CN1085352C - Electric photography photoactive elements, processing-box and electric photography apparatus - Google Patents

Electric photography photoactive elements, processing-box and electric photography apparatus Download PDF

Info

Publication number
CN1085352C
CN1085352C CN96110714A CN96110714A CN1085352C CN 1085352 C CN1085352 C CN 1085352C CN 96110714 A CN96110714 A CN 96110714A CN 96110714 A CN96110714 A CN 96110714A CN 1085352 C CN1085352 C CN 1085352C
Authority
CN
China
Prior art keywords
formula
electric photographic
substituted
photosensitive element
titanyl phthalocyanine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN96110714A
Other languages
Chinese (zh)
Other versions
CN1159613A (en
Inventor
铃木幸一
高井秀幸
国枝光弘
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Canon Inc
Original Assignee
Canon Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Canon Inc filed Critical Canon Inc
Publication of CN1159613A publication Critical patent/CN1159613A/en
Application granted granted Critical
Publication of CN1085352C publication Critical patent/CN1085352C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0664—Dyes
    • G03G5/0675—Azo dyes
    • G03G5/0694—Azo dyes containing more than three azo groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0664—Dyes
    • G03G5/0675—Azo dyes
    • G03G5/0679—Disazo dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0664—Dyes
    • G03G5/0675—Azo dyes
    • G03G5/0687—Trisazo dyes

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)

Abstract

An electrophotographic photosensitive member is disclosed which has a photosensitive layer on a conductive support. The photosensitive layer contains an oxytitanium phthalocyanine and an azo pigment represented by the following Formula (1): Ar &lparstr& N=N-Cp)n. Also, disclosed are a process cartridge and an electrophotographic apparatus using the electrophotographic photosensitive member.

Description

Electric photographic photosensitive element, handle box and electric photographic equipment including titanyl phthalocyanine
The present invention relates to a kind of electric photographic photosensitive element with the photosensitive layer comprising special charge generating material, a kind of handle box with the electric photographic photosensitive element and a kind of electric photographic equipment with the electric photographic photosensitive element are further related to.
It has been very significantly improved using the electric photographic photosensitive element of organic light-guide material for the use of its photonasty and durability (or behavior in service), and it has been widely used in actual use, described improvement is that the improvement of the photo-sensitive cell of function separation is caused, and described element is included and overlappingly formed by the charge generation layer containing charge generating material and the charge transfer layer containing charge transport material.Particularly in recent years since, be widely used as terminal printer instead of the non-impact printer of traditional impact printer, described non-percussion beats formula printer applications electric photographic technology.These printers are mainly the laser beam printer for making light source with laser.As light source, in view of the reason such as expense, size of equipment, uses semiconductor laser.There is the oscillation wavelength up to 790 ± 20nm currently as the semiconductor laser that trend is used, therefore, developed has effective photosensitive electric photographic photosensitive element in the long wavelength range.
As in the long wavelength range have photosensitive material, it is known in prior art that metal-free phthalocyanine and metal phthalocyanine, they have been used as charge generating material and used in practice.Specifically, in this kind of phthalocyanine compound, titanyl phthalocyanine (oxytitaniumphthalocyanine) has very high photonasty.
But, people are still finding with more preferable potential stability and more preferable light Memorability (photomemory) (potential decay of fluorescent lamp radiant section), are using the electric photographic photosensitive element of titanyl phthalocyanine.Correspondingly, it has been proposed that such as make charge generation layer thinner or reduce the titanyl phthalocyanine ratio means in charge generation layer.However, these measures may reduce photonasty.
In order to obtain panchromatic photonasty, proposed in Japanese Unexamined Patent Publication No 3-37656 and titanyl phthalocyanine and disazo pigment is applied in combination.But, this disazo pigment is little in the above-mentioned aspect of performance effect of improvement.
It is an object of the invention to provide a kind of electric photographic photosensitive element in Reusability with high photosensitivity, excellent potential stability and excellent smooth memory character.
It is a further object to provide a kind of handle box with the electric photographic photosensitive element and a kind of electric photographic equipment with the electric photographic photosensitive element.
The invention provides a kind of electric photographic photosensitive element comprising conductive carrier and the photosensitive layer on the conductive carrier；
The AZOpigments that described photosensitive layer is represented comprising titanyl phthalocyanine and by following formula (1).Formula (1)：
Ar  N=N-Cp)nWherein, Ar represents the substituted or unsubstituted aromatic hydrocarbon group that can be bonded together by linker or the substituted or unsubstituted heterocyclic group that can be bonded together by linker；Cp represents the coupling agent residue with phenolic hydroxyl group, and the Cp described at least one represents the coupling agent residue represented by following formula (2)；N represents 2-4 integer.Formula (2)：
Figure C9611071400072
Wherein, A represents the divalent group of substituted or unsubstituted aromatic hydrocarbon ring, or on ring the substituted or unsubstituted heterocycle comprising nitrogen-atoms divalent group.
Present invention provides a kind of handle box with above-mentioned electric photographic photosensitive element and a kind of electric photographic equipment with above-mentioned electric photographic photosensitive element.
Fig. 1 shows the x-ray diffraction pattern of the CuK α features of I type titanyl phthalocyanines.
Fig. 2 shows the x-ray diffraction pattern of the CuK α features of A type titanyl phthalocyanines.
Fig. 3 shows the x-ray diffraction pattern of the CuK α features of Type B titanyl phthalocyanine.
Fig. 4 shows the x-ray diffraction pattern of the CuK α features of Y-shaped oxygen titanium phthalocyanines.
Fig. 5 shows a kind of structural representation of electric photographic equipment, and the electric photographic equipment has the handle box containing electric photographic photosensitive element of the present invention.
The electric photographic photosensitive element of the present invention has the photosensitive layer on conductive carrier, the AZOpigments that the photosensitive layer is represented comprising titanyl phthalocyanine and by following formula (1).Formula (1)：
Ar  N=N-Cp)nWherein, Ar represents the substituted or unsubstituted aromatic hydrocarbon group that can be bonded together by linker or the substituted or unsubstituted heterocyclic group that can be bonded together by linker；Cp represents the coupling agent residue with phenolic hydroxyl group, and the Cp described at least one represents the coupling agent residue represented by following formula (2)；N represents 2-4 integer.Formula (2)：
Figure C9611071400082
Wherein, A represents the divalent group of substituted or unsubstituted aromatic hydrocarbon ring, or on ring the substituted or unsubstituted heterocycle comprising nitrogen-atoms divalent group.
The present invention is effective at following two aspects：Excellent potential stability and excellent light memory character can be achieved；Even if the specific AZOpigments does not have photonasty under about 800nm, the photonasty at about 800nm that titanyl phthalocyanine is possessed can be strengthened by the chemical sensitization of the AZOpigments.
Titanyl phthalocyanine for the present invention has following structures.Wherein, X1、X2、X3And X4Represent Cl or Br；K, m, p and r each be integer 0-4.
Titanyl phthalocyanine can have any crystal form.Preferably include A types disclosed in the grade of U.S. Patent number 4,664,997, Type B disclosed in the grade of U.S. Patent number 4,728,592, Y types disclosed in I types disclosed in the grade of U.S. Patent number 5,132,197 and JP patent application publication numbers 64-17066.Specifically, preferably I types are crystallized.The x-ray diffraction pattern of the CuK α features of the titanyl phthalocyanine of various crystal forms is respectively illustrated in Fig. 1,2,3 and 4.It can be synthesized according to known method disclosed in above-mentioned patent or other methods and manufacture the titanyl phthalocyanine with above-mentioned crystal form.
In the AZOpigments represented by formula (1), the group that Ar is represented in formula includes, for example, aromatic hydrocarbon ring such as benzene, naphthalene, fluorenes, phenanthrene, anthracene and pyrene；Heterocycle such as furans, thiophene, pyridine, indoles, benzothiazole, carbazole, acridone, dibenzothiophen, benzoxazole, oxadiazoles and thiazole；Above-mentioned aromatic hydrocarbon ring or heterocycle can Direct Bondings, or be bonded by aryl or non-aryl, the group that can be enumerated is xenyl, binaphthyl, diphenylamine, triphenylamine, N- methyldiphenyl bases amine, Fluorenone, phenanthrenequione, anthraquinone, benzanthrone, terphenyl, Er Ben oxadiazoles, 1,2- talan, diphenylethyllene benzene, azobenzene, azoxybenzene, Ben bases benzoxazole, diphenyl methane, diphenyl sulfone, diphenyl ether, benzophenone, tetraphenyl p-phenylenediamine, tetraphenyl benzidine, N- phenyl -2- pyridine radicals amine and N, N- diphenyl -2- pyridine radicals amine.
The substituent that Ar can have includes alkyl such as methyl, ethyl, propyl group and butyl；Alkoxy such as methoxyl group, ethyoxyl and propoxyl group；Halogen atom such as fluorine, chlorine, iodine and bromine atoms；Alkylamino such as dimethylamino and lignocaine；Hydroxyl；Nitro；Cyano group；And halogenated methyl.
In formula (2), included by the A groups represented, for example, such as adjacent phenylene, 2,3- naphthylenes, 2,3- pyrazines diyl, 3,4- pyrazoles diyl, 2,3- pyridines diyl, 4,5- pyridines diyl and 4,5- imidazoles diyl.
The substituent that A can have includes alkyl such as methyl, ethyl, propyl group and butyl；Alkoxy such as methoxyl group, ethyoxyl and propoxyl group；Halogen atom such as fluorine, chlorine, iodine and bromine atoms；Nitro；Cyano group；And halogenated methyl.A preferably unsubstituted adjacent phenylenes.
In the group represented in formula (1) by Cp, in addition to the coupling agent residue represented by formula (2), coupling agent residue may also comprise, for example, the group represented by following formula (3)-(8).Formula (3)：Formula (4)：
Figure C9611071400111
Formula (5)：Formula (6)：Formula (7)：Formula (8)：
In formula (3), (4), (5) and (6), X represents the atomic radical that must be combined with phenyl ring, to form substituted or unsubstituted aromatic ring or substituted or unsubstituted heterocycle, wherein aromatic ring and heterocycle includes, for example, naphthalene nucleus, anthracene nucleus, carbazole ring, benzo carbazole ring and dibenzofurans ring.Y in formula (8) represents the divalent group of substituted or unsubstituted aromatic hydrocarbons, or the divalent group of the substituted or unsubstituted heterocycle of nitrogen-atoms is included on ring, specifically include group such as adjacent phenylene, adjacent naphthylene, sub- all naphthyls (perinaphthylene), 1,2- anthrylene, 3,4- pyrazoles diyl, 2,3- pyridines diyl, 4,5- pyridines diyl and 6,7- indazoles diyl and 6,7- quinoline diyl.R in formula (3) and (4)1And R2Hydrogen atom, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl or substituted or unsubstituted heterocyclic radical are represented respectively.R1And R2It can also be together with each other to form substituted or unsubstituted cyclic amino by nitrogen-atoms.R in formula (5) and (6)3Represent hydrogen atom, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl or substituted or unsubstituted heterocyclic radical.R in formula (7)4Represent hydrogen atom, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl or substituted or unsubstituted heterocyclic radical.Abovementioned alkyl includes such as methyl, ethyl and propyl group；Aryl includes such as phenyl, naphthyl and anthryl；Aralkyl includes such as benzyl and phenethyl；Heterocyclic radical includes such as pyridine radicals, thienyl, carbazyl, benzimidazolyl and benzothiazolyl；The cyclic amino of nitrogen atom includes such as pyrroles, pyrrolin, pyrrolidines, pyrrolidones, indoles, indoline, carbazole, imidazoles, pyrazoles, pyrazoline, oxazines He phenoxazine in ring.Substituent includes halogen atom such as fluorine, chlorine, iodine and bromine atoms；Alkyl such as methyl, ethyl and propyl group；Alkoxy such as methoxyl group and ethyoxyl；Alkylamino such as dimethylamino and lignocaine；Phenylcarbamoyl；Nitro；Cyano group；With halogenated methyl such as trifluoromethyl.Z in formula (3) and (5) represents oxygen atom or sulphur atom, and m represents 0 or 1.
In formula (1), n represents integer 2-4, preferable 2 or 3.
The preferred embodiment for the AZOpigments that the present invention is represented by formula (1) is illustrated below.AZOpigments for the present invention is not limited to these.In described below, the concrete structure of typical pigment is provided by basic form first, then provides its variant.
When synthesis as hereinafter described, the coupling agent with the coupling agent residue represented by (2) is generally obtained in its isomer mixture form.Therefore, the example is also provided as a mixture.For example, " basic form 1：
            Cp1- N=N-Ar-N=N-Cp2Pigment 1
Ar：
Figure C9611071400131
Cp1And Cp2：With Refer to that pigment 1 is as follows the mixture of compound.
Figure C9611071400151
Basic form 1：
               Cp1- N=N-Ar-N=N-Cp2Typical pigments 1Ar：
Figure C9611071400152
Cp1And Cp2：
Figure C9611071400153
With
Figure C9611071400154
Typical pigments 2Ar： Cp1And Cp2：
Figure C9611071400162
With
Figure C9611071400163
Typical pigments 3Ar：
Figure C9611071400164
Cp1And Cp2：With Typical pigments 4Ar：
Figure C9611071400173
Cp1And Cp2：With
Figure C9611071400175
Typical pigments 5Ar： Cp1And Cp2：
Figure C9611071400182
With
Figure C9611071400183
Typical pigments 6Ar：
Figure C9611071400184
Cp1And Cp2：With Typical pigments 7Ar：
Figure C9611071400193
Cp1And Cp2：With
Figure C9611071400195
Typical pigments 8
Figure C9611071400196
Cp1And Cp2：
Figure C9611071400201
With
Figure C9611071400202
Typical pigments 9Ar：
Figure C9611071400203
Cp1And Cp2：With Typical pigments 10Ar： Cp1And Cp2：With Typical pigments 11Ar：
Figure C9611071400214
Cp1And Cp2：
Figure C9611071400221
With Typical pigments 12Ar：Cp1And Cp2：
Figure C9611071400224
With
Figure C9611071400225
Typical pigments 13Ar： Cp1And Cp2：
Figure C9611071400232
With
Figure C9611071400233
Typical pigments 14Ar：
Figure C9611071400234
Cp1And Cp2：With
Figure C9611071400242
Typical pigments 15Ar：Cp1And Cp2：
Figure C9611071400244
With Typical pigments 16Ar：
Figure C9611071400251
Cp1And Cp2：
Figure C9611071400252
With
Figure C9611071400253
Typical pigments 17Ar：
Figure C9611071400254
Cp1And Cp2：
Figure C9611071400261
With
Figure C9611071400262
Typical pigments 18Ar：Cp1And Cp2：
Figure C9611071400264
With
Figure C9611071400265
Typical pigments 19Ar：
Figure C9611071400271
Cp1：With
Figure C9611071400273
Cp2：
Figure C9611071400274
Typical pigments 20Ar：
Figure C9611071400275
Cp1：With
Figure C9611071400282
Cp2：
Figure C9611071400283
Typical pigments 21Ar：
Figure C9611071400284
Cp1：
Figure C9611071400285
With
Figure C9611071400286
Cp2：
Figure C9611071400291
Typical pigments 22Ar：
Figure C9611071400292
Cp1：With
Figure C9611071400294
Cp2：
Figure C9611071400295
Typical pigments 23Ar：Cp1：
Figure C9611071400302
With
Figure C9611071400303
Cp2：Typical pigments 24Ar：
Figure C9611071400305
Cp1：With Cp2：
Figure C9611071400313
Typical pigments 25Ar：
Figure C9611071400314
Cp1：With
Figure C9611071400322
Cp2：
Figure C9611071400323
With
Figure C9611071400324
Typical pigments 26Ar：Cp1：With Cp2：
Figure C9611071400333
With Typical pigments 27Ar：
Figure C9611071400335
Cp1：With
Figure C9611071400337
Cp2：Typical pigments 28Ar：
Figure C9611071400342
Cp1And Cp2：
Figure C9611071400343
With Typical pigments 29Ar：Cp1And Cp2：
Figure C9611071400352
With Typical pigments 30Ar：
Figure C9611071400354
Cp1：
Figure C9611071400355
With
Figure C9611071400356
Cp2：With Typical pigments 31Ar：
Figure C9611071400363
Cp1：
Figure C9611071400364
With Cp2：Typical pigments 32Ar：
Figure C9611071400371
Cp1：With Cp2：
Figure C9611071400374
Typical pigments 33Ar：
Figure C9611071400375
Cp1：
Figure C9611071400381
With
Figure C9611071400382
Cp2：Basic form 2：
Figure C9611071400384
Typical pigments 34Ar：
Figure C9611071400385
Cp1, Cp2And Cp3：
Figure C9611071400391
With
Figure C9611071400392
Typical pigments 35Ar：
Figure C9611071400393
Cp1, Cp2And Cp3：
Figure C9611071400394
With Typical pigments 36Ar：
Figure C9611071400401
Cp1, Cp2And Cp3：
Figure C9611071400402
With
Figure C9611071400403
Basic form 3
Figure C9611071400404
Typical pigments 37Ar：
Figure C9611071400411
Cp1, Cp2, Cp3And Cp4：
Figure C9611071400412
With
Figure C9611071400413
Typical pigments 38Ar：Cp1, Cp2, Cp3And Cp4：
Figure C9611071400421
With
Figure C9611071400422
In these examples of the present invention, all Cp are that the compound of the coupling agent residue represented by formula (2) is particularly preferred.More preferably typical pigments 1,3,4,5,6,28 or 29.
Coupling agent with the coupling agent residue represented by formula (2) can be synthesized by making hydroxyl -1,8- naphthalic anhydride and corresponding aminoaryl carboxylic acid amides carry out dehydrating condensation in suitable solvent.Solvent used includes nitrobenzene, dichloro-benzenes, three pyridines and dimethylbenzene.Phosphoryl chloride phosphorus oxychloride or polyphosphoric acid can be added as condensing agent.The synthesized coupling agent with the coupling agent residue represented by formula (2) is obtained with the form of mixtures of its isomers, and described isomers is represented by following formula (2-a) and (2-b).Any isomers can be used in the present invention.
Formula (2-a)
Figure C9611071400423
Formula (2-b)
Figure C9611071400431
Synthetic example 1 (synthesis of coupling agent)
10.0g 3- hydroxyls -1,8- naphthalic anhydride and 7.0g anthranilamides is added into 130ml nitrobenzene, is heated to reflux 12 hours.Make after reactant mixture cooling, filtering precipitation is disperseed and washed with toluene, is then disperseed and is washed with methanol, then, reprecipitation is repeated twice with DMF/methanol solution.Hereafter the sediment is disperseed and washed with methanol again, by the coupler mix represented by formula (2-a) and (2-b) for being dried to obtain 3.5g.
Fusing point：310-315℃；Mass spectrum：M/z=314.
The AZOpigments represented by formula (1) can be readily derived by following processes：
(a) corresponding amine is changed into diazonium form, then, in the presence of the alkali in Aquo System, with the coupling agent of the coupling agent residue represented with formula (2)；Or
(b) diazol is changed into borofluoride or nitridation Zn complex, then, in the presence of alkali such as sodium acetate, triethylamine or N-methylmorpholine, in a kind of organic solvent such as DMF or dimethyl sulfoxide (DMSO), with coupling agent.When the di-heavy nitrigen pigment that also there is the coupling agent residue beyond a kind of coupling agent residue represented by formula (2) together in the molecule is synthesized, they can be synthesized by following processes：
(a) first, make 1mol tetrazolium saltses and 1mol that there is the coupling agent of coupling agent residue of formula (2) expression, then, with the other coupling agents of 1mol；Or
(b) a kind of one amino is changed into diazonium form with the diamines of the protections such as acetyl group; then; with the coupling agent of the coupling agent residue represented with formula (2); then the protection group is hydrolyzed with hydrochloric acid etc.; the compound is changed into diazonium form again, then with other coupling agents.Also exist together in the molecule the coupling agent residue beyond a kind of coupling agent residue represented by formula (2) trisazo pigment and four AZOpigments can also same mode synthesize.
Synthetic example 2 (synthesis of typical pigments 1)
In 300ml beaker, the diamine compound of 150ml water, 20ml (0.23mol) concentrated hydrochloric acids and 7.3g (0.032mol) following formula is added,
Figure C9611071400441
Mixture is cooled to 0 DEG C, in 10 minutes in the case where keeping fluid temperature to be 2 DEG C or lower temperature, is added dropwise into mixture by the way that 4.6g (0.067mol) natrium nitrosum is dissolved in into the solution prepared in 10ml water.After stirring 15 minutes, reactant mixture is filtered with carbon, then under agitation, is added dropwise into reactant mixture by the way that 10.5g (0.096mol) sodium fluoborate is dissolved in into the solution prepared in 90ml water.The borofluoride being settled out is collected by filtration, is then washed, is then washed with acetonitrile with cold water, then dried at room temperature under reduced pressure.Yield：12.8g, 94%.
Then, in one 5 liters of beaker, 3 liters of DMF (DMF) is added, the coupler mix that then dissolving 13.2g (0.042mol) formula (2-a) and (2-b) is represented wherein.Resulting solution is cooled to fluid temperature for 5 DEG C.Hereafter, the 8.5g being previously obtained (0.020mol) borofluoride is dissolved in wherein, then in 5 minutes be added dropwise 5.1g (0.050mol) triethylamine.After stirring 2 hours, the pigment being settled out is collected by filtration and then is washed with DMF four times, is washed with water three times, is then freeze-dried.Yield：14.2g, 81%.
The electric photographic photosensitive element of the present invention includes a conductive carrier, on this carrier with photosensitive layer, the AZOpigments that the photosensitive layer is represented comprising titanyl phthalocyanine and formula (1).The photosensitive layer can have any of form.Particularly preferably the photosensitive layer of function divergence type, includes the charge generation layer and the electric charge migrating layer for including charge transporting material being formed on of the AZOpigments represented containing titanyl phthalocyanine and by formula (1).
The charge generation layer of the present invention can be the charge generation layer of the AZOpigments not only represented comprising titanyl phthalocyanine but also comprising formula (1)；Or the charge generation layer formed by the overlapping layer for including both respectively.
When mixing titanyl phthalocyanine with AZOpigments, preferably the weight ratio of titanyl phthalocyanine/AZOpigments is 95/5 to 70/30.If weight ratio during mixing is more than 95/5, required improvement may less, and if weight ratio is less than 70/30, in long wavelength region, photonasty may be reduced.
When the charge generation layer comprising titanyl phthalocyanine or the overlapping charge generation layer comprising AZOpigments, they can be using two kinds of following forms：Charge generation layer comprising AZOpigments is contacted with electric charge migrating layer, or the charge generation layer comprising titanyl phthalocyanine is contacted with electric charge migrating layer.Latter form is more efficiently in the present invention, is also preferred.The preferred thickness of charge generation layer comprising titanyl phthalocyanine is 0.1 to 0.5 μm.Charge generation layer comprising AZOpigments need not such big thickness, can be highly effective when about 0.05-0.2 μm of thickness.    
Charge generation layer can be formed in the following manner：The titanyl phthalocyanine and AZOpigments of the present invention are deposited on conductive carrier；Or a kind of coating solution is applied on conductive carrier by known method, described solution is obtained by the way that titanyl phthalocyanine and AZOpigments are dispersed in together with adhesive resin in suitable solution.Charge generation layer is preferably what is formed with thin layer, and its thickness is not more than 5 μm, particularly preferably from 0.1 to 1 μm.Adhesive resin used can be from a wide range of middle selection of various insulating resins or organic photoconductive polymer during by being coated on this layer formation.It preferably includes polyvinyl butyral resin, polyvinyl alcohol condensing benzaldehyde (polyviny1 benzal), polyarylate, makrolon, polyester, phenoxy resin, celluosic resin, acrylic resin and polyurethane.With the total restatement of charge generation layer, its consumption is no more than 80% weight, more preferably no more than 40% weight.Solvent used is preferably capable of those solvents for dissolving above-mentioned resin but insoluble electric charge migrating layer and the glue-line described later.It specifically includes ethers such as tetrahydrofuran and Isosorbide-5-Nitrae-dioxanes；Ketone such as cyclohexanone and MEK；Amide-type such as DMF；Esters such as methyl acetate and ethyl acetate；Aromatic hydrocarbons such as toluene, dimethylbenzene and chlorobenzene；Alcohols such as methanol；Ethanol and 2- propyl alcohol；And aliphatic halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethylene, carbon tetrachloride and trichloro ethylene.
Electric charge migrating layer is superimposed on charge generation layer above and below, it can be formed by being coated with a kind of coating solution, charge transporting material is dissolved in a kind of solvent by described coating solution to be prepared, and the material can be mixed arbitrarily with a kind of suitable adhesive resin.The thickness of the migrating layer is preferably 5 to 40 μm, particularly preferably 15 to 30 μm.
Charge transporting material is substantially divided into electron-transporting materials and hole transporting material.The electron-transporting materials include absorbing electronic materials, are typically：2,4,7- trinitrofluorenones, 2,4,5,7- tetranitro Fluorenones, chlorine anil (chloroanil) and tetracyano quino dimethane, or those obtained from polymer are made in these absorbing electronic materials.Hole transporting material includes polynuclear aromatic compound such as pyrene and anthracene；Heterocyclic compound such as carbazole type, indoles type, imidazole type, oxazoles type, thiazole Xing, oxadiazoles type, pyrazoles type, pyrazoline type, thiadiazole type or triazole-type compound；Hydrazone compound such as paradiethylaminobenzaldehyde-N, N- diphenyl hydrazones and N, N- diphenyl diazanyl -3- methine -9- ethyl carbazoles；Triarylamine compound such as three p-methylphenyl amine, 4- (di-p-tolyl amino) biphenyl, 2- (di-p-tolyl)-amino -9,9 '-dimethyl Fluorenone and 1- di-p-tolyls-amino pyrene；Compound of styryl such as α-phenyl -4 '-N, N diphenyl aminos -1,2- talan and 5- [4- (di-p-tolyl amino) benzal] -5H- dibenzo [a, d] cycloheptene；Benzidine compound；Triaryl methane compounds；Triphenylamine is used as main chain or the polymer of side chain, typically poly-N-vinyl carbazole and polyvinyl anthracene with a group for including any of these compounds.In addition to these organic charge transport materials, inorganic material such as selenium, selenium-tellurium, non-crystalline silicon and cadmium sulfide can also be used.These charge transporting materials can be used alone, and can also be together applied in combination by two or more.
When charge transporting material does not have filming performance, adhesive resin may be used.The resin specifically includes following material：Insulating resin such as acrylic resin, polyarylate, polyesters, polycarbonate-based, polystyrene, acrylonitrile/styrol copolymer, polyacrylamide, polyamide and chlorinated rubber；And organic photoconductive polymer such as poly-N-vinyl carbazole and polyvinyl anthracene.
Typical example for the conductive carrier of the present invention is aluminium, aluminium alloy, copper, zinc, stainless steel, vanadium, molybdenum, chromium, titanium, nickel, indium, gold and platinum.In addition, the carrier for including plastics (being typically polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate and acrylic resin) can also be used, described plastics have a tunic, the film forms any of these metal or alloy by vacuum moulding machine, comprising with a kind of conductive particle (exemplary such as carbon black and Argent grain) carrier any in the above-mentioned plastics of cover it, metal or alloy together with suitable adhesive, the plastics impregnated with conductive material or the carrier of paper are included.Carrier is probably cydariform, piece shape or with shape, and should be preferably made the form being best suitable for applied on electric photographic equipment.
In the present invention, the glue-line with barrier functionality and adhesive function can be provided between conductive carrier and photosensitive layer.The glue-line can use such as the formation such as nylon 6, nylon66 fiber, NYLON610, copolymer nylon and aikoxymethytated nylon, polyurethane, aluminum oxide of casein, polyvinyl alcohol, NC Nitroncellulose, polyamide.The thickness of glue-line is preferably more than 5 μm, more preferably 0.1-3 μm.
As an alternative embodiment of the invention, the electric photographic photosensitive element may include those elements with photosensitive layer, wherein mixing titanyl phthalocyanine, AZOpigments and the charge transporting material as described above of the present invention within the same layer.In this case, a kind of charge transfer complex containing poly-N-vinyl carbazole and trinitrofluorenone possibly serves for charge transporting material.Electric photographic photosensitive element in the present embodiment can be formed by being coated with to be dried after a solution, and described solution is that titanyl phthalocyanine as described above, the AZOpigments of the present invention and charge transporting material or charge transfer complex are dissolved in a kind of suitable resin solution and prepared.
In two kinds of electric photographic photosensitive elements, the AZOpigments that formula (1) is represented can be amorphous or crystalline crystal form.If desired, the AZOpigments that formula (1) is represented can also combination of two or more use, or be applied in combination together with known charge generating material.
In the present invention, it is further provided the main protective layer being made up of resin on photosensitive layer.
The electric photographic photosensitive element of the present invention cannot be only used for electrophotographic duplicator, and can be widely used in the field using electric photography, such as laser beam printer, CRT printers, LED printers, liquid crystal printer, laser beam engraving machine and facsimile machine.
Fig. 5 shows a kind of structural representation of electric photographic equipment, and the electric photographic equipment has the handle box of the charge member containing the present invention.
In Fig. 5, label 1 represents electric photographic photosensitive element, and it is with given peripheral speed with the side pointed by arrow upwards about the rotation driving of axle 2.Evenly over the circumference fill positive or negative given current potential with photo-sensitive cell 1 by primary charging mechanism 3.Then powered photo-sensitive cell is exposed under light 4 into optical image, light 4 is sent from the exposure mechanism (not shown) into image, exposed for slit exposure or laser beam flying.So, it is formed continuously electrostatic latent image on the circumference of photo-sensitive cell 1.
The electrostatic latent image being subsequently formed is developed by the operation of developing mechanism 5 by toner.Then, by the operation of transfer means 6 by the image continuously transfer printing of the toner development of formation to the surface of offset medium 7, offset medium is fed in the mode synchronous with the rotation of photo-sensitive cell 1 from paper supply section (not shown) to the part between photo-sensitive cell 1 and transfer means 6.
The offset medium 7 that image is transferred thereon is separated with the surface of photo-sensitive cell, makes offset medium by image fixing mechanism 8, herein, the image is fixed, and then offset medium in photocopying materials (copy) slave unit as printing.
After transferred image, toner remaining after transfer is removed from the surface of photo-sensitive cell 1 by cleaning device 9.Therefore, after being cleaned on the surface of photo-sensitive cell, by the pre-exposure light 10 launched by pre-exposure mechanism (not shown) eliminate institute it is electrically charged, then, be recycled and reused for image and formed.When primary charging mechanism is the contact charging mechanism using charging roller etc., pre-exposure is not essential.
In the present invention, the part that described equipment may be dealt with box by the connection of multiple integral types is combined and constituted, these parts come from each component, for example from above-mentioned electric photographic photosensitive element 1, primary charging mechanism 3, developing mechanism 5 and cleaning mechanism 9, so that handle box can be disassembled from electric photographic equipment such as duplicator or laser beam printer main body.For example, at least one in primary charging mechanism 3, developing mechanism 5 and cleaning mechanism 9 may be integrally supported on the box together with electric photographic photosensitive element 1 to form the handle box 11 disassembled in energy slave unit main body, and described unloading process is by being arranged on the guiding mechanism on described equipment body as track 12 is realized.
When electric photographic equipment is used as duplicator or printer, light 4 into image exposure is to pass through preimage or the light from preimage reflection, or pass through the light of the scanning radiation of laser beam, according to by reading preimage and information being changed into signal driving LED information display system or liquid crystal grating system that signal is obtained.
It invention will be further described by following embodiments.
Embodiment 1
By 50 parts of (parts by weight comprising 10% antimony oxide；It is as follows) scribble the titanium oxide powder of tin oxide, 25 parts of fusible phenolic resin type phenol resin, 20 portions of methyl cellosolves, 5 parts of methanol and oily (the polydimethylsiloxane--polyoxyalkylene copolymer of 0.002 part of silicon (oxygen alkane)；Weight average molecular weight：3000) scattered 2 hours by a sand mill, sand mill uses the bead of 1mm diameters.On obtained dispersion dip-coating to aluminium cylinder (diameter 80mm, long 360mm), then, dried 30 minutes at 140 DEG C, form the conductive layer that thickness is 20 μm.
On the conductive layer, the solution below dip-coating：5 parts of 6-66-610-12 polyamide quadripolymers are dissolved in solution made from the in the mixed solvent of 70 parts of methanol and 25 parts of butanol；It is subsequently dried, forms glue-line, its thickness degree is 1 μm.
To by by 10 parts of polyvinyl butyral resin (trade names：S-LEC BX-1；Can be from Sekisui Chemical Co., Ltd. it is commercially available) 7 parts of I- types titanyl phthalocyanines of addition and the AZOpigments of 3 parts of typical pigments 1 in the solution that 400 parts of cyclohexanone are obtained are dissolved in, described titanyl phthalocyanine has characteristic peaks in the x-ray diffraction pattern of CuK α features at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° of Bragg angle (2 θ ± 0.2 °) place (its diffraction pattern is shown in Fig. 1).The resulting mixture is disperseed 2 hours by a sand mill, sand mill uses the bead of 1mm diameters.Into the dispersion liquid so obtained, add 400 parts of ethyl acetate to dilute it.On obtained dispersion liquid dip-coating to above-mentioned glue-line, then dried 10 minutes at 80 DEG C, form charge generation layer, its thickness degree is 0.25 μm.
Then, by 10 parts of charge transporting materials with following structural formula
Figure C9611071400511
With 10 parts of bis-phenol-Z polycarbonate (weight average molecular weight：49000) it is dissolved in 60 parts of chlorobenzenes.On solution dip-coating to the charge generation layer of formation, then dried 1 hour at 110 DEG C, form electric charge migrating layer, its thickness degree is 20 μm.So as to produce an electric photographic photosensitive element.
Comparative example 1
Electric photographic photosensitive element is produced in the same manner as in Example 1, simply using 10 parts of I- type titanyl phthalocyanines, but without using AZOpigments.
Comparative example 2
Electric photographic photosensitive element is produced in the same manner as in Example 1, but without using AZOpigments.
Comparative example 3
Electric photographic photosensitive element is produced in the same manner as in Example 1, and the AZOpigments that simply AZOpigments is represented with following structural formula is replaced.
Figure C9611071400512
Performance evaluation
Embodiment 1 and comparative example the 1-3 electric photographic photosensitive element produced are respectively placed on laser beam printer (trade name：LBP-SX；Produced by CANON INC.), evaluated with the performance to them.First, the dark space current potential for making each photo-sensitive cell is -700V, is then placed in photo-sensitive cell under the illumination launched by 802nm lasers, laser intensity necessary to measurement makes clear zone current potential be -150V, that is, measures photonasty.Equally, variable quantity (the Δ V of measurement dark space current potential in continuous 5000 parts of A4 paper print proceduresD) and clear zone current potential variable quantity (Δ VL).Variable quantity is that negative value shows that the absolute value of current potential after printing diminishes；When variable quantity be on the occasion of when, show that the absolute value of current potential after printing becomes big.
Also light memory characteristic is evaluated.Particularly, first, fluorescent lamp (trade name has been used：FVL18 white lights；By Matsushita Electric Industrial Co., Ltd is produced), the electric photographic photosensitive element produced in embodiment 1 and comparative example 1-3 is partially disposed in lower 5 minutes of the intensity of illumination of 1500 Le respectively, and, after exposure, then at placement 5 minutes at room temperature (by shielding light formation unexposed portion).After, handled photo-sensitive cell is seated on above-mentioned laser beam printer respectively with measure the potential difference between the clear zone current potential in unexposed portion and the clear zone current potential in exposed portion (light memory=| the current potential of current potential-exposed portion of unexposed portion |).
The result of gained is shown in table 1.
Table 1TiOPC*/ pigment/photonasty current potential light memory AZOpigments adhesive resin variable quantity (w/w) (w/w) Δ VD       ΔVL
                       (μJ/cm2) (V)      (V)    (V)
Embodiment：1 7/3 10,/10 0.21-10+5 10 comparative examples：1         10/0   10/10        0.20     -60     -30    602         7/0    7/10         0.27     -40     -15    453         7/3    10/10        0.29     -25     +40    40*Oxygen titanium phthalein cyanogen
Find out from these results, the photonasty of embodiment 1 is equal to the photonasty of comparative example 1, reappearance is improved with light Memorability, the content of the titanyl phthalocyanine in the former is less than the latter.On the other hand, in comparative example 2, photonasty is relatively lower, and reappearance improves smaller with light memory characteristic, because the consumption of titanyl phthalocyanine is small, while not using AZOpigments again.Comparative example 3 employs conventional disazo pigment, does not obtain the effect of the present invention.
Embodiment 2
The dispersion liquid for charge generation layer is prepared in the same manner as in Example 1, and simply the dispersion liquid of titanyl phthalocyanine and the dispersion liquid of AZOpigments are prepared respectively.Here, the ratio of pigment and adhesive resin is 10/10 in each dispersion liquid.
Conductive carrier and glue-line are formed in the same manner as in Example 1, azo pigment dispersion is applied on the glue-line, and it is 0.1 μm to make thickness degree, it is subsequently dried, then titanyl phthalocyanine dispersion liquid is applied thereon, it is 0.25 μm to make thickness degree, re-dry, forms double-deck charge generation layer.Electric charge migrating layer is formed in the same manner as in Example 1.Therefore, electric photographic photosensitive element is produced.
Embodiment 3
Electric photographic photosensitive element is produced in method same as Example 2, simply AZOpigments charge generation layer is formed in reverse order with titanyl phthalocyanine charge generation layer.
The electric photographic photosensitive element that embodiment 2 and 3 is produced is evaluated in the same manner as example 1.The result of gained is as shown in table 2.In order to be compared, the result of the electric photographic photosensitive element produced in comparative example 1 is together illustrated, does not have AZOpigments in charge generation layer in the comparative example.
The electric camera photosensitive potential change amount light of table 2 memory photo-sensitive cell Δ VD      ΔVL
       (μJ/cm2) (V) (V) (V) embodiment 2：0.20-10 0 15 embodiment 3：0.24-5+20 5 comparative example 1：0.20         -60      -30            60
Find out from these results, in the present invention, repeatability and light memory characteristic are improved, and for photonasty, more preferably the charge generation layer comprising AZOpigments is arranged on conductive carrier on one side.
Embodiment 4-6
Production simply replaces I- type titanyl phthalocyanines corresponding to the electric photographic photosensitive element of embodiment 4,5 and 6 using A- types titanyl phthalocyanine, B- types titanyl phthalocyanine and Y-Shaped titanyl phthalocyanine in the same manner as in Example 1；The x-ray diffraction pattern of this several oxygen phthalocyanine is shown in Fig. 2,3 and 4.
Comparative example 4-6
To produce the electric photographic photosensitive element corresponding to comparative example 4,5 and 6 with the identical method of comparative example 1, A- types titanyl phthalocyanine, B- types titanyl phthalocyanine and Y-Shaped titanyl phthalocyanine is simply respectively adopted instead of I- type titanyl phthalocyanines.
In the same manner as example 1, the embodiment 4-6 and comparative example 4-6 electric photographic photosensitive elements produced are evaluated.The result of gained is shown in table 3.
Table 3TiOPC* TiOPC*The crystal formation AZOpigments adhesive resin variable quantity of/pigment/photonasty current potential light memory
(w/w) (w/w) Δ VD  ΔVLEmbodiment：                    (μJ/cm2) 7/3 10,/10 0.36-30-15 156Y types of (V) (V) (V) 4A 7/3 10,/10 0.37-25 0 105B types of type, 7/3 10,/10 0.25-20-10 20 comparative example：The 506Y types 1,0/0 10,/10 0.23-50-25 55 of 1,0/0 10,/10 0.37-60-20 455B types of 4A types 1,0/0 10,/10 0.35-70-30
*Oxygen titanium phthalein cyanogen
No matter it can be seen from the results above that the crystal formation of titanyl phthalocyanine, the present invention is effective.
Embodiment 7-16
Production corresponds to embodiment 7-16 electric photographic photosensitive element in the same manner as in Example 1, the AZOpigments that typical pigments 4,29,3,28,5,20,24,26,34 and 37 are simply respectively adopted replaces the AZOpigments of typical pigments 1, carries out similar evaluation.Obtained result is shown in table 4.In order to be compared, the result of embodiment 1 and comparative example 1 is together illustrated.
Table 4
Typical pigments photonasty potential change amount light is remembered
                               ΔVn     ΔVL
                 (μJ/cm2)    (V)       (V)        (V)
Embodiment：
7        4         0.22         -10       +5        15
8        29        0.20         -5        +10       5
9        3         0.23         -25        0        20
10       28        0.23         -20       -10       10
11       5         0.21         -10       +10       25
12       20        0.22         -20       -10       15
13       24        0.23         -15       -10       25
14       26        0.23         -5        +10       20
15    34        0.21       -10       0       10
16    37        0.23       -25      -10      25
Embodiment：11 0.21-10+5 10 comparative examples：  1       -         0.20       -60       -30     60
Embodiment 1-20
Production corresponds to embodiment 17-20 electric photographic photosensitive element in the same manner as in Example 1, and simply charge transporting material is respectively adopted the compound with following structural formula and replaced.The charge transporting material used in embodiment 17：The charge transporting material used in embodiment 18；
Figure C9611071400572
The charge transporting material used in embodiment 19：
Figure C9611071400573
The charge transporting material used in embodiment 20：
Comparative example 7-10
To produce the electric photographic photosensitive element corresponding to comparative example 7-10 with the identical method of comparative example 1, simply those charge transporting materials replacement for embodiment 17-20 is respectively adopted in charge transporting material.
In the same manner as in Example 1, the embodiment 17-20 and comparative example 7-10 electric photographic photosensitive elements produced are evaluated.Obtained result is shown in Table 5.
The electric camera photosensitive potential change amount light of table 5 memory photo-sensitive cell Δ VD      ΔVL
         (μJ/cm2) (V) (V) (V) embodiment 17：0.24-5+10 0 comparative example 7：0.22-40-15 40 embodiment 18：0.21-15-5 5 comparative example 8：The comparative example 9 of 0.20-60-25 55 embodiment 19 0.21-20-10 15：0.21-50-30 60 embodiment 20：0.25-25+10 25 comparative example 10：    0.23       -70        -45        65
Find out from these results, no matter the type of charge transporting material, the present invention is effective.

Claims (18)

1. a kind of electric photographic photosensitive element comprising conductive carrier and the photosensitive layer on the conductive carrier,
The AZOpigments that described photosensitive layer is represented comprising titanyl phthalocyanine and by following formula (1)；Formula (1)： 
Ar  N=N-Cp)n   
Wherein, Ar represents the substituted or unsubstituted aromatic hydrocarbon group that can be bonded together by linker or the substituted or unsubstituted heterocyclic group that can be bonded together by linker；Cp represents the coupling agent residue with phenolic hydroxyl group, and the Cp described at least one represents the coupling agent residue represented by following formula (2)；N represents 2-4 integer；
Formula (2)：
Figure C9611071400022
Wherein, A represents the divalent group of substituted or unsubstituted aromatic hydrocarbon ring, or on ring the substituted or unsubstituted heterocycle comprising nitrogen-atoms divalent group.
2. all Cp in electric photographic photosensitive element according to claim 1, wherein formula (1) are the groups represented by formula (2).
3. the A in electric photographic photosensitive element according to claim 2, wherein formula (2) is unsubstituted adjacent phenylene.
4. the n in electric photographic photosensitive element according to claim 3, wherein formula (1) is 2 or 3.
5. electric photographic photosensitive element according to claim 1, wherein described titanyl phthalocyanine has characteristic peaks in the x-ray diffraction pattern of CuK α features at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° of Bragg angle (2 θ ± 0.2 °) place.
6. electric photographic photosensitive element according to claim 4, wherein described titanyl phthalocyanine has characteristic peaks in the x-ray diffraction pattern of CuK α features at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° of Bragg angle (2 θ ± 0.2 °) place.
7. a kind of handle box, the box includes a kind of electric photographic photosensitive element and at least one mechanism selected from charging mechanism, developing mechanism and cleaning mechanism,
Described electric photographic photosensitive element includes conductive carrier and the photosensitive layer on the conductive carrier,
The AZOpigments that described photosensitive layer is represented comprising titanyl phthalocyanine and by following formula (1), formula (1)：
Ar  N=N-Cp)n
Wherein, Ar represents the substituted or unsubstituted aromatic hydrocarbon group that can be bonded together by linker or the substituted or unsubstituted heterocyclic group that can be bonded together by linker；Cp represents the coupling agent residue with phenolic hydroxyl group, and the Cp described at least one represents the coupling agent residue represented by following formula (2)；N represents 2-4 integer；
Formula (2)：
Wherein, A represents the divalent group of substituted or unsubstituted aromatic hydrocarbon ring, or on ring the substituted or unsubstituted heterocycle comprising nitrogen-atoms divalent group；And
Described is supported in electric photographic equipment main body on the whole selected from the mechanism for including charging mechanism, developing mechanism and cleaning mechanism, and can be disassembled from the electric photographic equipment main body.
8. all Cp in handle box according to claim 7, wherein formula (1) are the groups represented by formula (2).
9. the A in handle box according to claim 8, wherein formula (2) is unsubstituted adjacent phenylene.
10. the n in handle box according to claim 9, wherein formula (1) is 2 or 3.
11. handle box according to claim 7, wherein described titanyl phthalocyanine has characteristic peaks in the x-ray diffraction pattern of CuK α features at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° of Bragg angle (2 θ ± 0.2 °) place.
12. handle box according to claim 10, wherein described titanyl phthalocyanine has characteristic peaks in the x-ray diffraction pattern of CuK α features at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° of Bragg angle (2 θ ± 0.2 °) place.
13. a kind of electric photographic equipment, the equipment includes a kind of electric photographic photosensitive element, a kind of charging mechanism, exposure mechanism, developing mechanism and transfer means,
Described electric photographic photosensitive element includes conductive carrier and the photosensitive layer on the conductive carrier,
The AZOpigments that described photosensitive layer is represented comprising titanyl phthalocyanine and by following formula (1), formula (1)：
Ar  N=N-Cp)n
Wherein, Ar represents the substituted or unsubstituted aromatic hydrocarbon group that can be bonded together by linker or the substituted or unsubstituted heterocyclic group that can be bonded together by linker；Cp represents the coupling agent residue with phenolic hydroxyl group, and the Cp described at least one represents the coupling agent residue represented by following formula (2)；N represents 2-4 integer；
Formula (2)：
Figure C9611071400051
Wherein, A represents the divalent group of substituted or unsubstituted aromatic hydrocarbon ring, or on ring the substituted or unsubstituted heterocycle comprising nitrogen-atoms divalent group.
14. all Cp in electric photographic equipment according to claim 13, wherein formula (1) are the groups represented by formula (2).
15. the A in electric photographic equipment according to claim 14, wherein formula (2) is unsubstituted adjacent phenylene.
16. the n in electric photographic equipment according to claim 15, wherein formula (1) is 2 or 3.
17. electric photographic equipment according to claim 13, wherein described titanyl phthalocyanine has characteristic peaks in the x-ray diffraction pattern of CuK α features at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° of Bragg angle (2 θ ± 0.2 °) place.
18. electric photographic equipment according to claim 16, wherein described titanyl phthalocyanine has characteristic peaks in the x-ray diffraction pattern of CuK α features at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° of Bragg angle (2 θ ± 0.2 °) place.
CN96110714A 1995-05-17 1996-05-17 Electric photography photoactive elements, processing-box and electric photography apparatus Expired - Fee Related CN1085352C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP14142095 1995-05-17
JP141420/95 1995-05-17

Publications (2)

Publication Number Publication Date
CN1159613A CN1159613A (en) 1997-09-17
CN1085352C true CN1085352C (en) 2002-05-22

Family

ID=15291593

Family Applications (1)

Application Number Title Priority Date Filing Date
CN96110714A Expired - Fee Related CN1085352C (en) 1995-05-17 1996-05-17 Electric photography photoactive elements, processing-box and electric photography apparatus

Country Status (6)

Country Link
EP (1) EP0743561B1 (en)
KR (1) KR100230539B1 (en)
CN (1) CN1085352C (en)
DE (1) DE69611857T2 (en)
HK (1) HK1011735A1 (en)
SG (1) SG52802A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100349070C (en) * 2004-11-25 2007-11-14 同济大学 Azo/phthalocyanine composite single layer organic photoconductor and preparing method therefor

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6218063B1 (en) 1998-08-26 2001-04-17 Canon Kabushiki Kaisha Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus
JP2000162806A (en) 1998-11-30 2000-06-16 Canon Inc Electrophotographic photoreceptor, its production, process cartridge and electrophotographic device
US6773856B2 (en) 2001-11-09 2004-08-10 Canon Kabushiki Kaisha Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus
US8206880B2 (en) * 2009-06-05 2012-06-26 Ricoh Company, Ltd. Electrophotographic photoreceptor, and image forming apparatus and process cartridge therefor using the photoreceptor
JP5610907B2 (en) 2009-08-18 2014-10-22 キヤノン株式会社 Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus
JP5623886B2 (en) * 2009-12-09 2014-11-12 富士フイルム株式会社 Colored photosensitive composition, method for producing color filter, color filter, and liquid crystal display device

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63313165A (en) * 1987-06-17 1988-12-21 Canon Inc Electrophotographic sensitive body
JP2591648B2 (en) * 1988-03-29 1997-03-19 コニカ株式会社 Electrophotographic photoreceptor
JPH01257862A (en) * 1988-04-07 1989-10-13 Mitsubishi Paper Mills Ltd Electrophotographic planographic printing plate
JP2583787B2 (en) * 1988-04-22 1997-02-19 コニカ株式会社 Photoconductor
US5190839A (en) * 1988-07-04 1993-03-02 Konica Corporation Electrophotographic photoreceptor
JPH0337656A (en) * 1989-07-04 1991-02-19 Konica Corp Electrophotographic sensitive body
US5411828A (en) * 1992-02-05 1995-05-02 Canon Kabushiki Kaisha Electrophotographic photosensitive member, and electrophotographic apparatus, device unit and facsimile machine having the photosensitive member
EP0658814B1 (en) * 1993-11-29 1999-07-14 Canon Kabushiki Kaisha Electrophotographic photosensitive member, electrophotographic apparatus including same and electrophotographic apparatus unit
TW382078B (en) * 1994-06-10 2000-02-11 Canon Kk Electrophotographic photosensitive member, electrophotographic apparatus including same and electrophotographic apparatus unit

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100349070C (en) * 2004-11-25 2007-11-14 同济大学 Azo/phthalocyanine composite single layer organic photoconductor and preparing method therefor

Also Published As

Publication number Publication date
CN1159613A (en) 1997-09-17
EP0743561B1 (en) 2001-02-28
DE69611857D1 (en) 2001-04-05
KR960042234A (en) 1996-12-21
EP0743561A3 (en) 1998-01-21
KR100230539B1 (en) 1999-11-15
HK1011735A1 (en) 1999-07-16
EP0743561A2 (en) 1996-11-20
SG52802A1 (en) 1998-09-28
DE69611857T2 (en) 2001-08-02

Similar Documents

Publication Publication Date Title
JP4316634B2 (en) Electrophotographic photosensitive member containing enamine compound, image forming apparatus provided with the same, enamine compound and method for producing the same
WO2014021341A1 (en) Electrophotographic photo-receptor, electrophotographic photo-receptor cartridge, image-forming device, and triarylamine compound
JP4134200B2 (en) Electrophotographic photoreceptor and image forming apparatus
CN1085352C (en) Electric photography photoactive elements, processing-box and electric photography apparatus
JP4264440B2 (en) Electrophotographic photoreceptor and image forming apparatus
JP5126440B2 (en) Electrophotographic photosensitive member, electrophotographic photosensitive member cartridge, and image forming apparatus
JP4276959B2 (en) Novel amine-bisdiene and -bistriene compounds, and electrophotographic photoreceptors and image forming apparatuses using the same
JP2012128355A (en) Electrophotographic photoreceptor and image forming apparatus using the same
JP5353078B2 (en) Electrophotographic photosensitive member and image forming apparatus using compound having enamine skeleton
US20110136050A1 (en) Electrophotographic photoconductor and image forming apparatus including the same
US7364823B2 (en) Amine compound, electrophotographic photoreceptor using the amine compound and image forming apparatus having the same
JP4388975B2 (en) Electrophotographic photoreceptor containing triamine compound, image forming apparatus provided with the same, triamine compound and method for producing the same
JP4869390B2 (en) Electrophotographic photoreceptor and image forming apparatus having the same
JP2005023322A (en) Naphthalene tetracarboxylic acid diimide polymer, electrophotographic photosentitive body containing the same, electrophotographic cartridge, electrophotographic drum, and electrophotographic image-forming apparatus
JP2006076894A (en) Hydrazone compound and electrophotographic photo-sensitive body using the hydrazone compound, and image forming apparatus equipped with the electrophotographic photo-sensitive body
JP2001265035A (en) Electrophotographic photoreceptor, and process cartridge and electrophotographic device each using the same
JP3715767B2 (en) Electrophotographic photosensitive member, process cartridge having the electrophotographic photosensitive member, and electrophotographic apparatus
JP2005162641A (en) Amine compound and method for producing the same, and electrophotographic photoreceptor using the amine compound and image-forming apparatus equipped with the same
JP2008281782A (en) Electrophotographic photoreceptor and image forming apparatus
JP4819214B2 (en) Octaphenyltetraazaporphyrinatomagnesium, method for producing octaphenyltetraazaporphyrinatomagnesium, electrophotographic photoreceptor using the octaphenyltetraazaporphyrinatomagnesium, process cartridge and electrophotographic apparatus provided with the electrophotographic photoreceptor
US20120156600A1 (en) Electrophotographic photoconductor and image forming apparatus using the same
JP2008275779A (en) Electrophotographic photoreceptor and image forming apparatus including the same, and triarylamine dimer compound and method for producing the same
JP4661241B2 (en) Fluorine-substituted indium phthalocyanine, and electrophotographic photosensitive member, electrophotographic photosensitive member cartridge, and image forming apparatus using the same
JP4661613B2 (en) Electrophotographic photosensitive member, electrophotographic photosensitive member cartridge, and image forming apparatus
JP3197128B2 (en) Electrophotographic photoreceptor and electrophotographic apparatus provided with the electrophotographic photoreceptor

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20020522

Termination date: 20140517