CN103869639B - Electrophotographic photosensitive element, handle box, electronic photographing device and phthalocyanine crystal - Google Patents
Electrophotographic photosensitive element, handle box, electronic photographing device and phthalocyanine crystal Download PDFInfo
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- CN103869639B CN103869639B CN201310684783.5A CN201310684783A CN103869639B CN 103869639 B CN103869639 B CN 103869639B CN 201310684783 A CN201310684783 A CN 201310684783A CN 103869639 B CN103869639 B CN 103869639B
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Abstract
The present invention relates to electrophotographic photosensitive element, handle box, electronic photographing device and phthalocyanine crystal.Electrophotographic photosensitive element comprises supporting mass and is formed at the charge generation layer on this supporting mass and charge transport layer.Described charge generation layer comprises certain amines compound.
Description
Technical field
The present invention relates to electrophotographic photosensitive element, the handle box each with electrophotographic photosensitive element and electrofax
Equipment, and relate to phthalocyanine crystal.
Background technology
Due to be generally used for the semiconductor laser of the image exposing apparatus of electrophotographic photosensitive element have 650 to
The long oscillation wavelength of 820nm scope, the electrophotographic photosensitive element to the light of long wavelength range with ISO is at present
Development phase.Recently, the light to the semiconductor laser of short oscillation wavelength has the electrophotographic photosensitive element of ISO also
It is in the development phase to realize high-definition picture.
Known azo pigment and phthalocyanine color have ISO as to the light of long wavelength region to short wavelength region scope
Charge generation substance.
Although the electrophotographic photosensitive element using AZOpigments or phthalocyanine color has excellent photonasty, problem is to produce
Raw photocarrier tends to remaining in photosensitive layer and serves as memorizer, is easily caused potential change such as ghost image in some cases.
In order to solve the problem of phthalocyanine color, phthalocyanine color is applied in combination with specific AZOpigments.
In Japanese Patent Application Laid-Open S59-30541 publication, Japanese Patent Application Laid-Open 2007-138153 public affairs
Report and Japanese Patent Application Laid-Open 2009-301016 publication describe the 1-Phenylethanone. for electrophotographic photosensitive element
Compound.
Japanese Patent Application Laid-Open S59-30541 publication describes the absorbing wavelength as phthalocyanine vapor-deposited film
The acetylation benzene derivative of skew agent.
Japanese Patent Application Laid-Open 2007-138153 publication describes by making phthalocyanine crystal presoma and fluorobenzene
Derivant contact and manufacture is to have main peak at 27.2 ° at Bragg angle 2 θ in the X-ray diffraction using CuK α lonizing radiation
Oxytitanium phthalocyanine crystal.Describing according to it, the oxytitanium phthalocyanine crystal thus prepared has the crystal stability of improvement and improvement
Light sensitivitys.
According to Japanese Patent Application Laid-Open 2009-301016 publication, using alpha-aminoacetophenone compound as polymerization
Initiator adds to the protective layer of Electrifier frame, photoreceptor to improve hardening.
As it has been described above, carried out various trial for improving electrophotographic photosensitive element.In recent years, for improving Gao Pin further
Matter image, it is desirable to prevent the image deterioration caused in various environment due to ghost image.
Summary of the invention
Present invention aim to address the problems referred to above and provide minimizing not only under ambient temperature and moisture environment but also even low
The electrophotographic photosensitive element of the image deflects especially caused due to ghost image under critical conditions under temperature low moisture environments.The present invention
Another one purpose be to provide handle box and the electronic photographing device each with described electrophotographic photosensitive element.The present invention
Another purpose be to provide in crystal comprising the phthalocyanine crystal of certain amines compound.
The present invention provides electrophotographic photosensitive element, comprising: supporting mass；With the charge generation layer being formed on supporting mass
And charge transport layer；The amines that wherein said charge generation layer comprises charge generation substance and following formula (1) represents:
In formula (1), R1To R5Represent hydrogen atom, halogen atom, hydroxyl, carboxyl, alkoxy carbonyl, aryloxy group independently of one another
Carbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxyl, substituted or unsubstituted aryloxy group, there is substituent group
Amino, or substituted or unsubstituted ring amino.R1To R5At least one for the substituted ammonia of substituted or unsubstituted aryl
Base, with the substituted amino of substituted or unsubstituted alkyl or substituted or unsubstituted ring amino.
The present invention also provides for being detachably mounted to the handle box of the main body of electronic photographing device, wherein said handle box one
Bodyization ground supporting electrophotographic photosensitive element and the free charging device of choosing, developing unit, transfer device and cleaning device form
At least one device of group.
The present invention also provides for be had electrophotographic photosensitive element and charging device, image exposing apparatus, developing unit and turns
The electronic photographing device that printing equipment is put.
The present invention is additionally provided in the phthalocyanine crystal of the compound that contained in crystal (1) represents.
The present invention can provide minimizing not only under ambient temperature and moisture environment but also even the tightest under low temperature and low humidity environment
The electrophotographic photosensitive element of the image deflects caused due to ghost image under the conditions of severe.The present invention may also provide each have described
The handle box of electrophotographic photosensitive element and electronic photographing device.It is excellent that the present invention also can be provided as having of charge generation substance
The phthalocyanine crystal of good characteristic.
With reference to accompanying drawing, by the explanation of following exemplary embodiment, further characteristic of the invention becomes apparent.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the electronic photographing device being provided with the handle box with electrophotographic photosensitive element.
Fig. 2 is the x-ray diffractogram of powder of the hydroxygallium phthalocyanine crystal obtained in embodiment 1-1.
Fig. 3 is the x-ray diffractogram of powder of the hydroxygallium phthalocyanine crystal obtained in reference example 1-1.
Detailed description of the invention
Will be described in detail in accordance with the accompanying drawings now the preferred embodiments of the invention.
The amines comprised in the charge generation layer of the electrophotographic photosensitive element of the present invention has what following formula (1) represented
Structure.
In formula (1), R1To R5Represent hydrogen atom, halogen atom, hydroxyl, carboxyl, alkoxy carbonyl, aryloxy group independently of one another
Carbonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxyl, substituted or unsubstituted aryloxy group, there is substituent group
Amino or substituted or unsubstituted ring amino.R1To R5At least one for the substituted ammonia of substituted or unsubstituted aryl
Base, with the substituted amino of substituted or unsubstituted alkyl or substituted or unsubstituted ring amino.
R in formula (1)1To R5At least one can be with the substituted amino of substituted or unsubstituted alkyl.It is highly preferred that institute
State with the substituted amino of substituted or unsubstituted alkyl especially for dialkyl amido.
It is further preferred that described dialkyl amido is dimethylamino or diethylamino.
It is highly preferred that the amines that amines represents for following formula (2) especially.
R in formula (2)6Or R7Represent methyl or ethyl independently of one another.
R in formula (1)1To R5At least one can be substituted or unsubstituted ring amino.Substituted or unsubstituted ring amino
Example comprises substituted or unsubstituted piperazinyl, substituted or unsubstituted pyrrolidinyl, substituted or unsubstituted pyrrole radicals, replaces
Or unsubstituted triazolyl, substituted or unsubstituted imidazole radicals, substituted or unsubstituted pyridine radicals, substituted or unsubstituted pyrazine
Base, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted triazine radical, substituted or unsubstituted quinolyl, replace or do not take
The indolinyl in generation, substituted or unsubstituted acridinyl, substituted or unsubstituted morpholinyl (morpholinyl group),
Substituted or unsubstituted piperidyl, morpholino base (morpholino group), and substituted or unsubstituted piperidino
(piperidino group).Ring amino can be 3 to 8-ring amino.Structure at least one carbon atom looped can with oxygen atom or
Nitrogen-atoms etc. replace.It is particularly preferably morpholino base or the piperidino of hexatomic ring amino.
It is highly preferred that amines is the amines that following formula (3) represents.
Substituted alkyl, substituted alkoxyl, substituted aryloxy group, substituted amino, substituted aryl and take in formula (1)
The example of the respective substituent group of ring amino in generation can include alkyl such as methyl, ethyl, propyl group and butyl, aralkyl such as benzyl, alkane
Epoxide such as methoxyl group and ethyoxyl, dialkyl amido such as dimethylamino and diethylamino, alkoxy carbonyl such as methoxyl group carbonyl
Base and ethoxy carbonyl, phenyl, naphthyl, xenyl, nitrobenzophenone, tolyl, bromophenyl, cyano-phenyl, methoxyphenyl, second
Aminosulfonylphenyl, nitro, cyano group, formoxyl, alkoxyl, acetyl group, halogen atom such as fluorine atom, chlorine atom and bromine atoms, hydroxyl and
Halomethyl.Alkyl is preferred substituents especially.
The charge generation layer of the present invention can be the phthalocyanine crystal being included in crystal the amines that (1) Han formula represents
Layer.
R in the formula (1) being contained in phthalocyanine crystal1To R5Preferred substituents and the formula being contained in charge generation layer
(1) preferred substituents of the amines represented is identical.
Although below describe be contained in the present invention electrophotographic photosensitive element charge generation layer in amines and
The instantiation (exemplary compounds) of the amines being contained in phthalocyanine crystal, but the present invention is not limited to this.
Amines for the present invention can be obtained commercially or can be the most synthesized as described below.
Aminoacetophenone is used as raw material.Substituent group can be introduced by the substitution reaction between aminoacetophenone and halogenide
To amino.In the presence of metallic catalyst, the reaction between aminoacetophenone and aromatic halide takes for synthesis aryl
The amines in generation is particularly useful.Alternatively, reductive amination process amines substituted to synthesis alkyl is useful.
Alternatively, halo acetophenone is used as raw material.Amino can be drawn by the substitution reaction between halo acetophenone and amine
Enter the position to halogen.
The concrete synthesis example of exemplary compounds (3) is below described.In synthesis example, " part " refers to " mass parts ".Infrared
(IR) absorption spectrum is with Fourier transform infrared spectrometer (trade name: FT/IR-420 is manufactured by Jasco Corporation)
Measure.Nuclear magnetic resonance, NMR (NMR) spectrum nuclear magnetic resonance equipment (trade name: R-90 is manufactured by Hitachi, Ltd) measures.
[synthesis example 1]
The synthesis of exemplary compounds (3)
Under nitrogen flowing, comprising 1, in the eggplant type flask of 500 parts of toluene, adding 344 parts of dry cesium carbonates, 3.4 portions of vinegar
Acid palladium, 13 parts of (s)-BINAP (double (the diphenylphosphino)-1,1'-dinaphthalene of 2,2'-), 150 parts of 4'-bromoacetophenones, 100 parts
Quinoline.Heat at 100 DEG C and stir described mixture 15 hours.After cooling, add 500 parts of chloroforms and with being covered with diatomaceous mistake
Filter filtering reacting liquid.Solvent in evaporated under reduced pressure filtrate.Refined residue in silicagel column (solvent: toluene/ethyl acetate)
To prepare the yellow crystals of 82 parts of exemplary compounds (3).
The IR absorption spectrum of mensuration and mensuration are below described1The characteristic peak of H-NMR spectrum.
IR(cm-1, KBr): 2844,1661,1600,1244,1121,930,822
1H-NMR (ppm, CDCL3): δ=7.88 (d, 2H), 6.86 (d, 2H), 3.8-3.9 (m, 4H), 3.2-3.4 (m,
4H), 2.52 (s, 3H)
The charge generation substance being contained in charge generation layer can be phthalocyanine color or AZOpigments, this is because have height
Light sensitivitys.Especially, more preferably phthalocyanine color or phthalocyanine crystal.
The example of phthalocyanine color or phthalocyanine crystal includes containing axle ligand or the metal-free phthalocyanine of substituent group and metal phthalein
Cyanines.In phthalocyanine color and phthalocyanine crystal, preferably oxytitanium phthalocyanine crystal and gallium phthalocyanine crystal, although they are easily caused ghost image but tool
There is excellent light sensitivitys, be effective to the present invention.
In gallium phthalocyanine crystal, it is preferably with the X-ray diffraction of CuK α lonizing radiation is 7.4 ° ± 0.3 ° at Bragg angle 2 θ
At 28.2 ° ± 0.3 °, there is the hydroxygallium phthalocyanine crystal of crystal form at peak, with in the X-ray diffraction of CuK α lonizing radiation in Prague
θ ± 0.2 °, angle 2 is the gallium chlorine phthalocyaninate crystal of the crystal form at 7.4 °, 16.6 °, 25.5 ° and 28.3 ° with peak.Oxytitanium phthalocyanine crystal
In, it is preferably at the oxytitanium phthalocyanine crystal that Bragg angle 2 θ is the crystal form at 27.2 ° ± 0.2 ° with peak.
In particular it is preferred to at the hydroxyl that Bragg angle 2 θ is the crystal form at 7.4 ° ± 0.3 ° and 28.2 ° ± 0.3 ° with peak
Base gallium phthalocyanine crystal.
Especially, it is more preferably 7.3 ° in Bragg angle 2 θ ± 0.2 °, there is peak, at 24.9 ° and 28.1 ° at 28.1 °
There is the hydroxygallium phthalocyanine crystal of the crystal form of highest peak.In addition it is also preferred that for be 7.5 ° in Bragg angle 2 θ ± 0.2 °, 9.9 °,
There is at 16.3 °, 18.6 °, 25.1 ° and 28.3 ° the hydroxygallium phthalocyanine crystal of the crystal form at peak.
The example of the phthalocyanine being formed in the phthalocyanine crystal of the amines that contained in crystal (1) represents comprises can have axle
The metal-free phthalocyanine of ligand and metal phthalocyanine.Phthalocyanine can have substituent group.Particularly preferably oxytitanium phthalocyanine crystal and gallium phthalocyanine is brilliant
Body, although it is easily caused ghost image, but has excellent light sensitivitys, is effective to the present invention.
As described below, it is formed in the reality of the gallium phthalocyanine of the gallium phthalocyanine crystal of the amines that contained in crystal (1) represents
Example comprises gallium atom and has halogen atom, hydroxyl or the gallium Phthalocyanine of alcoxyl standard shaft ligand.Phthalocyanine ring can comprise substituent group such as
Halogen atom.
In crystal, preferably comprise the gallium phthalocyanine crystal of N,N-dimethylformamide further.
In gallium phthalocyanine crystal, preferably hydroxygallium phthalocyanine crystal, gallium bromophthalocyaninate crystal and gallium iodine phthalocyaninate crystal, they have
Excellent light sensitivitys, is effective to the present invention.In particular it is preferred to hydroxygallium phthalocyanine crystal.Hydroxygallium phthalocyanine crystal comprises tool
There is the gallium atom of hydroxyl axle ligand.Gallium bromophthalocyaninate crystal comprises the gallium atom with bromine atoms axle ligand.Gallium iodine phthalocyaninate is brilliant
Body comprises the gallium atom with atomic iodine axle ligand.
In hydroxygallium phthalocyanine crystal, especially, with in the X-ray diffraction of CuK α lonizing radiation at Bragg angle 2 θ it is more preferably
Having the hydroxygallium phthalocyanine crystal at peak at 7.4 ° ± 0.3 ° and 28.3 ° ± 0.3 °, it has the figure that minimizing is caused due to ghost image
Effect as defect.
The content of the amines that the formula (1) being contained in phthalocyanine crystal represents can be more than 0.05 mass % and 3.0 matter
Amount below %.
In crystal in the phthalocyanine crystal of contained (1) amines represented, amines formula (1) represented introduces
In crystal.
It is described in the manufacture method of the phthalocyanine crystal of the amines that contained in crystal (1) represents below.In crystal
The phthalocyanine crystal of the amines that contained (1) represents can pass through will be by acid molten (acid pasting) prepared phthalocyanine and formula
(1) amines represented and solvent mix merga pass wet lapping method and process and obtain being transformed into crystal.
Milled processed is use dispersion such as bead, steel ball and oxidation in lapping device such as sand mill and ball mill
The process of aluminum ball.Milling time can be about 10 to 60 hours.Particularly preferably in method, it is sampled with the interval of 5 to 10 hours
To check the Bragg angle of crystal.In milled processed, the amount of dispersion can be 10 to 50 quality times of gallium phthalocyanine.Use is molten
The example of agent comprises amide series solvent such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-METHYLFORMAMIDE, N-methyl
Acetamide and N-methyl propanamide, halogen series solvent such as chloroform, ether series solvent such as oxolane, sulfoxide series solvent such as diformazan is sub-
Sulfone.The amount of the solvent used can be 5 to 30 quality times of phthalocyanine.The amount of the amines that the formula (1) used represents can be phthalein
0.1 to 30 quality of cyanines times.
In the present invention, analyze the measurement data by NMR measurement and the phthalocyanine crystal of thermogravimetric (TG) measurement gained to determine
The amines that the phthalocyanine crystal of the present invention the most contained in crystal (1) represents.
Such as, maybe it is carried out after grinding when the amines represented with solvent dissolution type (1) is ground processing
Time, the NMR of the phthalocyanine crystal carrying out gained measures.When the compound that formula (1) represents being detected from the phthalocyanine crystal of gained,
Judge the amines that contained in crystal (1) represents.
On the other hand, the amines represented when formula (1) does not dissolves in the solvent used in milled processed and insoluble in grinding
After cleaning solvent time, carry out gained phthalocyanine crystal NMR measure.When the amines that formula (1) represents being detected, pass through
Following methods judges.
The phthalocyanine crystal that individually carries out the amines that represented by addition formula (1) and obtain, represent except being added without formula (1)
Amines outside the respective TG of the phthalocyanine crystal prepared in the same manner and the only amines that formula (1) represents measure.
When the TG measurement result of the phthalocyanine crystal obtained by adding amines is construed under being added without amines preparation
During the mixing of the predetermined ratio of the independent measurement result of phthalocyanine crystal and amines, it is judged that for phthalocyanine crystal and amines shape
Simple mixtures or amines is become to be attached to the surface of phthalocyanine crystal.
On the other hand, when the TG measurement result of phthalocyanine crystal obtained by adding amines shows, and it is not added with amine
Compound and the TG measurement result of phthalocyanine crystal prepared is compared, in the temperature that temperature has reduced higher than the weight of only amines
Under degree, when weight reduces increase, it is judged that the amines that contained in crystal (1) represents.
TG measurement, X-ray diffraction analysis and the MR of the phthalocyanine crystal carrying out the present invention under the following conditions measure.
[TG measurement]
Measuring instrument: TG/DTA measurement apparatus (being manufactured by Seiko Instruments Inc) simultaneously.(trade name: TG/
DTA 220U)
Atmosphere: nitrogen stream (300cm3/min)
Measurement scope: 35 DEG C to 600 DEG C
Temperature rate-of-rise: 10 DEG C/min
[powder x-ray diffraction analysis]
Measuring instrument: X-ray diffraction analysis instrument RINT-TTRII (is manufactured by Rigaku Corporation)
X-ray tube: Cu
X-ray tube voltage: 50KV
X-ray tube current: 300mA
Scan method: 2 θ/θ scanning
Sweep speed: 4.0 °/min
Sampling interval: 0.02 °
Start angle (2 θ): 5.0 °
Stop angle (2 θ): 40.0 °
Adnexa: standard sample sample platform
Wave filter: do not use
Incident monochromatic: to use
Counting monochromator (counter monochrometer): do not use
Divergent slit: open
Indulge and dissipate restriction slit: 10.00mm
Scatter slit: open
Light-receiving slit: open
Flat board monochromator: use
Enumerator: scintillation counter
[NMR measurement]
Measuring instrument: AVANCE III 500 (being manufactured by Bruker)
Solvent: weight sulphuric acid (D2SO4)
The phthalocyanine crystal comprising the compound that the formula (1) of the present invention represents in crystal has excellent merit as photoconductive body
Can, and in addition to can be applicable to electrophotographic photosensitive element, it is also applied to solaode, sensor and switching device etc..
The electrophotographic photosensitive element of the present invention includes the charge generation layer containing charge generation substance as photosensitive layer and contains
The charge transport layer of electric charge conveying material.Any one Wei upper strata of charge generation layer and charge transport layer although (face side),
But more preferably charge generation layer is lower floor (supporting side).
Suitable use has the supporting mass (conductance supporting body) of electric conductivity.The example of conductance supporting body comprises by metal (conjunction
Gold) (such as aluminum and rustless steel) supporting mass of making and be coated with what the metal of conductive film, alloy, plastics or paper were made by surface
Supporting mass.The shape of supporting mass can be the most cylindric or membranaceous.
The priming coat (also referred to as intermediate layer) with barrier effect and adhesive effect is configured in supporting mass and photosensitive layer (electricity
Lotus transfer layer or charge generation layer) between.
Priming coat and can be dried prepared by applying priming coat formation coating fluid on supporting mass or following conductive layer
Film formed.Coating fluid can be prepared by dissolving resin in a solvent.The example of resin comprises polyvinyl alcohol, polycyclic oxygen
Ethane, ethyl cellulose, methylcellulose, casein, polyamide, glue and gelatin.Priming coat can have film thickness be 0.3 to
5.0μm。
Conductive layer is configured between supporting mass and priming coat the irregular and defect to cover on supporting mass surface and subtracts
Few interference fringe.
Conductive layer and can be dried and solidify the film prepared by applying conductive layer formation coating fluid on supporting mass
Formed.Conductive layer formation coating fluid can be by dispersed electro-conductive granule in a solvent (such as white carbon black, metallic particles and burning
Composition granule) and resin glue prepare.The film thickness that conductive layer can have is 5 to 40 μm, more preferably 10 to 30 μm.
Charge generation layer can be formed by applying charge generation layer formation coating fluid the dry film prepared.Electric charge
Producing layer formation coating fluid can be by dispersion amines in a solvent and charge generation substance or the phthalein comprising amines
Cyanines crystal, and prepared by resin glue.The film thickness that charge generation layer can have is 0.05 to 1 μm, more preferably 0.1 to
0.3μm。
The content of the amines in charge generation layer relative to the gross mass of charge generation layer can be 0.05 mass % with
Go up and below 15 mass %, more than more preferably 0.1 mass % and below 10 mass %.Amines in charge generation layer
Content can be below more than 0.1 mass % and 20 mass % relative to charge generation substance, more than more preferably 0.3 mass % and
Below 10 mass %.
The content of the charge generation substance in charge generation layer can be 30 mass % relative to the gross mass of charge generation layer
Above and below 90 mass %, more than more preferably 50 mass % and below 80 mass %.
The amines being contained in charge generation layer can be amorphous or crystallization.Can be applied in combination two or more
Amines.
Example for the resin glue of charge generation layer comprises polyester, acrylic resin, phenoxy resin, poly-carbon
Acid esters, polyvinyl butyral resin, polystyrene, polyvinyl acetate, polysulfones, polyarylate, vinylidene chloride, acrylonitrile copolymer
With polyvinyl alcohol condensing benzaldehyde (polyvinyl benzal).Particularly preferably polyvinyl butyral resin and polyvinyl alcohol contracting benzene first
Aldehyde.
Charge transport layer can be formed by applying charge transport layer formation coating fluid the dry film prepared.Electric charge
Transfer layer formation coating fluid can be prepared by the conveying material of dissolved charge in a solvent and resin glue.
The film thickness that charge transport layer can have is 5 to 40 μm, more preferably 10 to 25 μm.
The content of electric charge conveying material can be more than 20 mass % and 80 mass % relative to the gross mass of charge transport layer
Hereinafter, more than more preferably 30 mass % and below 60 mass %.
Electric charge conveying material example comprise triarylamine compound, hydrazone compound, stilbene compounds, pyrazoline compounds,
Azole compounds, thiazolium compounds and triallyl methane compound.In particular it is preferred to triarylamine compound.
Example for the resin glue of charge transport layer comprises polyester, acrylic resin, phenoxy resin, poly-carbon
Acid esters, polystyrene, polyvinyl acetate, polysulfones, polyarylate, vinylidene chloride, acrylonitrile copolymer.In particular it is preferred to it is poly-
Carbonic ester and polyarylate.
Dipcoat method (dip coating), spraying process, rotation is included for forming the example of the method for application of the coating fluid of each layer
Coating, pearl coating, knife coating and bundle coating.
On photosensitive layer (charge generation layer or charge transport layer), protective layer can be set to protect photosensitive layer.
Protective layer can be coated with by applying the protective layer formation prepared by dissolving resin in a solvent on photosensitive layer
Cloth liquid dry and that solidification is prepared film are formed.Described film can solidify with heating, electron beam or ultraviolet.For protecting
The example of the resin of sheath comprise polyvinyl butyral resin, polyester, Merlon (e.g., Merlon Z and modified polycarbonate),
Nylon, polyimides, polyarylate, polyurethane, SB, Styrene-acrylic copolymer and styrene-
Acrylonitrile copolymer.
The film thickness that protective layer can have is 0.05 to 20 μm.
Protective layer can comprise conductive particle, UV absorbent, or lubricity particfes such as the resin particle containing fluorine atom.
The example of conductive particle comprises metal oxide particle such as granules of stannic oxide.
Fig. 1 is the signal of the electronic photographing device of the handle box being provided with the electrophotographic photosensitive element with the present invention
Figure.
The electrophotographic photosensitive element 1 with cylindrical shape (drum type) (processes speed with predetermined peripheral speed in the direction of the arrow
Degree) rotate driving around axle 2.
During rotary course, the surface electrostatic making electrophotographic photosensitive element 1 with charging device 3 is charged to positive or negative
Predetermined potential.Subsequently, electrophotographic photosensitive element is irradiated with the image exposure light 4 from image exposing apparatus (not shown)
The surface of 1 is to form the electrostatic latent image corresponding with target image information.Image exposure light 4 is corresponding to from such as exposing for slit
Light or the time series electricity data image signal of the target image information with the image exposing apparatus output of scanned laser beam exposure
And modulate intensity.
The electrostatic latent image being formed on the electrophotographic photosensitive element 1 surface toner being stored in developing unit 5 shows
Shadow (regular development or discharged-area development) is to form toner image on the surface of electrophotographic photosensitive element 1.Will be formed in electricity
Toner image transfer device 6 on the surface of sub-photosensitive component 1 is transferred to transfer materials 7.In this case, will
The bias of the opposite polarity polarity of the electric charge having and remain on toner applies to transfer device 6 (figure from grid bias power supply
Not shown).With with electrophotographic photosensitive element 1 rotate Tong Bu by the transfer materials 7 of paper from paper-feeding section (not shown)
Take out with supply between electrophotographic photosensitive element 1 and transfer device 6.
To there is the transfer materials 7 of the toner image transferred from electrophotographic photosensitive element 1 from electronic photographic sensitive structure
The surface of part 1 separates and is delivered to the image forming apparatus 8 for toner image.Thus print from electronic photographing device
Go out image formed matter (printout or copy).
After toner image is transferred to transfer materials 7, the surface cleaning device 9 of electrophotographic photosensitive element 1 clean with
Remove attachment material such as toner (toner of residual after transfer).Recently in the cleaner-less system of exploitation, available development sets
Standby grade directly removes toner after transfer.Subsequently, neutralize with the pre-exposure light 10 from pre-exposure equipment (not shown)
The surface of electrophotographic photosensitive element 1, is then recycled and reused for image and is formed.For there is the contact charging device 3 of charging roller not
It is necessarily required to pre-exposure equipment.
Select free electrophotographic photosensitive element 1, charging device 3, developing unit 5 and group multiple of cleaning device 9 composition
Assembly can be contained in container and integrally support to form the handle box being detachably mounted to electronic photographing device main body.
Such as, by least one and electronic photographic sensitive structure of the group of selecting free charging device 3, developing unit 5 and cleaning device 9 to form
Part 1 the most integrally supports to form box.Described box composition guide 12 (such as the guide rail of electronic photographing device main body)
It is detachably mounted to the handle box 11 of electronic photographing device main body.
Image exposure light 4 can be the reflection light beam of the original copy from electronic photographing device (such as photocopier and printer) or saturating
Cross the transmitted light beam of the original copy of electronic photographing device (such as photocopier and printer).Alternatively, image exposure light 4 can be by sound
Ying Yu reads the scanning of laser beam of signal, the driving of LED array or the driving of liquid crystal shutter array of sensor from original copy
The radiotherapy beam produced.
The electrophotographic photosensitive element 1 of the present invention can be widely used in electrofax application such as laser beam printer,
CRT printer, LED printer, FAX, liquid crystal printer and laser plate-making.
[embodiment]
With reference to specific examples below, the present invention is described in further detail, although the present invention is not limited to this.Embodiment and
(Fischerscope, by Fischer for the film thickness eddy current film thickness meter of each layer of the electrophotographic photosensitive element in comparative example
Instrumens K.K. manufactures) or obtain based on the proportion from the mass conversion of per unit area.
[embodiment 1-1]
Hydroxy gallium phthalocyanine by with Japanese Patent Application Laid-Open 2011-94101 described in synthesis example 1 and enforcement subsequently
Prepared by process identical in example 1-1.Then, by 0.5 part of hydroxy gallium phthalocyanine, 1.0 parts of exemplary compounds (1) (product code:
D1575, is manufactured by Tokyo Chemical Industry Co., Ltd.), 9.5 parts of DMFs are put into and are had 15
To grind 48 hours under room temperature (23 DEG C) in the ball mill of the bead of a diameter of 0.8mm of part.By with N, N-dimethyl formyl
The dispersion liquid of amine prepares hydroxygallium phthalocyanine crystal.During filtration, filter oxolane fully cleans.Vacuum drying filtering residue so that
Obtain 0.5 part of hydroxygallium phthalocyanine crystal.The x-ray diffractogram of powder of the hydroxygallium phthalocyanine crystal prepared is shown in Fig. 2.
Being measured by NMR, conversion based on proton ratio confirms: the exemplary compounds (1) of 0.39 mass % and 1.83
The N,N-dimethylformamide of quality % is contained in hydroxygallium phthalocyanine crystal.Owing to exemplary compounds (1) is dissolved in N, N-bis-
Methylformamide, finds that exemplary compounds (1) is contained in hydroxygallium phthalocyanine crystal.
[embodiment 1-2]
In addition to replace the exemplary compounds (1) in embodiment 1-1 by the exemplary compounds (3) prepared in synthesis example 1,
0.45 part of hydroxygallium phthalocyanine crystal is obtained by the process identical with embodiment 1-1.The hydroxygallium phthalocyanine crystal prepared
X-ray diffractogram of powder is identical with Fig. 2.
Measured by NMR, it was demonstrated that the exemplary compounds (3) of 0.42 mass % and the N of 1.83 mass %, N-dimethyl methyl
Amide is contained in hydroxygallium phthalocyanine crystal.Owing to exemplary compounds (3) is dissolved in DMF, find exemplary
Compound (3) is contained in hydroxygallium phthalocyanine crystal.
[embodiment 1-3]
In addition to replace 1.0 parts of exemplary compounds (3) in embodiment 1-2 with 0.5 part of exemplary compounds (3), pass through
The process identical with embodiment 1-2 obtains 0.45 part of hydroxygallium phthalocyanine crystal.The powder X-ray of the hydroxygallium phthalocyanine crystal prepared
X ray diffration pattern x is identical with Fig. 2.
Measured by NMR, it was demonstrated that the exemplary compounds (3) of 0.23 mass % and the N of 1.89 mass %, N-dimethyl methyl
Amide is contained in hydroxygallium phthalocyanine crystal.
[reference example 1-1]
In addition to without 1.0 parts of exemplary compounds (1) in embodiment 1-1, with the place identical with embodiment 1-1
Reason obtains 0.4 part of hydroxygallium phthalocyanine crystal.The x-ray diffractogram of powder of the hydroxygallium phthalocyanine crystal prepared is shown in Fig. 3.
[embodiment 2-1]
First, be coated with the barium sulfate particle of stannum oxide (trade name: Passtran PC1, by Mitsui by 60 parts
Mining&Smelting Co., Ltd. manufacture), (trade name: TITANIX JR, by Tayca for 15 parts of titan oxide particles
Corporation manufacture), (trade name: Phenolite J-325, by DIC Corporation for 43 parts of resol type phenol resins
Manufacture, Gu composition: 70 mass %), (trade name: SH28PA, by Dow Corning Toray Co., Ltd. for 0.015 part of silicone oil
Manufacture), (trade name: Tospearl 120, by Momentive Performance Materials for 3.6 parts of silicone resins
Inc. manufacture), 50 parts of 2-methoxy-1-propanols, and 50 parts of methanol put in ball mill, and disperse 20 hours to prepare conductive layer
Formation coating fluid.
Conductive layer formation coating fluid dip coated is applied on the aluminum cylinder (diameter: 24mm) as supporting mass,
Prepared film is dried 30 minutes to be formed and having the conductive layer that film thickness is 15 μm at 140 DEG C.
Subsequently, by 10 parts of copolymer polyamide resins, (trade name: Amilan CM8000, by Toray Industries, Inc.
Manufacture) and 30 parts of methoxymethylated 6-nylon resins (trade name: Tresin EF-30T, by Nagase Chemtex
Corporation manufactures) it is dissolved in the mixed solvent of 400 parts of methanol and 200 parts of n-butyl alcohol to prepare priming coat formation coating fluid.
Priming coat formation coating fluid dip coated is applied over conductive layer, by prepared dried coating film to form tool
The priming coat having film thickness to be 0.5 μm.
Subsequently, by 10 parts of hydroxygallium phthalocyanine crystals (charge generation substance) prepared in embodiment 1-1,5 parts of polyethylene
Butyral (trade name: S-LEC BX-1 is manufactured by Sekisui Chemical Co., Ltd.), and 250 parts of Ketohexamethylene put into
The sand mill of the bead with a diameter of 1mm processes 4 hours with dispersion.In dispersion liquid, add 250 parts of ethyl acetate with
Dilution dispersion liquid, thus prepare charge generation layer formation coating fluid.
Charge generation layer formation coating fluid dip coated is applied over priming coat.By prepared film at 100 DEG C
It is dried 10 minutes, to be formed, there is the charge generation layer that film thickness is 0.16 μm.
The compound (electric charge conveying material) that subsequently, 8 parts of following formulas (4) represented and 10 parts of Merlon (trade name:
Iupilon Z-200, is manufactured by Mitsubishi Engineering-Plastics Corporation) it is dissolved in 70 part of one chlorine
Benzene is to prepare charge transport layer formation coating fluid.
Charge transport layer formation coating fluid is applied over charge generation layer by dip coated.Prepared film is existed
It is dried at 110 DEG C 1 hour, to be formed, there is the charge transport layer that film thickness is 23 μm.
Thus manufacture the electrophotographic photosensitive element of embodiment 2-1 of cylindrical shape (drum type).
[embodiment 2-2]
Except replacing embodiment 2-1 is preparing charge generation layer shape with the hydroxygallium phthalocyanine crystal prepared in embodiment 1-2
Outside hydroxygallium phthalocyanine crystal during one-tenth coating fluid, in the way of identical with embodiment 2-1, manufacture the electricity in embodiment 2-2
Sub-photosensitive component.
[embodiment 2-3]
Except replacing embodiment 2-1 is preparing charge generation layer shape with the hydroxygallium phthalocyanine crystal prepared in embodiment 1-3
Outside hydroxygallium phthalocyanine crystal during one-tenth coating fluid, in the way of identical with embodiment 2-1, manufacture the electronics in embodiment 2-3
Photosensitive component.
[embodiment 2-4]
Except the preparation of the charge generation layer formation coating fluid in embodiment 2-1 is become following in addition to, with embodiment 2-1
In identical mode manufacture the electrophotographic photosensitive element in embodiment 2-4.
First, by 10 parts of reference example 1-1 prepare hydroxygallium phthalocyanine crystal (charge generation substance), 0.5 part exemplary
(trade name: S-LEC BX-1, by Sekisui Chemical Co., Ltd. system for compound (1), 5 parts of polyvinyl butyral resins
Make), and 250 parts of Ketohexamethylene put in the sand mill of the bead with a diameter of 1mm and process 4 hours with dispersion.Then, will
250 parts of ethyl acetate additions are used for diluting to dispersion liquid, to prepare charge generation layer formation coating fluid.
[embodiment 2-5]
Except with in 1.0 parts of exemplary compounds (1) replacement embodiments 2-4 when preparing charge generation layer formation coating fluid
0.5 part of exemplary compounds (1) outward, in the way of identical with embodiment 2-4, manufacture the electrofax sense in embodiment 2-5
Light component.
[embodiment 2-6]
Except with in 0.1 part of exemplary compounds (3) replacement embodiment 2-4 when preparing charge generation layer formation coating fluid
0.5 part of exemplary compounds (1) outward, in the way of identical with embodiment 2-4, manufacture the electrofax sense in embodiment 2-6
Light component.
[embodiment 2-7]
Except with in 0.5 part of exemplary compounds (3) replacement embodiment 2-4 when preparing charge generation layer formation coating fluid
0.5 part of exemplary compounds (1) outward, in the way of identical with embodiment 2-4, manufacture the electrofax sense in embodiment 2-7
Light component.
[embodiment 2-8]
Except with in 1.0 parts of exemplary compounds (3) replacement embodiments 2-4 when preparing charge generation layer formation coating fluid
0.5 part of exemplary compounds (1) outward, in the way of identical with embodiment 2-4, manufacture the electrofax sense in embodiment 2-8
Light component.
[embodiment 2-9]
Except with in 0.5 part of exemplary compounds (6) replacement embodiment 2-4 when preparing charge generation layer formation coating fluid
0.5 part of exemplary compounds (1) outward, in the way of identical with embodiment 2-4, manufacture the electrofax sense in embodiment 2-9
Light component.
[embodiment 2-10]
Except with in 0.5 part of exemplary compounds (8) replacement embodiment 2-4 when preparing charge generation layer formation coating fluid
0.5 part of exemplary compounds (1) outward, in the way of identical with embodiment 2-4, manufacture the electrofax in embodiment 2-10
Electrifier frame, photoreceptor.
[embodiment 2-11]
Except with 0.5 part of exemplary compounds (9), (product code: D1446, by Tokyo Chemical Industry
Co., Ltd. manufactures) replace 0.5 part of exemplary compounds when preparing charge generation layer formation coating fluid in embodiment 2-4
(1) outward, in the way of identical with embodiment 2-4, the electrophotographic photosensitive element in embodiment 2-11 is manufactured.
[comparative example 2-1]
Except replacing embodiment 2-1 is preparing charge generation layer shape with the hydroxygallium phthalocyanine crystal prepared in reference example 1-1
Outside hydroxygallium phthalocyanine crystal during one-tenth coating fluid, the electronics in comparison example 2-1 in the way of identical with embodiment 2-1
Photosensitive component.
[comparative example 2-2]
Except showing with when preparing charge generation layer formation coating fluid 0.5 part in 0.5 part of 1-Phenylethanone. replacement embodiment 2-4
Example compound (1) outward, manufactures the electrophotographic photosensitive element in comparative example 2-2 in the way of identical with embodiment 2-4.
[comparative example 2-3]
Except replacing in embodiment 2-4 with 0.5 part of 2-(dimethylamino)-1-(4-morphlinophenyl)-2-benzyl-1-butanone
0.5 part of exemplary compounds (1) when preparing charge generation layer formation coating fluid outward, with identical with embodiment 2-4
Mode manufacture the electrophotographic photosensitive element in comparative example 2-3.
[comparative example 2-4]
Except with in 0.5 part of 3-chloro-4-fluoro acetophenone replacement embodiment 2-4 when preparing charge generation layer formation coating fluid
0.5 part of exemplary compounds (1) outward, in the way of identical with embodiment 2-4, manufacture the electrofax sense in comparative example 2-4
Light component.
[evaluation of the electrophotographic photosensitive element in embodiment 2-1 to 2-11 and comparative example 2-1 to 2-4]
The ghost image of embodiment 2-1 to 2-11 and the electrophotographic photosensitive element of comparative example 2-1 to 2-4 is commented
Valency.
Laser beam printer (the trade name: Color Laser that will be manufactured by Hewlett Packard Japan, Ltd.
Jet CP3525dn) transform for use as the electronic photographing device evaluated.As the result of transformation, pre-exposure light is the most luminous and can
Become ground and control charge condition and image exposure amount.Additionally, the electrophotographic photosensitive element of manufacture is installed on cyan handle box
In and be connected to the position of cyan handle box so that it can not install other color handle box to laser beam printer master
Operate in the case of body.
During output image, only cyan handle box is installed to main body only to use cyan toner to export monochrome image.
Adjust charge condition and image exposure amount to be arranged by initial potential under the ambient temperature and moisture environment of 23 DEG C/55%RH
For dark space be-500V and clear zone is-100V.Survey at the surface potential of the drum type electrophotographic photosensitive element arranged for current potential
In amount, potential probes (trade name: model 6000B-8 is manufactured by Trek Japan Co., Ltd.) is also installed on aobvious by transformation box
Shadow position.Cylindric electronics is measured with surface potential instrument (trade name: model 344 is manufactured by Trek Japan Co., Ltd.)
The current potential of the central part of photosensitive component.
Evaluate ghost image the most under the same conditions.Subsequently, carry out the logical paper long duration test of 1,000, evaluate durable
At once ghost image after with 15 hours after test.Evaluation result under ambient temperature and moisture environment is described in table 1.
Subsequently, by electrophotographic photosensitive element low temperature at 15 DEG C/10%RH together with the electronic photographing device evaluated
3 days are stood to evaluate ghost image under low moisture environments.At identical conditions, carry out the logical paper long duration test of 1,000, comment
At once ghost image after with 15 hours after valency long duration test.Evaluation result under low temperature and low humidity environment is also described in table 1.
In logical paper long duration test, the image of the word E of 1% printing rate is formed at the common paper of A4 size with cyan monochrome
On.
Ghost image is evaluated as follows.It is evaluated based on the ghost image in the total 8 that following sequence exports continuously:
First upper output solid white image, exports 4 class ghost image figures respectively on amounting to 4, exports solid black chromatic graph on one
Picture, and again on amounting to 4, export 4 class ghost image figures respectively.Ghost image figure includes: as solid white background, away from printing
In original position (away from the upper end 10mm of paper) the 30mm width range of image, 4 with the reality on 25mm limit the most arranged in parallel
Heart black squares image.In the scope below the original position 30mm width range of print image, print 4 class halftonings
Print pattern is to be divided into grade.
4 class ghost image figures be arranged in the scope below the original position 30mm width range of print image, only half color
The figure that case of changing the line map is different.Halftone pattern includes following 4 classes:
(1) transversely * has and the print pattern (laser explosure) at 1 interval at 1；
(2) transversely * has and the print pattern (laser explosure) at 2 intervals at 2；
(3) transversely * has and the print pattern (laser explosure) at 3 intervals at 2；With
(4) " osmanthus horse " (similar to the gambade in chessboard) pattern print pattern (laser explosure) (as
" osmanthus horse " chess piece in Japan's Chinese chess is similar to the movement that horse jump direction is similar, has 2 printed in 6 squares
Pattern).
*: laterally refer to the scanning direction (horizontal direction of output paper) of laser scanner.
Ghost image is divided into level below.Judge that the effect of the present invention, at class 4, is insufficient in 5 and 6.
Grade 1: invisible ghost image in any ghost image figure.
Grade 2: fuzzy visible ghost image in specific ghost image figure.
Grade 3: fuzzy visible ghost image in any ghost image figure.
Class 4: visible ghost image in specific ghost image figure.
Class 5: visible ghost image in any ghost image figure.
Class 6: high-visible ghost image in specific ghost image figure.
Table 1: the evaluation result of ghost image
Although the present invention is described with reference to exemplary, it is understood that show disclosed in the invention is not limited in
Example embodiment.The scope of claim gives wide in range explanation to comprise and all improving and equivalent structure and function.
Claims (17)
1. an electrophotographic photosensitive element, it comprises: supporting mass；With the charge generation layer being formed on described supporting mass and electricity
Lotus transfer layer；
It is characterized in that, described charge generation layer comprises: charge generation substance；The amines represented with following formula (1)；
Wherein,
R1To R5The most independently represent hydrogen atom, halogen atom, hydroxyl, carboxyl, alkoxy carbonyl, aryloxycarbonyl, replacement or do not take
The alkyl in generation, substituted or unsubstituted alkoxyl, substituted or unsubstituted aryloxy group, the amino with substituent group or replacement
Or unsubstituted ring amino；With
R1To R5At least one for the substituted amino of substituted or unsubstituted aryl, with substituted or unsubstituted alkyl replacement
Amino, or substituted or unsubstituted ring amino.
Electrophotographic photosensitive element the most according to claim 1, wherein R1To R5At least one for replace or unsubstituted
The substituted amino of alkyl.
Electrophotographic photosensitive element the most according to claim 2, wherein said substituted with substituted or unsubstituted alkyl
Amino is dialkyl amido.
Electrophotographic photosensitive element the most according to claim 3, wherein said dialkyl amido is dimethylamino or two
Ethylamino.
Electrophotographic photosensitive element the most according to claim 1, wherein said amines is the amination that following formula (2) represents
Compound:
Wherein R6And R7Represent methyl or ethyl independently of one another.
Electrophotographic photosensitive element the most according to claim 1, wherein R1To R5At least one for substituted or unsubstituted
Ring amino.
Electrophotographic photosensitive element the most according to claim 6, wherein said substituted or unsubstituted ring amino is morpholine
For base or piperidino.
Electrophotographic photosensitive element the most according to claim 1, wherein said amines is the amination that following formula (3) represents
Compound:
Electrophotographic photosensitive element the most according to claim 1, the described amines in wherein said charge generation layer
Content be below more than 0.1 mass % and 20 mass % relative to described charge generation substance.
Electrophotographic photosensitive element the most according to claim 1, wherein said charge generation substance is phthalocyanine crystal.
11. electrophotographic photosensitive elements according to claim 1, wherein said charge generation layer is to include phthalocyanine crystal
Layer, the amines represented containing formula (1) in described phthalocyanine crystal.
12. electrophotographic photosensitive elements according to claim 11, the wherein described amine compounds in described phthalocyanine crystal
The content of thing is below more than 0.05 mass % and 3.0 mass %.
13. according to the electrophotographic photosensitive element described in claim 10 or 11, and wherein said phthalocyanine crystal is gallium phthalocyanine crystal.
14. electrophotographic photosensitive elements according to claim 13, wherein said gallium phthalocyanine crystal is to radiate with CuK α
In the X-ray diffraction of line, at the hydroxyl gallium phthalein that Bragg angle 2 θ is the crystal form at 7.4 ° ± 0.3 ° and 28.2 ° ± 0.3 ° with peak
Cyanines crystal.
15. 1 kinds of handle boxes, it is detachably mounted to the main body of electronic photographing device, it is characterised in that will want according to right
Seek the electrophotographic photosensitive element described in 1 to 14 any one and select free charging device, developing unit, transfer device and cleaning
At least one apparatus integration ground supporting of the group of device composition is to form described handle box.
16. 1 kinds of electronic photographing devices, it is characterised in that it comprises:
According to the electrophotographic photosensitive element described in any one of claim 1 to 14；With
Charging device, image exposing apparatus, developing unit and transfer device.
17. 1 kinds of phthalocyanine crystals, it is characterised in that comprise the compound that following formula (1) represents in described phthalocyanine crystal:
Wherein
R1To R5The most independently represent hydrogen atom, halogen atom, hydroxyl, carboxyl, alkoxy carbonyl, aryloxycarbonyl, replacement or do not take
The alkyl in generation, substituted or unsubstituted alkoxyl, substituted or unsubstituted aryloxy group, the amino with substituent group or replacement
Or unsubstituted ring amino；With
R1To R5At least one for the substituted amino of substituted or unsubstituted aryl, with substituted or unsubstituted alkyl replacement
Amino, or substituted or unsubstituted ring amino.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-273727 | 2012-12-14 | ||
| JP2012273727 | 2012-12-14 | ||
| JP2013242104A JP2014134772A (en) | 2012-12-14 | 2013-11-22 | Electrophotographic photosensitive member, process cartridge, electrophotographic apparatus, and phthalocyanine crystal |
| JP2013-242104 | 2013-11-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103869639A CN103869639A (en) | 2014-06-18 |
| CN103869639B true CN103869639B (en) | 2016-11-30 |
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ID=
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| US5514505A (en) * | 1995-05-15 | 1996-05-07 | Xerox Corporation | Method for obtaining improved image contrast in migration imaging members |
| JP2009080403A (en) * | 2007-09-27 | 2009-04-16 | Konica Minolta Business Technologies Inc | Electrophotographic photoreceptor |
| US20120028179A1 (en) * | 2010-07-29 | 2012-02-02 | Hongguo Li | Electrophotographic photoreceptor, image forming method, image forming apparatus, and process cartridge for image forming apparatus using the photoreceptor |
| CN102621830A (en) * | 2010-12-21 | 2012-08-01 | 夏普株式会社 | Electrophotographic photoconductor and image forming apparatus using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3532496A (en) * | 1966-06-28 | 1970-10-06 | Xerox Corp | Xerographic plates and processes employing homogeneous dispersions of vitreous selenium and sensitizing dyes as the photoconductive layer |
| US5514505A (en) * | 1995-05-15 | 1996-05-07 | Xerox Corporation | Method for obtaining improved image contrast in migration imaging members |
| JP2009080403A (en) * | 2007-09-27 | 2009-04-16 | Konica Minolta Business Technologies Inc | Electrophotographic photoreceptor |
| US20120028179A1 (en) * | 2010-07-29 | 2012-02-02 | Hongguo Li | Electrophotographic photoreceptor, image forming method, image forming apparatus, and process cartridge for image forming apparatus using the photoreceptor |
| CN102621830A (en) * | 2010-12-21 | 2012-08-01 | 夏普株式会社 | Electrophotographic photoconductor and image forming apparatus using the same |
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