriate solvent is applied on the charge generation layer and dry, formation charge-transport layer 37.If desired, also softening agent, leveler, antioxidant or other additive can be mixed coating liquid.These additives can be used alone or be used in combination.

[0125] method that is used to be coated with coating liquid can be that traditional method such as dip-coating, spraying, pearl are coated with, nozzle coating, rotary coating or ring be coated with.

[0126] next, individual layer photoconductive layer 33 will be described.This layer can be by forming by charge generating material being distributed to photoelectric conductor material prepared in the binder resin.Individual layer photoconductive layer 33 can be by coating with charge generating material, charge transport material and binder resin dissolving or be dispersed in the coating liquid for preparing in the appropriate solvent, and drying coated liquid and forming.

[0127] if desired, softening agent, leveler, antioxidant or other additive can be mixed coating liquid.

[0128] binder resin comprises the resin that above-described and charge-transport layer 37 and charge generation layer 35 are relevant.Needless to say, preferably use above-mentioned charge transport polymkeric substance.By the quality of per 100 parts of binder resins, the amount of charge generating material is preferably 5 parts to 40 parts by mass.By the quality of per 100 parts of binder resins, the amount of charge transport material is preferably 0 part to 190 parts by mass, more preferably by mass 50 parts to 150 parts.Photoconductive layer can followingly form: use dispersion mixer that charge generating material, binder resin and charge transport dispersion of materials are gone in the solvent (for example tetrahydrofuran (THF), diox, ethylene dichloride or hexanaphthene); And by dip-coating, spraying, pearl be coated with, nozzle is coated with and the resulting coating liquid of ring coating.The thickness of photoconductive layer suitably is that about 5 μ m are to about 25 μ m.

[0129] in photo-conductor of the present invention, can between conductive carrier 31 and photoconductive layer, provide lower floor (underlying layer).Lower floor is usually mainly by resin formation.Consider and next use solvent to form photoconductive layer, described resin preferably has high resistance to ordinary organic solvents.The example of resin comprises water soluble resin (for example polyvinyl alcohol, casein and sodium polyacrylate); Spirit-soluble resin (for example nylon copolymer and methoxymethyl nylon); With the curable resin (for example urethane resin, melamine resin, phenol resins, alkyd-melamine resin and Resins, epoxy) that forms three-dimensional net structure.The particulate pigment of metal oxide can be contained in lower floor, metal oxide such as titanium oxide, silicon-dioxide, aluminum oxide, zirconium white, stannic oxide or Indium sesquioxide, and it for example is used for, and the prevention ripple produces (moiregeneration) and reduces residual electric potential.

[0130] similar to the formation photoconductive layer, use appropriate solvent and coating process can form lower floor.In the present invention, lower floor also can be formed by silane coupling agent, titanium coupling agent or chromium coupling agent.In addition, lower floor can be the Al that forms by anodic oxidation ₂O ₃Film; From organic materials (for example poly-to inferior dimethyl benzene (polyphenylene ethyl)) or inorganic materials (SiO for example ₂, SnO ₂, TiO ₂, ITO or CeO ₂), by the film of film under vacuum preparation method formation; Or other known film.The thickness of lower floor suitably is that 0 μ m is to 5 μ m.

[0131] in photo-conductor of the present invention, can on photoconductive layer, provide protective layer 39 to protect.Protective layer 39 can be by for example following resin formation: ABS resin; the ACS resin; alkene-ethylene monomer copolymer; the chlorating polyethers; the aryl resin; phenol resins; polyacetal; polymeric amide; polyamidoimide; polyacrylic ester; polyene propyl group sulfone; polybutene; polybutyleneterephthalate; polycarbonate; polyethersulfone; polyethylene; polyethylene terephthalate; polyimide; acrylic resin; polymethylpentene; polypropylene; polyphenylene oxide; polysulfones; polystyrene; polyarylate; the AS resin; butadiene-styrene copolymer; urethane; polyvinyl chloride; poly(vinylidene chloride) or Resins, epoxy.Consider that from the dispersive ability of reinforcing filler and the viewpoint of minimizing residual electric potential and film defective applying polycarbonate or polyarylate are particularly advantageous.

[0132] protective layer of photo-conductor contains filler material to strengthen its resistance to abrasion.Being used to disperse the solvent of filler material can be the above-mentioned any solvent (for example tetrahydrofuran (THF), diox, toluene, methylene dichloride, mono chloro benzene, ethylene dichloride, pimelinketone, methyl ethyl ketone and acetone) that is used to form charge-transport layer 37.Preferably, employed solvent shows during being coated with and is highly volatile.Do not show under the situation of solvent of above-mentioned characteristic, during dispersion show full-bodied solvent can be that high-volatile solvent is used in combination during being coated with.Use such solvent or the mixture can greatly reinforcing filler dispersive ability, and reduce residual electric potential.

[0133] protective layer can contain the amine compound (describing below) that prevents agent as rubber or resin material variation.Equally, adding charge transport material (or polymkeric substance)---it is described about charge-transport layer 37 in the above, is being favourable aspect minimizing residual electric potential and the raising picture quality.

[0134] method that is used to form protective layer can be that traditional method such as dip-coating, spraying, pearl are coated with, nozzle coating, rotary coating or ring be coated with.Consider the advantageous applications spraying from obtaining the film forming inhomogeneity viewpoint of institute's shape.

[0135] in photo-conductor of the present invention, can between photoconductive layer and protective layer, provide the middle layer.The middle layer is mainly formed by binder resin usually.The example of binder resin comprises polymeric amide, alcohol soluble nylon, water-soluble poval butyral, polyvinyl butyral acetal and polyvinyl alcohol.Form the middle layer by above-mentioned conventional coating process.The thickness in middle layer suitably is that about 0.05 μ m is to about 2 μ m.

[0136] in the present invention; for the environmental stability that improves photo-conductor (especially; prevent that susceptibility from reducing and residual electric potential increases), antioxidant, softening agent, lubricant, UV light absorber or leveler can be mixed each layer of charge generation layer, charge-transport layer, lower floor and protective layer.The typical example of these additives is listed below.

＜＜antioxidant〉〉

[0137] example of antioxidant includes but not limited to list below.

(a) phenolic compound:

2,6-di-t-butyl-p-Cresol, butylated hydroxyanisol, 2,6-di-t-butyl-4-ethylphenol, Octadecane base-3-(4 '-hydroxyl-3 ', 5 '-DI-tert-butylphenol compounds), 2,2 '-methylene radical-two-(4-methyl-6-tert butyl phenol), 2,2 '-methylene radical-two-(4-ethyl-6-tert.-butyl phenol), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 4,4 '-butylidene is two-and (3 methy 6 tert butyl phenol), 1,1,3-three-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, four-[methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester] methane, two [3,3 '-two (4 '-hydroxyl-3 '-tert-butyl-phenyl) butyric acid] glycol ester, tocopherol etc.

(b) Ursol D:

N-phenyl-N '-sec.-propyl-Ursol D, N, N '-two sec-butyls-Ursol D, N-phenyl-N-sec-butyl-Ursol D, N, N '-two-sec.-propyl-Ursol D, N, N '-dimethyl-N, N '-di-t-butyl-Ursol D etc.

(c) quinhydrones:

2,5-two uncle's octyl group quinhydrones, 2,6-two-dodecyl quinhydrones, 2-dodecyl quinhydrones, 2-dodecyl-5-chlorohydroquinone, uncle's 2-octyl group-5-toluhydroquinone, 2-(2-octadecyl)-5-toluhydroquinone etc.

(d) sulfur-containing organic compound:

Dilauryl-3,3 '-thiodipropionate, distearyl-3,3 '-thiodipropionate, two-tetradecyl-3,3 '-thiodipropionate etc.

(e) organophosphorus compound:

Triphenyl phosphine, three (nonyl phenyl) phosphine, three (dinonyl phenyl) phosphine, three cresols phosphines, three (2,4-dibutyl phenoxy group) phosphine etc.

＜＜softening agent〉〉

[0138] example of softening agent includes but not limited to list below.

(a) phosphate plasticizer:

Triphenylphosphate, tritolyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, trichloroethyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenylphosphate etc.

(b) phthalate plasticizers:

Dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, dimixo-octyl phthalate, dinoctyl phthalate, Dinonylphthalate, diisononyl phthalate, Di Iso Decyl Phthalate, phthalic acid two (undecane) ester, phthalic acid two (tridecane) ester, dicyclohexyl phthalate, butyl benzyl phthalate, butyl lauryl phthalate, O-phthalic acid methyl oil base ester, phthalic acid octyl group ester in the last of the ten Heavenly stems, dibutyl phthalate, dioctyl phthalate (DOP) etc.

(c) aromatic carboxylic acid's ester plasticizer:

Trioctyl trimellitate, tri trimellitate n-octyl, oxybenzene octyl formate etc.

(d) fatty group dibasic acid softening agent:

Polycizer W 260, di-n-hexyl adipate, di-2-ethylhexyl adipate, hexanodioic acid n-caprylic acid ester, hexanodioic acid n-octyl-positive ester in the last of the ten Heavenly stems, diisodecyl adipate, Octyl adipate, di(2-ethylhexyl)azelate, dimethyl sebacate, ethyl sebacate, Uniflex DBS, dioctyl sebacate, Diisooctyl Sebacate, sebacic acid two-2-ethoxy ethyl ester, dioctyl succinate, succsinic acid two isodecyl esters, tetrahydro-2-ethylhexyl phthalate, di-n-octyl tetrahydrophthalate etc.

(e) aliphatic ester derivatives:

Butyl oleate, XU 61518.10, methyl acetyl ricinoleate, pentaerythritol ester, Dipentaerythritol six esters, triacetin, tributyrin etc.

(f) alcohol ester softening agent:

Methyl acetyl ricinoleate, acetyl butyl ricinoleate, butyl phthalyl butyl glycolate, tributyl acetylcitrate etc.

(g) epoxy plasticizer:

Epoxidized soybean oil, epoxidised linseed oil, butyl epoxy stearate, epoxystearic acid ester in the last of the ten Heavenly stems, octyl epoxy stearate, epoxystearic acid benzyl ester, epoxy di-2-ethylhexyl hexahy-, epoxy hexahydrophthalic acid didecyl ester etc.

(h) binary alcohol esters softening agent:

Diethylene glycol dibenzoate, triglycol two-2 Ethylbutanoic acid ester etc.

(i) chloro-plasticizer:

The methyl esters of the methyl esters of clorafin, chlorodiphenyl, chlorination lipid acid, methoxyl group chlorination lipid acid etc.

(j) polyester plasticizer:

Polypropylene adipate (PPA), poly-sebacic acid propylene glycol ester, polyester, acetylize polyester etc.

(k) sulfonic acid:

Para toluene sulfonamide, orthotoluene sulfonamide, tolysulfonyl ethamine, adjacent toluenesulfonyl ethylamine N-, tolylsulfonyl-N-ethanamide, tolysulfonyl-N-Cyclohexamide etc.

(1) citric acid derivant:

Triethyl citrate, acetyl triethyl citrate, tributyl citrate, tributyl acetylcitrate, acetyl tributyl citrate three-2-ethylhexyl, acetyl tributyl citrate n-octyl ester in the last of the ten Heavenly stems etc.

(m) other:

Terphenyl, partially hydrogenated terphenyl, camphor, 2 nitro biphenyl, dinonyl naphthalene, methyl abietate etc.

＜＜lubricant〉〉

[0139] example of lubricant includes but not limited to list below.

(a) hydrocarbon compound:

Whiteruss, paraffin, Microcrystalline Wax, oligomerization polyethylene etc.

(b) fatty acid cpds:

Lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid, mountain Yu acid etc.

(c) fatty acid amide compound:

Stearylamide, palmitic amide, amine hydroxybenzene, methylene-bis stearylamide, ethylenebisstearamide etc.

(d) ester compound:

Lipid acid-low-carbon-ester, lipid acid-polyol ester, lipid acid-macrogol ester etc.

(e) alcohol compound:

Cetyl alcohol, Stearyl alcohol, ethylene glycol, polyoxyethylene glycol, Polyglycerine etc.

(f) metallic soap:

Lead stearate, cadmium stearate, barium stearate, calcium stearate, Zinic stearas, Magnesium Stearate etc.

(g) naturally occurring wax:

Carnauba wax, gama wax, beeswax, spermaceti, Chinese wax, montanin wax etc.

(h) other:

Silicone compounds, fluorine cpd etc.

＜＜UV light absorber〉〉

[0140] example of UV light absorber includes but not limited to list below.

(a) benzophenone:

2-dihydroxy benaophenonel, 2,4 dihydroxyl benzophenone, 2,2 ', 4-trihydroxybenzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2,2 '-dihydroxyl-4-methoxy benzophenone etc.

(b) salicylate:

Salol, 2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester etc.

(c) benzotriazole category:

(2 '-hydroxyphenyl) benzotriazole, (2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, (2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, (2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl) 5-chlorobenzotriazole etc.

(d) cyanoacrylate:

Ethyl-2-cyano group-3,3-diphenylacrylate ester, methyl-2-methoxycarbonyl-3 (to methoxyl group) acrylate etc.

(e) quencher (metal complex salts):

(2,2 '-thiobis (uncle's 4-octyl group) phenol) nickel n-Butyl Amine 99, nickel dibutyl dithiocarbamate, dicyclohexyl phosphorodithioic acid cobalt etc.

(f) HALS (hindered amine):

Two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, 1-[2-[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy]-2,2,6,6-tetramethyl pyridine, 8-benzyl-7,7,9,9-tetramethyl--3-octyl group-1,3,8-thriazaspiro [4,5] undecane-2,4-diketone, 4-benzoyloxy-2,2,6,6-tetramethyl piperidine etc.

[0141] with reference to the accompanying drawings, will describe electrophotographic method of the present invention and electronic photographing device in detail below.

[0142] Fig. 7 is the synoptic diagram that is used to describe electrophotographic method of the present invention and electronic photographing device.The method and apparatus that describes in detail below belongs to scope of the present invention.

[0143] in Fig. 7, photo-conductor 1 has cydariform.Alternatively, photo-conductor 1 can have stratiform or ring-band shape.Around photo-conductor 1, provide charger 3, pre-transfer charger 7, transfer printing charger 10, separating charger 11, precleaning charger 13, imaging exposed portion 5, electric charge to eliminate lamp 2, developing element 6, hairbrush 14, cleaning blade 15, eraser 4, resistance roller 8 and disconnecting hook 12.Each charger can be any known charger, for example corona tube charger, grid electrode charger, solid-state charger and charging roller.

[0144] generally speaking, transferring member can be above-mentioned any charger.Advantageously, transferring member is the transfer printing charger shown in Figure 7 and the combination of separating charger.

[0145] being used for imaging exposed portion 5, electric charge, to eliminate the light source of lamp 2 etc. can be for example luminescent lamp, tungsten lamp, halogen lamp, mercury lamp, sodium vapor lamp, photodiode (LED), laser diode (LD) or electroluminescent (EL) lamp of common luminaire.Equally, have the light of expecting wavelength, can use spectral filter for application.Spectral filter can be that for example sharp cutoff filter, bandpass optical filter, near infrared cutoff wavelength spectral filter, dichroic filter, interference light filter or colour temperature transform spectral filter.Photo-conductor 1 in transfer step, electric charge removal process, cleaning or pre-exposure step with rayed (each step comprises rayed).

[0146] uses toner particles on photo-conductor 1, to make image developing by developing element 6, and ink powder image is transferred to transfer paper 9.During this transfer printing, some toner particles are retained on the photo-conductor 1.By hairbrush 14 and cleaning blade 15 this residual toner particle is removed from photo-conductor.In some cases, only carrying out ink powder by cleaning brush removes.Cleaning brush can be known brush such as hairbrush or magnetic hairbrush (magfur brush).

[0147] photoelectric conductor for electronic photography just is being provided (bearing) charging, photoelectric conductor for electronic photography experience imaging exposure then, thereby electrostatic latent image just (is being born) in formation thereon.When using negative (just) charging toner particles (charge detection particulate) just carrying out (bear) latent electrostatic image developing, obtain positive image, otherwise when using when just (bearing) toner particles of charging and just carrying out (bearing) latent electrostatic image developing the acquisition negative image.The developing element that carries out said process can use known method.Electric charge is eliminated element also can use known method.

[0148] Fig. 8 illustrates another embodiment of electrophotographic method of the present invention.The equipment of Shi Yonging has light source (imaging exposure source) 24, developing apparatus (not having diagram), transfer printing charger 25, light source 26, cleaning brush 27 and the electric charge elimination light source 28 of photo-conductor 21, driving

roll

22a and 22b, charger 23, imaging exposure in the method.Photo-conductor 21 has photoconductive layer at least, also contains filler in the upper strata.In the method, when photo-conductor 21 driven rolls drive, has recirculation like this: comprise charger 23 chargings, the 24 imaging exposures of imaging exposure source, developing apparatus development, 25 transfer printings of transfer printing charger, light source 26 precleaning exposures, cleaning brush 27 cleanings and the elimination of electric charge elimination light source 28 electric charges.In the equipment shown in Fig. 8,, carry out precleaning exposure (in this case, carrier has optical transparence) by using up from side in the face of the carrier of photo-conductor 21.

[0149] above-mentioned electrophotographic method is an illustrative embodiments of the present invention, and needless to say, other embodiment also can be implemented.For example, although the precleaning exposure is carried out in the carrier side of Fig. 8, also can on the photoconductive layer side, carry out this exposure.Similarly, with different, also can should use up and carry out imaging exposure and electric charge elimination by from side in the face of the photo-conductor carrier in the situation shown in Fig. 8.

[0150] in addition, although in Fig. 8, after imaging exposure, precleaning exposure and electric charge are eliminated exposure, use light irradiates light electric conductor, but, can carry out other rayed (for example pre-transfer is exposed and is used for the pre-exposure that imaging exposes) by known rayed step is provided.

[0151] above-mentioned image formation component can be fixed in duplicating machine, facsimile recorder or the printer; Perhaps can be installed in wherein with the form of process cartridge.Process cartridge is one piece apparatus (parts), and it comprises photo-conductor, charge member, exposure element, developing element, transferring member, cleaning element and electric charge elimination element.The shape of process cartridge etc. can change, and its typical example is shown in Figure 9.In Fig. 9,

reference number

16,17,18,19 and 20 is represented photo-conductor, charger, cleaning brush, imaging exposed portion and developer roll respectively.Embodiment

[0152] hereinafter, the present invention will be described by embodiment, and it should not be understood that to limit the invention to this.In an embodiment, " in mass, part (a or many parts) " can be called " part (a or many parts) " for short.(embodiment 1) (generation of an imide compound)

[0153] with naphthalene-1,4,5, (5.36g, 20.0mmol), N, dinethylformamide (30mL) and acetate (3mL) join in the bottle 8-tetracarboxylic dianhydride (TOKYO CHEMICAL INDUSTRY CO., the product of LTD.), reflux then.Under agitation, in about 2 hours, will be at N, (2.42g, 21.0mmol) solution dropwise joins in the formed mixture 2-heptyl amice in the dinethylformamide (6mL).Further, under refluxing, made mixture reaction 5 hours.After cooling, under reduced pressure, evaporating solvent.Toluene is joined in the residuum, and by removing by filter insoluble substance.By silica gel chromatography purifying filtrate,, thereby produce an imide compound (yield: 41.3%) of following structural (i) expression of 3.02g then from hexanaphthene/toluene recrystallization.The fusing point of finding this compound is 149.0 ℃ to 150.0 ℃.

Structural formula (i)

[0154] above-claimed cpd is carried out ultimate analysis.The result is shown in the table 6.

Table 6

	C	H	N
	C	H	N	Discovery value (measured value)	69.05	5.27	3.74
Calculated value	69.03	5.24	3.83	Discovery value (measured value)	69.05	5.27	3.74

[0155] by KBr tabletting method (tablet method), make above-claimed cpd carry out infrared spectra.Resulting infrared absorption spectrum is 1,787cm ^-1Place's performance is derived from the absorption peak of anhydride moiety, and 1,670cm ^-1Place's performance is derived from the absorption peak of imide moieties.

(corresponding to the generation of the naphthalenetetracarbacidic acidic diimide derivatives of numbering 1 compound)

[0156] under argon gas stream, with the imide compound that obtains above (1.83g 5.00mmol) is dissolved in N, dinethylformamide (anhydrous, 10mL).With N, and dinethylformamide (anhydrous, 1 in 5mL), (0.300g, solution 5.00mmol) under agitation joins in the solution 1-dimethylhydrazine (TOKYO CHEMICAL INDUSTRY CO., the product of LTD.).At room temperature, stirred formed solution 2 hours.Under reduced pressure, evaporating solvent (N, dinethylformamide), thus form orange red (tango) crystal.Use silicagel column (eluant: toluene/ethyl acetate (2/1 volume ratio)) this crystal of purifying.The orange crystal of purifying is from toluene/normal hexane recrystallization.By the dry resulting crystal of drying machine, in this drying machine, under reduced pressure heat, thus the naphthalenetetracarbacidic acidic diimide derivatives (yield: 73.0%) of the orange-yellow spicule form that generation 1.49g following structural is (ii) represented.The fusing point of finding this compound is 166.0 ℃ to 167.0 ℃.

Structural formula (ii)

[0157] resulting compound is carried out ultimate analysis.The result is shown in the table 7.

Table 7

	C	H	N
	C	H	N	The discovery value	67.91	6.10	10.22
Calculated value	67.80	6.18	10.31	The discovery value	67.91	6.10	10.22

(embodiment 2)

(generation of the compound of numbering 30)

[0158] (1.83g 5.00mmol) joins N to the part of an imide compound that will obtain in embodiment 1, in the dinethylformamide (15mL).With 1, (1.06g 5.00mmol) joins in this mixture 1-dibenzyl hydrazine (TOKYO CHEMICALINDUSTRYCO., the product of LTD.), stirs 3.5 hours in 60 ℃, argon gas stream then.Vapourisation under reduced pressure solvent (N, N '-dimethyl formamide), thus red crystals formed.Use silicagel column (eluant: toluene/ethyl acetate (30/1 volume ratio)) this crystal of purifying.From the resulting orange red crystal of ethyl acetate/ethyl alcohol recrystallization.By the dry resulting crystal of drying machine, heating under the decompression in this drying machine, thus produce 2.21g following structural numbering 30 compounds that (iii) represent, yellow spicule form (yield: 78.9%).The fusing point of finding this compound is 147.0 ℃ to 148.0 ℃.

Structural formula (iii)

[0159] resulting compound is carried out ultimate analysis.The result is shown in the table 8.

Table 8

	C	H	N
	C	H	N	The discovery value	74.98	5.88	7.53
Calculated value	75.11	5.94	7.51	The discovery value	74.98	5.88	7.53

(embodiment 3 to 21)

[0160] similar to embodiment 1 with 2, manufacturing and analysis and embodiment 3 to 21 corresponding compounds.The result illustrates at table 9-1 and 9-2.

Table 9-1

Table 9-2

(embodiment A-1)

(generation of compound (A-1))

The generation of＜one imide compound 〉

[0161] with 1,4,5,8-naphthalene tetracarboxylic acid dianhydride (5.36g, 20mmol), N, dinethylformamide (anhydrous, 30mL) and acetate (3mL) add in the bottle, reflux then.In under agitation 2 hours, with N, (anhydrous, 6mL) (2.42g, 21mmol) solution dropwise adds formed mixture to middle 2-heptyl amice to dinethylformamide.Further, under refluxing, made mixture reaction 5 hours.After the cooling, the vapourisation under reduced pressure solvent.Toluene is joined in the residuum, by removing by filter insolubles.By silica gel chromatography purifying filtrate, then from hexanaphthene/toluene recrystallization, thus the imide compound of generation 3.02g.

Ultimate analysis is (with C ₂₁H ₁₉NO ₅)

Table 10

	C	H	N
	C	H	N	Discovery value (%)	69.05	5.27	3.74
Calculated value (%)	69.03	5.24	3.83	Discovery value (%)	69.05	5.27	3.74

[0162] by KBr tabletting method (tablet method), above-claimed cpd is carried out infrared spectra.Resulting infrared absorption spectrum is 1,787cm ^-1Place's performance is derived from the absorption peak of anhydride moiety, and 1,670cm ^-1Place's performance is derived from the absorption peak of imide moieties.

(generation of target compound)

The part of a imide compound that [0163] will obtain above (1.83g, 5mmol), N, dinethylformamide (anhydrous, 30mL) and acetate (1mL) join in the bottle.Under agitation, (0.60g 6mmol) dropwise joins in the mixture with the 1-amino piperidine.Formed mixture heating up is arrived about 80 ℃, and it was further reacted 4 hours.After the cooling, the vapourisation under reduced pressure solvent.With washing with alcohol residuum (product), filter then.From normal hexane-toluene and the ethanol-toluene resulting product of recrystallization repeatedly, thereby produce the target naphthalenetetracarbacidic acidic diimide derivatives (compound (A-1)) of 1.54g.

Fusing point: 184.5 ℃ to 185.5 ℃

Ultimate analysis is (with C ₂₆H ₂₉N ₃O ₄)

Table 11

	C	H	N
	C	H	N	Discovery value (%)	69.85	6.41	9.44
Calculated value (%)	69.78	6.53	9.39	Discovery value (%)	69.85	6.41	9.44

[0164] by the KBr tabletting method, above-claimed cpd is carried out infrared spectra.Resulting infrared absorption spectrum is 1,787cm ^-1The place does not have to show the absorption peak that is derived from anhydride moiety, and 1,683cm ^-1With 1,660cm ^-1Place's performance is derived from the strong absorption peak of amide moieties.

(embodiment A-2)

(generation of compound (A-14))

[0165] part of an imide compound that will in embodiment A-1, obtain (1.83g, 5mmol), N, dinethylformamide (anhydrous, 30mL) and acetate (2mL) join in the bottle.Stir down, (0.77g 6mmol) dropwise joins in the mixture with 1-amino-lupetidine.Formed mixture heating up is arrived about 80 ℃, and it was further reacted 5 hours.After the cooling, the vapourisation under reduced pressure solvent.Toluene is joined in the residuum (product), wash the organic layer of formation with water, then by the silica gel chromatography purifying, thus the target naphthalenetetracarbacidic acidic diimide derivatives (compound (A-14)) of generation 1.48g.Fusing point: 95.0 ℃ to 98.0 ℃

Ultimate analysis is (with C ₂₈H ₃₃N ₃O ₄)

Table 12

	C	H	N
	C	H	N	Discovery value (%)	70.77	7.04	8.69
Calculated value (%)	70.71	6.99	8.84	Discovery value (%)	70.77	7.04	8.69

[0166] by the KBr tabletting method, above-claimed cpd is carried out infrared spectra.Resulting infrared absorption spectrum is 1,787cm ^-1The place does not have to show the absorption peak that is derived from anhydride moiety, and 1,683cm ^-1With 1,660cm ^-1Place's performance is derived from the strong absorption peak of amide moieties.

(embodiment A-3)

(generation of compound (A-21))

[0167] part of an imide compound that will in embodiment A-1, obtain (1.83g, 5mmol), N, dinethylformamide (anhydrous, 30mL) and acetate (2mL) join in the bottle.Stir down, (0.69g 6mmol) dropwise joins in the mixture with the amino high piperidines of 1-.Formed mixture heating up is arrived about 80 ℃, and it was further reacted 4 hours.After the cooling, the vapourisation under reduced pressure solvent.With methanol wash residuum (product), filter then.By the resulting product of silica gel chromatography purifying, thus the target naphthalenetetracarbacidic acidic diimide derivatives (compound (A-21)) of generation 1.53g.

Fusing point: 132.0 ℃ to 133.0 ℃

Ultimate analysis is (with C ₂₇H ₃₁N ₃O ₄)

Table 13

	C	H	N
	C	H	N	Discovery value (%)	70.35	6.79	9.23
Calculated value (%)	70.26	6.77	9.10	Discovery value (%)	70.35	6.79	9.23

[0168] by the KBr tabletting method, above-claimed cpd is carried out infrared spectra.Resulting infrared absorption spectrum is 1,787cm ^-1The place does not have to show the absorption peak that is derived from anhydride moiety, and 1,679cm ^-1With 1,654cm ^-1Place's performance is derived from the strong absorption peak of amide moieties.

(embodiment A-4)

(generation of compound (A-29))

[0169] with the imide compound that obtains in the embodiment A-1 (3.65g, 10mmol) and N, dinethylformamide (anhydrous, 40mL) join in the bottle.Stir down, (1.38g 12mmol) dropwise joins in the mixture with 1-amino-4-methylpiperazine.Formed mixture was at room temperature further reacted 6 hours.The vapourisation under reduced pressure solvent.With methanol wash residuum (product), filter then.From hexanaphthene-toluene and the ethanol-toluene resulting product of recrystallization repeatedly, thereby produce the target naphthalenetetracarbacidic acidic diimide derivatives (compound (29)) of 3.7g.

Fusing point: 210.0 ℃ to 210.5 ℃

Ultimate analysis is (with C ₂₆H ₃₀N ₄O ₄)

Table 14

	C	H	N
	C	H	N	Discovery value (%)	67.58	6.68	12.09
Calculated value (%)	67.51	6.54	12.11	Discovery value (%)	67.58	6.68	12.09

[0170] by the KBr tabletting method, above-claimed cpd is carried out infrared spectra.Resulting infrared absorption spectrum is 1,787cm ^-1The place does not have to show the absorption peak that is derived from anhydride moiety, and 1,683cm ^-1With 1,658cm ^-1Place's performance is derived from the strong absorption peak of amide moieties.

(embodiment A-5)

(generation of compound (A-41))

[0171] imide compound that embodiment A-1 is obtained (3.65g, 10mmol), N, dinethylformamide (anhydrous, 60mL) and acetate (5mL) join in the bottle.Stir down, (1.23g 12mmol) dropwise joins in the mixture with the amino morpholine of N-.Formed mixture heating up is arrived about 80 ℃, and it was further reacted 2 hours.After the cooling, the vapourisation under reduced pressure solvent.With methanol wash residuum (product), filter then.From hexanaphthene-toluene and the ethanol-toluene resulting product of recrystallization repeatedly, thereby produce the target naphthalenetetracarbacidic acidic diimide derivatives (compound (41)) of 3.62g.

Fusing point: 200.0 ℃ to 201.5 ℃

Ultimate analysis is (with C ₂₅H ₂₇N ₃O ₅)

Table 15

	C	H	N
	C	H	N	Discovery value (%)	66.95	6.24	9.22
Calculated value (%)	66.80	6.05	9.35	Discovery value (%)	66.95	6.24	9.22

[0172] by the KBr tabletting method, above-claimed cpd is carried out infrared spectra.Resulting infrared absorption spectrum is 1,787cm ^-1The place does not have to show the absorption peak that is derived from anhydride moiety, and 1,683cm ^-1Place's performance is derived from the strong absorption peak of amide moieties.

(embodiment A-6)

(generation of compound (A-2))

(generation of an imide compound)

[0173] with 1,4,5, and 8-naphthalene tetracarboxylic acid acid anhydride (2.7g, 10mmol) and N, dinethylformamide (anhydrous, 25mL) join in the bottle, reflux then.Stir down, in about 1 hour, with N, (anhydrous, 5mL) (1.34g, 10.3mmol) solution dropwise joins in the mixture 2-amino-octane in dinethylformamide.Under refluxing, formed mixture was further reacted 6 hours.After the cooling, the vapourisation under reduced pressure solvent.Toluene is joined in the residuum, and by removing by filter insolubles.By silica gel chromatography purifying filtrate, then from the hexanaphthene recrystallization, thus the imide compound of generation 1.6g.

Ultimate analysis is (with C ₂₂H ₂₁NO ₅)

Table 16

	C	H	N
	C	H	N	Discovery value (%)	69.69	5.41	3.66
Calculated value (%)	69.66	5.58	3.69	Discovery value (%)	69.69	5.41	3.66

[0174] by the KBr tabletting method, above-claimed cpd is carried out infrared spectra.Resulting infrared absorption spectrum is 1,787cm ^-1Place's performance is derived from the absorption peak of anhydride moiety, and 1,667cm ^-1Place's performance is derived from the absorption peak of imide moieties.

(generation of target compound)

[0175] a imide compound that will obtain above (1.90g, 5mmol), N, dinethylformamide (anhydrous, 30mL) and acetate (2mL) join in the bottle.Under agitation, (0.60g 6mmol) dropwise joins in the mixture with the 1-amino piperidine.Formed mixture heating up is arrived about 80 ℃, and it was further reacted 4 hours.After the cooling, the vapourisation under reduced pressure solvent.With methanol wash residuum (product), filter then.From the hexanaphthene resulting product of recrystallization repeatedly, thereby produce the target naphthalenetetracarbacidic acidic diimide derivatives (compound (A-2)) of 2.13g.

Fusing point: 187.5 ℃ to 188.0 ℃

Ultimate analysis is (with C ₂₇H ₃₁N ₃O ₄)

Table 17

	C	H	N
	C	H	N	Discovery value (%)	70.34	6.65	9.22
Calculated value (%)	70.26	6.77	9.10	Discovery value (%)	70.34	6.65	9.22

[0176] by the KBr tabletting method, make above-claimed cpd carry out infrared spectra.Resulting infrared absorption spectrum is 1,787cm ^-1The place does not have to show the absorption peak that is derived from anhydride moiety, and 1,675cm ^-1With 1,660cm ^-1Place's performance is derived from the strong absorption peak of amide moieties.

(embodiment A-7)

(generation of compound (A-42))

[0177] with the imide compound that obtains in the embodiment A-6 (1.90g, 5mmol), N, dinethylformamide (anhydrous, 30mL) and acetate (3mL) join in the bottle.Stir down, (0.61g 6mmol) dropwise joins in the mixture with the amino morpholine of N-.Formed mixture heating up is arrived about 80 ℃, and it was further reacted 5 hours.After the cooling, the vapourisation under reduced pressure solvent.With methanol wash residuum (product), filter then.From normal hexane-toluene and the ethanol-toluene resulting product of recrystallization repeatedly, thereby produce the target naphthalenetetracarbacidic acidic diimide derivatives (compound (42)) of 2.20g.

Fusing point: 198.5 ℃ to 200.0 ℃

Ultimate analysis is (with C ₂₆H ₂₉N ₃O ₅)

Table 18

	C	H	N
	C	H	N	Discovery value (%)	67.44	6.35	9.17
Calculated value (%)	67.37	6.31	9.06	Discovery value (%)	67.44	6.35	9.17

[0178] by the KBr tabletting method, make above-claimed cpd carry out infrared spectra.Resulting infrared absorption spectrum is 1,787cm ^-1The place does not have to show the absorption peak that is derived from anhydride moiety, and 1,675cm ^-1Place's performance is derived from the strong absorption peak of amide moieties.

Application Example (according to the embodiment A-3 of JP-A2007-108682)

[0179] the following manufacturing of the photoelectric conductor for electronic photography that in Application Example, uses.

[0180] uses ball mill, will be as metal-free phthalocyanine pigment (Fastogen Blue8120B of charge generating material, Dainippon Ink and Chemicals, the product of Incorporated) (30 parts) disperseed 2 hours in pimelinketone (970 parts), thereby preparation dispersive charge generating material mixture.Independently, with polycarbonate resin (Zpolyca, viscosity-average molecular weight: 40,000, the product of TEIJIN CHEMICALS LTD.) (49 parts), naphthalenetetracarbacidic acidic diimide derivatives (aforesaid compound (1), as the charge transport material) (20 parts), be dissolved in the tetrahydrofuran (THF) (340 parts) as the following compounds (A-i) (29.5 parts) and the silicone oil (KF50-100CS, Shin-Etsu Chemicals Co., the product of Ltd) (0.1 part) of charge transport material.The charge generating material dispersed mixture (66.6 parts) for preparing is previously joined in the solution, stir then, thereby preparation is used to form the coating liquid (photoconductive layer-coating liquid) of photoconductive layer.

[0181] with aluminium drum (diameter: 30mm, length: 340mm)---it has 20 μ m or circle is still less beated, photoconductive layer-coating liquid that immersion prepares above also therefrom proposes, so that form photoconductive layer (thickness: 25 μ m), following dry 15 minutes at 120 ℃ then thereon.

[0182] photoelectric conductor for electronic photography that will so make is installed among the IPSiO Color 8100 (RicohCompany, the product of Ltd.) of transformation, and wherein the wavelength set of the LD that will be used to write down is 780nm, and supplying unit just changed into charges.Next, make the IPSiO Color 8100 of transformation print off 50,000 full-colour images continuously, wherein rectangular sheet (rectangular patch) and character with 6% image area than mixing.In original state or after printing 50,000, with regard to the electromotive force (exposure area current potential) of picture quality, exposure area and the electromotive force (territory, non-exposed area current potential) in territory, non-exposed area, the assessment photoelectric conductor for electronic photography.

[0183] particularly, picture quality, exposure area current potential and territory, non-exposed area current potential are following determines.

Territory, non-exposed area current potential: after original charge, be moved to the electromotive force (in current the detection, regulating charger) of the photoconductor surface of developing location with the voltage of application+700V from start to finish

Exposure area current potential: after charging and imaging exposure (exposure fully), be moved to the electromotive force of the photoconductor surface of developing location

Picture quality: in the full-colour image of output, based on the existence of the background spot that causes of charging ununiformity or there be not (when observing the background spot at white portion, photoelectric conductor for electronic photography is cited as " B ", otherwise is chosen as " A ")

Formula (A-i)

The result

Table 19

	Territory, non-exposed area current potential+V)	The exposure area current potential+V)	Picture quality
	Territory, non-exposed area current potential+V)	The exposure area current potential+V)	Picture quality	Original state	700	85	A
After printing 50,000	680	120	A	Original state	700	85	A

[0184] data that obtain from detection show, the good electron transfer capacity of naphthalenetetracarbacidic acidic diimide derivatives performance of the present invention, and advantageously be used for photoelectric conductor for electronic photography as the organic photoconductor material.

(embodiment 22)

(photoelectric conductor for electronic photography)

[0185] according to the embodiment 3 of JP-A2007-108682, following manufacturing photoelectric conductor for electronic photography of the present invention.

[0186] uses ball mill, will be as metal-free phthalocyanine pigment (Fastogen Blue8120B of charge generating material, Dainippon Inkand Chemicals, the product of Incorporated) (30 parts) disperseed 2 hours in pimelinketone (970 parts), thus preparation dispersive charge generating material mixture.Independently, with polycarbonate resin (Zpolyca, viscosity-average molecular weight: 40,000, the product of TEIJIN CHEMICALS LTD.) naphthalenetetracarbacidic acidic diimide derivatives of (49 parts), embodiment 16 (20 parts), have following structural charge transport material (29.5 parts) and silicone oil (KF50-100CS (iv), Shin-Etsu Chemicals Co., the product of Ltd) (0.1 part) is dissolved in the tetrahydrofuran (THF) (340 parts).The charge generating material dispersed mixture (66.6 parts) for preparing is previously joined in the solution, stir then, thereby preparation is used to form the coating liquid (photoconductive layer-coating liquid) of photoconductive layer.

[0187] with aluminium drum (diameter: 30mm, length: 340mm)---it has 20 μ m or circle is still less beated, photoconductive layer-coating liquid that immersion prepares above also therefrom proposes, so that form photoconductive layer (thickness: 25 μ m), following dry 15 minutes at 120 ℃ then thereon.

[0188] photoelectric conductor for electronic photography that will so make is installed among the IPSiO Color 8100 (RicohCompany, the product of Ltd.) of transformation, and wherein the wavelength set of the LD that will be used to write down is 780nm, and supplying unit just changed into charges.Next, make the IPSiO Color 8100 of transformation print off 50,000 full-colour images continuously, wherein rectangular sheet and character with 6% image area than mixing.In original state or after printing 50,000, with regard to picture quality, exposure area current potential and territory, non-exposed area current potential, the assessment photoelectric conductor for electronic photography.Particularly, picture quality, exposure area current potential and territory, non-exposed area current potential are by following detection.

[0189] territory, non-exposed area current potential: after original charge, be moved to the electromotive force (in current the detection, regulating charger) of the photoconductor surface of developing location with the voltage of application+700V from start to finish

[0190] exposure area current potential: after charging and imaging exposure (exposure fully), be moved to the electromotive force of the photoconductor surface of developing location

[0191] picture quality: in the full-colour image of output, based on the existence of the background spot that causes of charging ununiformity or there be not (when observing the background spot at white portion, photoelectric conductor for electronic photography is cited as " B ", otherwise is chosen as " A ")

Structural formula (iv)

(result)

(original state)

Territory, non-exposed area current potential: 700 (V)

Exposure area current potential: 80 (V)

Picture quality: A

(after printing 50,000)

Territory, non-exposed area current potential: 690 (V)

Exposure area current potential: 105 (V)

Picture quality: A

[0192] data that obtain from detection show, the good electron transfer capacity of naphthalenetetracarbacidic acidic diimide derivatives performance of the present invention, and advantageously be used for photoelectric conductor for electronic photography as the organic photoconductor material.

(embodiment 23)

[0193] on the aluminium right cylinder by dip-coating order coating lower floor coating liquid, charge generation layer coating liquid with the charge-transport layer coating liquid---each has following component, 3.5 μ m), charge generation layer (thickness: 0.2 μ m) and charge-transport layer (thickness: 23 μ m) (number 2 photo-conductor) dry then to form lower floor's (thickness:.

Lower floor's coating liquid

Titania powder (product of ISHIHARA SANGYO KAISHA LTD, TIPAQUE CR-EL): 400 parts

Melamine resin (Dainippon Ink and Chemicals, the product of Incorporated, SUPERBECKAMINE G821-60): 65 parts

Synolac (Dainippon Ink and Chemicals, the product of Incorporated, BECKOLITEM6401-50): 120 parts

2-butanone: 400 parts

The charge generation layer coating liquid

Has following structural (Fluorenone disazo pigment v): 12 parts

Structural formula (v)

Polyvinyl butyral acetal (product of Union Carbide Corporation, XYHL): 5 parts

2-butanone: 200 parts

Pimelinketone: 400 parts

The charge-transport layer coating liquid

Polycarbonate resin (Zpolyca, the product of TEIJIN CHEMICALS LTD): 10 parts

Number 8 compound naphthalenetetracarbacidic acidic diimide derivatives: 10 parts

Tetrahydrofuran (THF): 100 parts

The photoelectric conductor for electronic photography that [0193b] will so make is installed in the electrophotographic printing print cartridge.The electrophotographic printing print cartridge is installed among the imagio MF2200 (Ricoh Company, the product of Ltd.) of transformation, uses positive corona pipe chargingmethod and laser diode (LD, wavelength: 655nm) as the light source that is used for the imaging exposure.With territory, the non-exposed area potential setting of the imagio MF2200 that transforms is 800 (V), repeats printing test then.The duplicate printing test is equivalent to 100,000 and prints continuously.In this detects, assessment initial pictures or print the quality of the image that prints after 100,000.Image blurring (point resolution) following detection of image: before printing 100,000 and after, make the imagio MF2200 of transformation print 10 continuously and have 600dpi * 600dpi picture element density and have the dot image (dotted image) of 5% image density; Under stereoscopic microscope, observe the shape of the point that forms; And according to following five level evaluation edge sharpnesss (edge sharpness) (significantly, class 5 is best, and grade 1 is the poorest).

(grade of dot image assessment)

5: observe sharp-edged, good

4: observe very slight fuzzy edge, but good

3: observe slight fuzzy edge, but in fact good

2: observe fuzzy edge, and depend on the picture pattern existing problems

1: point can not be differentiated mutually

The result is shown in the table 20.

(embodiment 24 to 37 (photoelectric conductor for electronic photography))

[0194] step of repetition embodiment 23, just number 8 compound naphthalenetetracarbacidic acidic diimide derivatives and be changed to each, thereby make and analyze the photoelectric conductor for electronic photography of numbering 3 to 16 in the compound shown in the table 20 1,3,5,7,9,11,13,15,17,21,23,25,29 and 33.The result is shown in the table 20.

Table 20

(embodiment 38)

[0195] step of repetition embodiment 23, just the charge-transport layer coating liquid is changed to the charge-transport layer coating liquid with following composition, and use negative corona pipe charging (grid electrode) charging, thereby make and assess the photoelectric conductor for electronic photography of numbering 17.The result is shown in the table 21.

The charge-transport layer coating liquid

Polycarbonate resin (Zpolyca, the product of TEIJIN CHEMICALSLTD.): 10 parts

Number 8 compound naphthalenetetracarbacidic acidic diimide derivatives: 1 part

Charge transport material with following structural (I-3): 9 parts

Tetrahydrofuran (THF): 100 parts

(embodiment 39 to 52)

Repeat the step of embodiment 38, just number 8 compound naphthalenetetracarbacidic acidic diimide derivatives and be changed to

compound

1,3,5,7,9,11,13,15,17,21,23,25,29 shown in the table 21 and each of 33, thereby make the photoelectric conductor for electronic photography of numbering 18 to 31.The result is shown in the table 21.

Table 21

(embodiment 53 to 56)

[0197] step of repetition embodiment 38 is just numbered each that 8 compound naphthalenetetracarbacidic acidic diimide derivatives are changed to

compound

1,16,20 and 30; And the content of the charge transport material I-3 of charge-transport layer coating liquid is changed to 7 parts, thereby makes and assessment photoelectric conductor for electronic photography 32 to 35.The result is shown in the table 22.

Naphthalenetetracarbacidic acidic diimide derivatives: 1 part

Charge transport material I-3:7 part

Table 22

(embodiment 57 to 60)

[0198] step of repetition embodiment 53, just charge transport material (I-3) is changed to charge transport material given below (II-3), thereby makes and assess No. the 36th to 39, photoelectric conductor for electronic photography.The result is shown in the table 23.

Table 23

(embodiment 61 to 64)

[0199] step of repetition embodiment 53, just charge transport material (I-3) is changed to charge transport material given below (III-3), thereby makes and assess No. the 40th to 43, photoelectric conductor for electronic photography.The result is shown in the table 24.

Table 24

(embodiment 65 to 68)

[0200] step of repetition embodiment 53, just charge transport material (I-3) is changed to charge transport material given below (IV-3), thereby makes and assess No. the 44th to 47, photoelectric conductor for electronic photography.The result is shown in the table 25.

Table 25

(embodiment 69 and 70)

[0201] step of repetition embodiment 38, just the charge generation layer coating liquid is changed to the charge generation layer coating liquid with following composition; And the charge-transport layer coating liquid is changed to the charge-transport layer coating liquid with following component, thereby makes and assessment photoelectric conductor for electronic photography 48 and 49.The result is shown in the table 26.The generation of＜TiOPc 〉

[0202] similar to the synthetic embodiment 4 of JP-A2001-019871, produce TiOPc.Particularly, with 1,3-diimino isoindoline (29.2g) mixes with tetramethylene sulfone (200mL), and under nitrogen gas stream, (20.4g) dropwise joins in the mixture with four titanium butoxide.After dropwise adding is finished, formed mixture progressively is heated to 180 ℃.Under agitation, make mixture reaction 5 hours, simultaneously temperature of reaction is remained on 170 ℃ to 180 ℃ temperature.After reaction is finished, make the reaction mixture cooling.The material of filtering-depositing, and, be blue up to it with the powder that the chloroform washing is obtained.With the blue powder several that methanol wash obtains, further use hot water (80 ℃) washing then for several times, thereby produce rough titanyl phthalocyanine (titanyl phthalocyanine).Rough titanyl phthalocyanine is dissolved in the vitriol oil of 20 volumes, and under agitation solution is dropwise joined in the frozen water of 100 volumes.Filter out sedimentary crystallization, and the resulting crystal of water repeated washing, have neutral pH up to washing liq, thereby produce the wet cake of titanyl phthalocyanine pigment.Notice that this cake is at the x-ray diffraction pattern shown in drying regime performance Figure 10.Under agitation, the wet cake (2g) that obtains was previously mixed 4 hours with dithiocarbonic anhydride (20g).Further, (100g) joins in the mixture with methyl alcohol, stirs (1 hour) then, filters and drying, thereby produces the TiOPc crystal powder.

The charge generation layer coating liquid

[0203] shows the TiOPc that powder X-ray D as shown in Figure 10 composes: 8 parts

Polyvinyl butyral acetal (BX-1): 5 parts

2-butanone: 400 parts

The charge-transport layer coating liquid

Polycarbonate resin (Zpolyca): 10 parts

Naphthalenetetracarbacidic acidic diimide derivatives: 1 part

Charge transport material (I-3) with following structural: 7 parts

Toluene: 70 parts

Table 26

(embodiment 71)

[0204] the photoconductive layer coating liquid that will have a following component be coated on the aluminium right cylinder (diameter: dry then 100mm), have individual layer photoconductive layer (thickness: photoelectric conductor for electronic photography 30 μ m) (numbering 50 photo-conductors) thereby make.

[photoconductive layer coating liquid]

The metal-free phthalocyanine pigment of X-type (Fastogen Blue 8120B:Dainippon Ink and Chemicals, the product of Incorporated): 2 parts

Charge transport material (II-3) with following structural: 30 parts

Number 1 naphthalenetetracarbacidic acidic diimide derivatives: 20 parts

Bisphenol Z polycarbonate (Panlite TS-2050, the product of TEIJIN CHEMICALS LTD.): 50 parts

Tetrahydrofuran (THF): 500 parts

The photoelectric conductor for electronic photography of so making is installed in imagio Neo 752 (the Ricoh Company of transformation, Ltd. product), use corona tube chargingmethod (using grid electrode type corona tube charger) and laser diode (LD, wavelength: 780nm) as the light source that is used for the imaging exposure.Territory, the non-exposed area current potential (surface) of the imagio Neo 752 that transforms is set at+700 (V), repeats printing test then.The duplicate printing test is equivalent to 100,000 and prints continuously.In this detects, assess the initial pictures quality, and assess its quality and exposure area current potential printing the image that prints after 100,000.Similar to embodiment 27, determine image blurring (point resolution) of image.The result is shown in the table 27.

(embodiment 72 to 74)

Repeat the step of embodiment 71, just number 1 naphthalenetetracarbacidic acidic diimide derivatives (numbering 1 compound) and be changed to each, thereby make and assess photoelectric conductor for electronic photography of the present invention in the compound number shown in the table 27 16,20 and 30.

Table 27

(embodiment 75)

[0205] will be coated on aluminium right cylinder (diameter: 30mm) with the identical photoconductive layer coating liquid that in embodiment 71, uses, dry then, thus manufacturing has individual layer photoconductive layer (thickness: photoelectric conductor for electronic photography 30 μ m) (photo-conductor numbering 54).

[0206] photoconductive layer similar to embodiment 38, that assessment so obtains.The result is shown in the table 28.

(embodiment 76 to 78)

[0207] repeats the step of embodiment 75, just number 1 naphthalenetetracarbacidic acidic diimide derivatives and be changed to the

compound number

16,20 and 30 shown in the table 28, thereby make photoelectric conductor for electronic photography of the present invention.

Table 28

(embodiment 79)

[0208] the charge generation layer coating liquid that has the charge-transport layer coating liquid of following component and have a following component is coated on aluminium right cylinder (diameter: 100mm) in proper order, dry then, thus 20 μ m) and charge generation layer (thickness: photoelectric conductor for electronic photography 0.1 μ m) (photo-conductor numbers 58) make and have charge-transport layer (thickness:.Similar to embodiment 71, the assessment photoelectric conductor for electronic photography.The result is shown in the table 29.(component of charge-transport layer coating liquid)

Bisphenol-a polycarbonate (Panlite C-1400, the product of TEIJIN CHEMICALS LTD.): 10 parts

Toluene: 100 parts

The naphthalenetetracarbacidic acidic diimide derivatives of numbering 1: 10 parts

(component of charge generation layer coating liquid)

Polyvinyl butyral acetal (XYHL, the product of UCC): 0.5 part

Pimelinketone: 200 parts

Methyl ethyl ketone: 80 parts

(embodiment 80 to 82)

[0209] repeats the step of embodiment 79, just number 1 naphthalenetetracarbacidic acidic diimide derivatives and be changed to compound 16,20 shown in the table 29 and each of 30, thereby make and assess photoelectric conductor for electronic photography of the present invention.

Table 29

(comparing embodiment 1)

[0211] repeats the step of embodiment 23, just number 8 naphthalenetetracarbacidic acidic diimide derivatives and be changed to the have following structural quinone derivatives of (I-4), thereby make and the comparison photoelectric conductor for electronic photography of assessment numbering 1.The result is shown in the table 30.

(comparing embodiment 2)

[0211] step of repetition embodiment 38 only is to use the charge-transport layer coating liquid that does not contain naphthalenetetracarbacidic acidic diimide derivatives and contain the charge transport material (I-3) of 10 deals, thereby makes and assess the comparison photoelectric conductor for electronic photography of numbering 2.The result is shown in the table 30.

(comparing embodiment 3)

[0212] step of repetition embodiment 57, just naphthalenetetracarbacidic acidic diimide derivatives is changed to the have following structural tetraphenyl methane compound (describing among the JP-A2000-231204) of (I-5), thereby makes and the comparison photoelectric conductor for electronic photography of assessment numbering 3.The result is shown in the table 30.

(comparing embodiment 4)

[0213] repeat the step of embodiment 69, just naphthalenetetracarbacidic acidic diimide derivatives is changed to the have following structural hindered amines antioxidant of (I-6), thereby makes and the comparison photoelectric conductor for electronic photography of assessment numbering 4.The result is shown in the table 30.

(comparing embodiment 5)

[0213b] repeats the step of embodiment 71, change numbering 1 naphthalenetetracarbacidic acidic diimide derivatives (20 parts) the charge transport material of into (I-7) (18 parts) that have following structural and have the charge transport material of following structural (I-8) (2 parts), thereby make and the comparison photoelectric conductor for electronic photography of assessment numbering 5.The result is shown in the table 30.

(comparing embodiment 6)

[0214] repeats the step of embodiment 71, change the naphthalenetetracarbacidic acidic diimide derivatives (20 parts) of numbering 1 the charge transport material of into (I-9) (20 parts) that have following structural, thereby make and the comparison photoelectric conductor for electronic photography of assessment numbering 6.The result is shown in the table 30.

(comparing embodiment 7)

[0215] step of repetition embodiment 80, just number the charge transport material that 1 naphthalenetetracarbacidic acidic diimide derivatives (10 parts) is changed to the charge transport material of (I-10) (9 parts) that have following structural and has following structural (I-11) (1 part), thereby make and the comparison photoelectric conductor for electronic photography of assessment numbering 7.The result is shown in the table 30.

Table 30

Understand from resulting data that [216] contain the exposure area current potential even the less increase of performance after printing 100,000 of the photo-conductor of naphthalenetetracarbacidic acidic diimide derivatives of the present invention, this shows that it can provide high quality graphic consistently.By comparison, relatively photo-

conductor

1,3 and 4 has quite high exposure area current potential, and this causes image density and resolving power variation.After printing 100,000, these compounds provide the image with the point that can not differentiate each other, and this is owing to the grade performance that reduces greatly causes.From understanding in the data shown in table 20 and 26, photo-conductor of the present invention in addition when the positive chargingmethod of utilization or even print 100,000 after, provide excellent images, and performance image blurring (the high point resolution) that reduce.Independently, compare the photo-conductor increase still less although compare the exposure area current potential performance of photo-

conductor

2,5,6 and 7 than other, they show the resolving power bigger than photo-conductor of the present invention and reduce after repeated use.

(embodiment 83 to 89 and comparing embodiment 8)

[0216b] make photoelectric conductor for electronic photography of the present invention and relatively photo-conductor 2 in moisture eliminator, left standstill 4 days, in described moisture eliminator, with nitrogen oxide (NOx) adjustment of gas concentration to 50ppm.Afterwards, use every kind of photo-conductor to form image, and the image that obtains before image that will so form and the above-mentioned processing compare.

Table 31

The embodiment numbering	The photo-conductor numbering	The initial pictures quality	Make the picture quality after leaving standstill
The embodiment numbering	The photo-conductor numbering	The initial pictures quality	Make the picture quality after leaving standstill	83	2	5	5
84	18	5	5	83	2	5	5
84	18	5	5	85	34	5	5
86	38	5	4	85	34	5	5
86	38	5	4	87	49	5	5
88	50	5	4	87	49	5	5
88	50	5	4	89	60	5	5
Comparing embodiment 8	Compare photo-conductor 2	5	1	89	60	5	5

[0217] resistance of oxidizing gas---promptly to---shows enhanced protection effect greatly to understand that from the data of table 31 photo-conductor that contains naphthalenetetracarbacidic acidic diimide derivatives of the present invention descends to resolving power.Simultaneously, although relatively photo-conductor 2 shows the preferable image quality at first, because the effect of oxidizing gas, its resolving power shows greatly and descends.

Claims

1. naphthalenetetracarbacidic acidic diimide derivatives, it is represented by following general formula (1):

General formula (1)

2. naphthalenetetracarbacidic acidic diimide derivatives, it is represented by following general formula (I):

General formula (I)

R wherein _aExpression contains the essential divalent group of azo-cycle together with nitrogen-atoms and carbon atom formation; The nitrogenous loop section of following general formula (II) expression is represented that replace or unsubstituted, saturated or unsaturated ring, and it can further contain nitrogen-atoms or Sauerstoffatom; When described nitrogenous loop section is that described substituting group can form condensed ring together with a described part that contains azo-cycle when having a plurality of substituent ring; And R _bExpression amino that replace or unsubstituted branched-chain alkyl or amino replace or unsubstituted branched alkoxy alkyl.

General formula (II)

3. naphthalenetetracarbacidic acidic diimide derivatives according to claim 2, the part of wherein said general formula (II) expression are that replace or unsubstituted piperidines, replacement or unsubstituted tetramethyleneimine, replacement or unsubstituted high piperidines, replacement or unsubstituted piperazine or replacement or unsubstituted morpholine.

4. photoelectric conductor for electronic photography, it comprises conductive carrier and the photoconductive layer that is provided on the described conductive carrier, wherein said photoconductive layer contains the first charge transport material, the naphthalenetetracarbacidic acidic diimide derivatives that the described first charge transport material contains following general formula (1) or (I) represents:

General formula (1)

R wherein ¹And R ², it is identical or different, each expression that replace or unsubstituted alkyl or replacement or unsubstituted aromatic hydrocarbon group; R ³Expression has the alkyl or the aromatic hydrocarbon group of 1 to 8 carbon atom; R ⁴, R ⁵, R ⁶And R ⁷, it is identical or different, each expression hydrogen atom, replacement or unsubstituted alkyl or that replace or unsubstituted aromatic hydrocarbon group; And R ¹And R ²Can be connected with formation contain nitrogen-atoms replacement or unsubstituted heterocyclic group; And do not comprise wherein R ¹, R ²And R ³All be the compound of methyl and R wherein ¹And R ²All be methyl, R ³It is the compound of 1-octyl group;

General formula (I)

General formula (II)

5. photoelectric conductor for electronic photography according to claim 4, wherein said photoconductive layer further comprise the second charge transport material.

6. photoelectric conductor for electronic photography according to claim 5, the wherein said second charge transport material are the derivatives of following general formula (2) expression:

General formula (2)

General formula (3)

General formula (4)

R wherein ¹¹The group of expression hydrogen atom, alkyl, alkoxyl group, halogen atom or following general formula (5) expression; M1 is 1 to 3 integer; And when m1 is 2 or more for a long time, R ¹¹Can be identical or different;

General formula (5)

7. photoelectric conductor for electronic photography according to claim 5, the wherein said second charge transport material are the derivatives of following general formula (6) expression:

General formula (6)

R wherein ¹⁴, R ¹⁶And R ¹⁷Each expression hydrogen atom, amino, alkoxyl group, thioalkoxy group, aryloxy, methylene-dioxy, replacement or unsubstituted alkyl, halogen atom or that replace or unsubstituted aromatic hydrocarbon group; R ¹⁵Expression hydrogen atom, alkoxyl group, replacement or unsubstituted alkyl or halogen atom; K, 1, m2 or n are 1,2,3 or 4 integers; When k is 2,3 or 4 integer, R ¹⁴Can be identical or different; When 1 when being 2,3 or 4 integer, R ¹⁵Can be identical or different; When m2 is 2,3 or 4 integer, R ¹⁶Can be identical or different; During with the integer that as n is 2,3 or 4, R ¹⁷Can be identical or different.

8. photoelectric conductor for electronic photography according to claim 5, the wherein said second charge transport material are the derivatives of following general formula (7) expression:

General formula (7)

General formula (8)

R wherein ²¹Expression hydrogen atom, alkyl, alkoxy or halogen atom; M3 is 1 to 3 integer; And when m3 is 2 or more for a long time, R ²¹Can be identical or different;

General formula (9)

9. photoelectric conductor for electronic photography according to claim 5, the wherein said second charge transport material are the derivatives of following general formula (10) expression:

General formula (10)

General formula (3)

General formula (4)

R wherein ¹¹The group of expression hydrogen atom, alkyl, alkoxyl group, halogen atom, following general formula (5) expression; M1 is 1 to 3 integer; And when m1 is 2 or more for a long time, R ¹¹Can be identical or different;

General formula (5)

10. photoelectric conductor for electronic photography according to claim 4, wherein said photoconductive layer comprises conductive carrier, charge generation layer and charge-transport layer in order.

11. photoelectric conductor for electronic photography according to claim 4, wherein said photoconductive layer comprises conductive carrier, charge-transport layer and charge generation layer in order.

12. photoelectric conductor for electronic photography according to claim 4, wherein said photoconductive layer has single layer structure.