CN101416119A - Electrophotographic photoreceptor and electrophotographic apparatus - Google Patents
Electrophotographic photoreceptor and electrophotographic apparatus Download PDFInfo
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- CN101416119A CN101416119A CNA2007800121536A CN200780012153A CN101416119A CN 101416119 A CN101416119 A CN 101416119A CN A2007800121536 A CNA2007800121536 A CN A2007800121536A CN 200780012153 A CN200780012153 A CN 200780012153A CN 101416119 A CN101416119 A CN 101416119A
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Abstract
An electrophotographic photoreceptor which can respond to a reduction in diameter of photoreceptor and a process having high circumferential speed, due to the demand in the miniaturization and increase in the speed of copiers and printers. The photoreceptor has high sensitivity in long-wavelength region, and is free from deterioration of electric characteristics even after repeated use, is highly stabile. The electrophotographic photoreceptor has a conductive support member and a photosensitive layer laminated thereon, which includes at least a charge-generating agent, a charge-transfer agent, and a binder resin. The charge-generating agent is oxytitanium phthalocyanine, which has a Bragg angle (2theta + 0.2 DEG) providing a maximumpeak at 27.2 DEG in the X-ray diffraction spectra using CuKalpha as a radiation source. The electron charge-transfer agent includes a compound represented by the following formula.
Description
Technical field
The TiOPc (oxytitanium phthalocyanine) that the present invention relates to contain specific crystal formation as the charge generation agent, contain the Electrophtography photosensor of specific compound as charge transfer agent.
Background technology
In recent years, as adopting electrofax exposure light source mode, non-impacting type printing machine, mainly use long wavelengths' such as semiconductor laser or LED light source.And,, gradually adopt the fast technology of pathization, linear velocity of photoreceptor along with miniaturization, the high speed of manifolder, printer device.Therefore, Electrophtography photosensor uses the charge generation agent that has sensitivity at long wavelength region usually.In the past, often used phthualocyanine pigment as above-mentioned material.As everyone knows, the sensitivity of this phthualocyanine pigment is according to its crystal formation and difference.In addition, along with province's electrification in recent years, for the output of the exposure light source that suppresses electro-photography apparatus such as printing machine, Electrophtography photosensor improves the requirement of high sensitivityization.
(1) in the phthualocyanine pigment, the example that has highly sensitive pigment at long wavelength region has: TiOPc.In TiOPc, introduced several crystal formations, wherein located to show that at 27.2 ° the pigment at maximum diffraction peak is high sensitivity.But, when in high-speed process, using this pigment, reuse the potential property deterioration of back photoreceptor, in the gained image, produce veil, black streaking and density unevenness etc.
Think this be because: the high sensitivity characteristic of utilizing TiOPc to have, the generation of electric charge is more, although therefore have advantages such as hyperresponsiveness usually, but when being used for high-speed process, electric charge remains in the photographic layer, on photoreceptor, form storage and residual, in the electronic camera technology of next step, appear on the image as memory phenomenon.In addition, also relevant with the charge delivery capability of charge transfer agent, both combinations most important (for example with reference to patent documentation 1).Patent documentation 1: Japanese kokai publication hei 1-106069 communique
Therefore, people require to develop the highly sensitive of long wavelength region, even use repeatedly at a high speed, electrofax characteristic, particularly initial stage current potential and use repeatedly after the also stable Electrophtography photosensor of reappearance of current potential.In addition, even use charge generation agent with high charge generation efficient, but, then not only can't obtain enough sensitivity, and various environments for use, also can't obtain images with high image quality from hot and humid to low temperature and low humidity if the phasic property of itself and charge transfer agent is poor.Though from all angles the phasic property of charge generation agent and charge transfer agent is studied, present situation is clearly not find both phasic properties as yet.
(2) on the other hand, as the method for making Electrophtography photosensor, studying the whole bag of tricks, forming coating fluid in the solvent, making its film forming method on conductive board again but usually adopt charge generation agent or charge transfer agent etc. are dispersed in together with binder resin.
Usually, charge transfer layer is charge transfer agent and resinoid bond to be dissolved in the coating solvent make coating fluid, this coating fluid is coated on carries out drying on the electric conductivity supporter and form.
But charge transfer agent is all to be difficult to abundant dissolving in all kinds of solvents, also to be difficult to abundant dissolved substances in various resinoid bonds.
In the past, as the coating solvent, studied the use of methylene chloride or ethylene dichloride.These coating solvents, it is higher to be considered to above-mentioned charge carrying substances or resinoid bond dissolubility therein, and boiling point is low, obtains the homogeneity of coating film thickness easily, also easily dry (for example with reference to patent documentation 2).
Patent documentation 2: TOHKEMY 2001-125288 communique
Patent documentation 3: TOHKEMY 2000-314977 communique
Patent documentation 4: TOHKEMY 2004-354673 communique
But, when methylene chloride or ethylene dichloride are used for the coating solvent, if after the coating of charge transfer layer forms, fully carry out heat drying the coating solvent is evaporated fully, then in Organophotoreceptor, produce the part that the partial-band piezoelectric voltage descends, form image noise, have the problem that image quality is descended.
In addition, to carry out long-time heating in order addressing the above problem when dry, to exist the problem that cracks and form image noise at charge transfer layer, exist to be difficult to the problem determining suitable drying condition, be difficult to improve the volume production productive rate.
(3) nearest, along with the exploitation of electro-photography apparatus such as the manifolder of digital form, printing machine is used, the requirement of high image qualityization, miniaturization, high speed is further improved.
Particularly in the short high speed manifolder of the traveling time from the step of exposure to the development step, existence can't be reproduced problems such as dot image or fine rule brightly, therefore people's motion has been arranged: Electrophtography photosensor separates function and forms the laminate-type Electrophtography photosensor of photographic layer and practical application containing to be dispersed in the charge transfer layer in the resinoid bond at charge generation layer that long wavelength region has a highly sensitive charge generation agent and the charge transfer agent that makes high anti-brush, high degree of excursion.
Summary of the invention
Invent problem to be solved
Problem of the present invention is to provide Electrophtography photosensor, miniaturization, high speed along with manifolder, printer device, this photoreceptor can satisfy the requirement of the fast technology of pathization, the linear velocity of photoreceptor, and has high sensitivity at long wavelength region, even use the electrical characteristics also can deterioration repeatedly, and stability be high.
The Electrophtography photosensor of the present invention also aims to provide the image noise that prevents Electrophtography photosensor or crackle, can high productivity producing.
In addition, also provide electro-photography apparatus such as the manifolder that is applicable to towards the digital form of high image qualityization, miniaturization, high speed, printing machine high-resolution Electrophtography photosensor and use the electro-photography apparatus of this Electrophtography photosensor.
Solve the method for problem
The inventor etc. further investigate repeatedly in order to solve above-mentioned problem, found that: the TiOPc at the X-ray diffraction peak that the use demonstration is specific has solved above-mentioned prior art problem as the Electrophtography photosensor of the charge transfer agent of charge generation agent, use specific compound, thereby has finished the present invention.
The inventor etc. further further investigate, and found that: as the coating solvent, when tetrahydrofuran remains on the photographic layer, compare during with other coating dissolvent residuals, as the excellent of Electrophtography photosensor.
What form based on above-mentioned knowledge the present invention relates to Electrophtography photosensor, this photoreceptor has electric conductivity supporter and the photographic layer that is configured on the above-mentioned electric conductivity supporter, contain charge generation agent and charge transfer agent in the above-mentioned photographic layer, above-mentioned charge generation agent is a TiOPc, and this TiOPc is being to locate to have the Bragg angle (2 θ) that manifests maximum peak at 27.2 ° ± 0.2 ° in the radiogenic X ray diffracting spectrum with CuK α; Above-mentioned charge transfer agent contains any one or two kinds of above compounds of the compound group that is selected from following chemical formula (A1a)～(A1d):
Chemical formula (A1a)
Chemical formula (A1b)
Chemical formula (A1c)
Chemical formula (A1d)
The present invention relates to Electrophtography photosensor, above-mentioned photographic layer is to make the evaporation of above-mentioned tetrahydrofuran after being dissolved in above-mentioned charge transfer agent in the tetrahydrofuran and form, and contains above-mentioned tetrahydrofuran in the above-mentioned photographic layer.
The present invention relates to Electrophtography photosensor, above-mentioned TiOPc locates to have diffraction peak for 9.7 °, 14.2 °, 18.0 °, 24.2 ° and 27.2 ° at Bragg angle (2 θ ± 0.2 °).
The present invention relates to Electrophtography photosensor, it is antioxidant that above-mentioned photographic layer contains aromatic amine.
The present invention relates to electro-photography apparatus, this device has: Electrophtography photosensor; Make the Charging system of above-mentioned electrophotographic photoreceptor belt electricity; With charged above-mentioned Electrophtography photosensor exposure, form the exposure device of sub-image on above-mentioned Electrophtography photosensor surface; And make toner (toner), and make attached to the above-mentioned toner on the above-mentioned Electrophtography photosensor and be transferred on the printed medium attached to the developing apparatus on the above-mentioned sub-image on above-mentioned Electrophtography photosensor surface.Wherein above-mentioned Electrophtography photosensor has electric conductivity supporter and the photographic layer that is configured on the above-mentioned electric conductivity supporter, contain charge generation agent and charge transfer agent on the above-mentioned photographic layer, above-mentioned charge generation agent is a TiOPc, and this TiOPc is being to locate to have the Bragg angle (2 θ) that manifests maximum peak at 27.2 ° ± 0.2 ° in the radiogenic X ray diffracting spectrum with CuK α; Above-mentioned charge transfer agent contains any one or two kinds of above compounds of the compound group that is selected from following chemical formula (A1a)～(A1d):
Chemical formula (A1a)
Chemical formula (A1b)
Chemical formula (A1c)
Chemical formula (A1d)
The present invention relates to electro-photography apparatus, this device carry out charged, the formation of above-mentioned sub-image of above-mentioned Electrophtography photosensor, above-mentioned toner adhere to transfer printing with above-mentioned toner after, charged after under above-mentioned Electrophtography photosensor needn't remove the situation of electricity, carrying out.
The present invention relates to electro-photography apparatus, wherein above-mentioned Electrophtography photosensor is below 0.1 second from the exposure position with above-mentioned Electrophtography photosensor exposure to the linear velocity that makes above-mentioned toner attached to the developing location on the above-mentioned sub-image.
The present invention relates to electro-photography apparatus, wherein above-mentioned Charging system is the contact electrification device that directly contacts with above-mentioned Electrophtography photosensor.
The invention effect
Electrophtography photosensor with the combination of charge generation agent and charge transfer agent of the present invention, its residual electric potential is extremely low, even also image retention can not occur when using in can wiping type (eraserless) electro-photography apparatus, demonstrates the electrofax characteristic of excellence.By the characteristic difference of embodiment described later and comparative example as can be known: Electrophtography photosensor of the present invention has repetition stability, satisfies high market demands.
The present invention has obtained can not occurring because of the decline of partial-band piezoelectric voltage the crackle of image noise or charge transfer layer, photostability, charging property excellence, Electrophtography photosensor of can under the image quality good state, stablize, high productivity being produced and the electro-photography apparatus that uses this photoreceptor.
The accompanying drawing summary
Fig. 1 shows the X-ray diffractogram of phthalocyanine composition of the present invention.
Fig. 2 shows the X-ray diffractogram of phthalocyanine composition of the present invention.
Fig. 3 shows the X-ray diffractogram of β type TiOPc.
Fig. 4 shows the summary pie graph of electro-photography apparatus of the present invention.
Fig. 5 shows summary pie graph that can wiping type electro-photography apparatus of the present invention.
Fig. 6 shows the X-ray diffractogram of α type TiOPc.
Fig. 7 is the sectional view of an example of Electrophtography photosensor of the present invention.
Fig. 8 is the sectional view of other examples of Electrophtography photosensor of the present invention.
Fig. 9 shows the summary pie graph of colored printing of the present invention with electro-photography apparatus.
Symbol description
1 ... electro-photography apparatus; 11 ... photoreceptor (Electrophtography photosensor); 22 ... charge generation layer; 23 ... charge transfer layer; 25 ... photographic layer; 13 ... power supply; 12 ... Charging system (live part); 14 ... exposure device; 15 ... developing apparatus; 16 ... transfer device; 17 ... cleaning device; 18 ... remove electrical equipment; 19 ... fixing device
The best mode that carries out an invention
Electrophtography photosensor of the present invention is to contain the TiOPc with specific X ray diffracting spectrum in the photographic layer on matrix to form as charge generating material.
Describe the preferred implementation of Electrophtography photosensor of the present invention in detail.The present invention for example adopts: formation contains the charge generation layer of charge generation agent at least on the electric conductivity supporter, formation thereon contains the function divergence type Electrophtography photosensor of the charge transfer layer of charge transfer agent at least.Under this situation, form photographic layer by charge generation layer and charge transfer layer.
Formation method as charge generation layer, can make and in all sorts of ways, for example can use phthalocyanine composition of the present invention as the charge generation agent, itself and resinoid bond are are together dispersed or dissolved with appropriate solvent, the gained coating fluid is coated on the predetermined supporter as bottom, makes it dry as required and form.
Charge transfer layer contains charge transfer agent described later at least, and this charge transfer layer for example can be by using the bonding charge transfer agent of resinoid bond to form on as the charge generation layer of its bottom.
Formation method as charge transfer layer, can make and in all sorts of ways, but can adopt usually charge transfer agent and resinoid bond are are together dispersed or dissolved with appropriate solvent, the gained coating fluid is coated on the charge generation layer as bottom, make its dry method.
In addition, also, charge generation layer and charge transfer layer carry out laminated contrary laminate-type Electrophtography photosensor etc. applicable to being turned upside down.And, also applicable to the mono-layer electronic photographic photoreceptor that in one deck, contains charge generation agent and charge transfer agent.
Mono-layer electronic photographic photoreceptor can utilize charge generation agent TiOPc and charge transfer agent described later are together mixed, disperse with resinoid bond, the gained coating fluid is coated on the conductive base as bottom, and makes it dry method and make.
The example that can be used for electric conductivity supporter of the present invention has: metal simple-substance or their alloy processomes such as aluminium, brass, stainless steel, nickel, chromium, titanium, gold, silver, copper, tin, platinum, molybdenum, indium.Shape can be any, and can also end can be arranged for no reason so long as flexible shape such as laminar, film like, band shape gets final product.
The diameter of electric conductivity supporter is effective especially below following, the preferred 30mm of 60mm.
Wherein, preferred aluminium alloys such as JIS3000 system, JIS5000 system, JIS6000 system, utilization extruding-flatiron (the Extrusion Ironing also of using, EI) method, extruding-drawing (Extrusion Drawing, ED) method, drawing-flatiron (Drawing Ironing, DI) (Impact Ironing, II) commonsense method such as method is carried out molded electric conductivity supporter for method, impact-flatiron.And, can be surface to this electric conductivity supporter utilize adamas etc. to carry out surface treatments such as surfacing cut processing or grinding, anodized or do not carry out above-mentioned processing, processing no cutting tube etc. any.
Can further utilize evaporation, plating etc. to form the film of conductive material at matrix surfaces such as above-mentioned metal or alloy.Matrix itself can be made of conductive material, but also can utilize methods such as evaporation, plating to form the film of above-mentioned metal or carbon etc. at non-conductive plastic plate and film surface, makes it have electric conductivity.
Its kind or shape are not particularly limited, can use various materials to constitute matrix with electric conductivity.
In addition, when using resin, can also make conductive agents such as containing metal powder or conductive carbon in the resin, perhaps use electroconductive resin to form and use resin as matrix as matrix.
And, when in matrix, using glass, can coat with tin oxide, indium oxide, silver iodide on its surface, make it have electric conductivity.
In addition, can on supporter, form resin bed.This resin bed has the function of the defective that improves gluing function, prevents barrier functionality, metallized aluminum tube-surface from the aluminum pipe inflow current etc.Can use various resins such as polyvinyl resin, acryl resin, epoxy resin, polycarbonate resin, urethane resin, vestolit, vinyl acetate resin, polyvinyl butyral resin, polyamide, nylon resin, alkyd resin, melamine resin in this resin bed.Above-mentioned resin bed can be made of independent resin, also two or more mixed with resin can be constituted.In addition, can be in layer dispersed metal compound, carbon, silicon dioxide, toner etc.And,, can also contain various pigment, electronics acceptance material or the sub-material etc. of powering in order to improve characteristic.
As the charge generation agent, using is being at 27.2 ° of TiOPcs of locating to show maximum peak of Bragg angle (2 θ ± 0.2 °) with CuK α in the radiogenic X ray diffracting spectrum.The example of the X-ray diffractogram of employed TiOPc is seen Fig. 1, Fig. 2.
Need to prove that the diffraction peak shown in above-mentioned is to extract the diffraction peak of measuring under the state of TiOPc after forming photographic layer from photographic layer.By using this TiOPc, can be provided in the influence that long wavelength region has excellent sensitivity and is not subjected to environment for use, particularly humidity, show the Electrophtography photosensor of stable properties.
In the past, the X ray diffracting spectrum that is used for the TiOPc of Electrophtography photosensor was to form the Powdered TiOPc of required crystal formation, the coating fluid that contains resin or dispersion solvent etc. made in the time of maybe will forming photographic layer with synthetic back to make the material of piller (pellet) shape be that sample is measured.
But, in the stage before photographic layer forms,, also can't correctly judge the crystal formation of TiOPc contained in the photographic layer even measure the X ray diffracting spectrum of TiOPc.That is, when forming photographic layer, there are various external causes, might be different before photographic layer forms with formation back diffracting spectrum.
Promptly, on charge generation layer in the laminate-type photoreceptor of laminated charge transfer layer, coating forms the coating fluid that contains the charge generation agent on supporter, carry out drying as required, the coating fluid that coating afterwards contains charge transfer agent forms charge transfer layer, carrying out drying makes each layer fixing, form photographic layer by above-mentioned steps, therefore utilize the external cause of the heat that produces by drying steps, form with contacting of the solvent that uses in the coating fluid etc. with charge transfer layer, the diffracting spectrum generation crystallization of charge generation agent is shifted, and the diffracting spectrum of the diffracting spectrum of coating fluid state and the end-state of photoreceptor might may not show identical crystal formation.Therefore, in fact, after forming photographic layer, must take out the charge generation agent and measure for the diffracting spectrum of the charge generation agent of the state of studying the performance function.
When from photographic layer, extracting TiOPc, must be noted that making TiOPc that crystallization not take place shifts.In addition, contain resinoid bond or charge transfer agent etc. in photographic layer, it becomes obstacle aspect the mensuration X ray diffracting spectrum.Therefore, must remove resinoid bond or charge transfer agent etc., suitably selection does not change the solvent of the crystal formation of TiOPc.
In photographic layer,, TiOPc beyond the present invention or AZO pigments etc. together can be mixed with TiOPc of the present invention in order to obtain suitable luminous sensitivity wavelength or sensitization.The phasic property of sensitivity good aspect preferred above-mentioned substance.In addition, for example can use monoazo pigment, disazo pigment, trisazo pigment, polyazo pigment, indigo pigment, intellectual circle's pigment, toluidine pigment, pyrazoline pigment, perylene dye, quinoline a word used for translation ketone pigment, pyralium salt etc.
As the resinoid bond that is used to form photographic layer, its example has: polycarbonate resin, styrene resin, acryl resin, the styrene-propene acid resin, the ethane-acetic acid ethyenyl ester resin, acrylic resin, vestolit, chlorinated polyether, vinyl chloride-vinyl acetate resin, vibrin, furane resin, the nitrile resin, alkyd resin, polyacetal resin, the polymethylpentene resin, polyamide, urethane resin, epoxy resin, polyarylate resin, the diaryl resin, polysulfone resin, polyethersulfone resin, polyene propyl group sulphone resin, silicone resin, ketone resin, polyvinyl butyral resin, polyether resin, phenolics, EVA (Ethylene/vinyl acetate) resin, ACS (vinyl cyanide/haloflex/styrene) resin, resins such as ABS (acrylonitrile/butadiene/styrene) resin and epoxy aromatic ester.
Above-mentioned resin can use with monomer, also can be use mixing two or more.When the mixed with resin that molecular weight is different is used, can improve hardness and mar proof, therefore preferred.Need to prove that when photographic layer comprised charge generation layer and charge transfer layer, above-mentioned resin can be used for arbitrary layer.
The example that is used for the solvent of coating fluid has: alcohols such as methyl alcohol, ethanol, n-propanol, isopropyl alcohol, butanols; Saturated aliphatic hydrocarbon such as pentane, hexane, heptane, octane, cyclohexane, cycloheptane; Aromatic hydrocarbon such as toluene, dimethylbenzene; Chlorohydrocarbons such as methylene chloride, ethylene dichloride, chloroform, chlorobenzene; Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran (THF), methyl cellosolve; Ketones such as acetone, butanone, methyl isobutyl ketone, cyclohexanone; Ester classes such as ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate; Ether solvents such as diethyl ether, dimethoxy-ethane, tetrahydrofuran, dioxolane, diox or anisole; N, dinethylformamide, dimethyl sulfoxide (DMSO) etc.Preferred especially ketone series solvent, ester series solvent, ether series solvent or halogenated hydrocarbons series solvent, wherein preferred tetrahydrofuran.Above-mentioned solvent can use separately, perhaps uses as two or more mixed solvents.
The compound that contains general formula (A1) expression in the Electrophtography photosensor of the present invention is as charge transfer agent.Still it should be noted that the compound of general formula (A1) expression is identical compound with the compound of general formula (C1) expression.
General formula (A1)
[in the formula, R
1～R
3Independent respectively expression hydrogen, halogen atom, can to have substituent carbon number be that 1～6 alkyl, carbon number are 6～12 replacement or unsubstituted aryl].
The phasic property of above-mentioned charge transfer agent and TiOPc of the present invention is good, and environment resistant strong Electrophtography photosensor can be provided.
In the compound of general formula (A1) expression, particularly the phasic property of compound of (A1a)～(A1d) expression and TiOPc of the present invention is good, and is therefore preferred.
Below, provide concrete compound, but be not limited to these.Still it should be noted that the compound of chemical formula (A1a)～(A1d) expression is respectively identical compound with the compound of chemical formula described later (C1a)～(C1d) expression:
Chemical formula (A1a)
Chemical formula (A1b)
Chemical formula (A1c)
Chemical formula (A1d)
Under this situation, with respect to 1 weight portion binder resin, the content of above-mentioned charge transfer agent is preferably 0.3～2.0 weight portion.If the content of this compound is less than 0.3 weight portion, then electrical characteristics such as residual electric potential rising worsen.And when the content of this compound during more than 2.0 weight portions, mechanical properties such as mar proof descend.
And, the compound of chemical formula (A1a)～(A1d) expression can also be mixed use with other charge transfer agents.Under this situation, containing of the compound of chemical formula (A1a)～(A1d) and other compounds is proportional for chemical formula (A1a)～(A1d): other compounds=50: 50～5: 95, preferred 30: 70～5: 95 scope.
As other charge transfer agents, can use: electroconductive polymer compounds such as Polyvinyl carbazole, halogenated polyethylene base carbazole, polyvinyl pyrene, polyvinyl indoles and quinoxaline, polyvinyl benzothiophene, polyvinyl anthracene, polyvinyl acridine, polyvinyl pyrazoline, polyacetylene, polythiophene, polypyrrole, polyphenyl, the inferior ethene of polyphenyl, polyisothianaphthene, polyaniline, polydiacetylene, poly-heptadiene, polypyridine two bases, poly quinoline, polyphenylene sulfide, poly-Off エ ロ セ ニ レ Application, poly-ペ リ Na Off チ レ Application, poly-phthalocyanine.In addition, as low molecular compound, can use: trinitro-fluorenone, tetracyanoethylene, tetra cyanogen subculture dimethyl benzene quinone, quinone, two benzoquinones, naphthoquinones, anthraquinone and derivant thereof; Polynuclear aromatic compounds such as anthracene, pyrene, phenanthrene; Nitrogen-containing heterocycle compounds such as indoles, carbazole, imidazoles; Fluorenone, Wu, oxadiazole, oxazole, pyrazoline, hydrazone, triphenyl methane, triphenylamine, enamine, Stilbene etc.In addition, can also use the polymer solid electrolyte etc. of metallic ion such as Li doped ion in macromolecular compounds such as polyethylene oxide, polypropyleneoxide, polyacrylonitrile, polymethylacrylic acid.And, the organic charge that can also use power supply sub-property compound and electronic acceptance compound by tetrathiafulvalene-tetra cyanogen subculture dimethyl benzene quinone representative to form shifts complex compound etc., above-mentioned substance can only add a kind of or two or more compound is added, and obtains required photoreceptor characteristic.
At the coating fluid that is used for making Electrophtography photosensor of the present invention (for example charge transfer layer coating fluid, charge generation layer coating fluid, single-layer type photographic layer coating fluid), in the scope that does not undermine characteristic, can add antioxidant, ultraviolet light absorber, free radical scavenger, softening agent, rigidizer, crosslinking chemical etc., seek to improve characteristic, permanance, the mechanical property of photoreceptor.Particularly antioxidant, ultraviolet light absorber help to improve the permanance of photoreceptor, are useful adjuvants.
Wherein, preferred aromatic amine is an antioxidant in this photographic layer, its example has: the N-phenyl-1-naphthylamine, N-phenyl-N '-isopropyl p-phenylenediamine (PPD), N, the N-diethyl p-phenylenediamine, N-phenyl-N '-ethyl-2-dimethyl-p-phenylenediamine, N-ethyl-N hydroxyethyl p-phenylenediamine (PPD), the alkylation diphenylamine, N, N '-diphenyl-para-phenylene diamine, N, N '-diallyl p-phenylenediamine (PPD), N-phenyl-1,3-dimethylbutyl p-phenylenediamine (PPD), 4,4 '-dioctyl diphenylamine, 4,4 '-dioctyl diphenylamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 2,2,4-trimethyl-1, the 2-dihydroquinoline, the N-PBNA, N, N '-two-2-naphthyl p-phenylenediamine etc.
Phenol is that antioxidant is preferred: 2,6-DI-tert-butylphenol compounds, 2,6-di-t-butyl-4-metoxyphenol, the 2-tert-butyl group-4-metoxyphenol, 2,4-dimethyl-6-tert-butyl phenol, 2,6-di-tert-butyl-4-methy phenol, butylated hydroxy anisole (BHA), propionic acid stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl) single phenol such as ester, alpha-tocopherol, betatocopherol, n-octadecane base-3-(3 ', 5 '-di-t-butyl-4 '-hydroxyphenyl) propionic ester system; 2,2 '-di-2-ethylhexylphosphine oxide (the 6-tert-butyl group-4-methylphenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 4,4 '-thiobis (the 6-tert-butyl group-3-methylphenol), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethyl-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, four [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionic ester] polyphenol system such as methane etc., the above-mentioned antioxidant more than a kind or 2 kinds can be contained in the photographic layer simultaneously.
Ultraviolet light absorber is preferred: 2-(5-methyl-2-hydroxyphenyl) benzotriazole, 2-[2-hydroxyl-3, two (the α of 5-, α-Er Jiajibianji) phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2-(the 3-tert-butyl group-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-benzotriazoles such as 5-chlorobenzotriazole, 2-(3,5-two tertiary pentyls-2-hydroxyphenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole system; Salicylic acids such as phenyl salicytate, p-t-butylphenyl salicylate, p-octylphenyl salicylate system.Can contain the above-mentioned ultraviolet light absorber more than a kind or 2 kinds in the photographic layer simultaneously.
With respect to binder resin, the phenol that is added in the Electrophtography photosensor of the present invention is that the addition of antioxidant is preferably the scope of 3～20% (weight).On the other hand, with respect to binder resin, the addition of ultraviolet light absorber is preferably the scope of 3～30% (weight).
In addition, add dispersion stabilizer, antisettling agent, anti-colour break-up agent, levelling agent, defoamer, tackifier, matting agent etc., can improve the finished product outward appearance of photoreceptor and the life-span of coating fluid.
And; on photographic layer, can form the organic film of vinyl-formal resin, polycarbonate resin, fluororesin, urethane resin, silicone resin etc. or comprise the film of the siloxane structure body that the hydrolysate by silane coupling agent forms, sealer is set.Under this situation, the permanance of photoreceptor improves, and is therefore preferred.Can also this sealer be set in order to improve other functions except that permanance improves.
Next, electro-photography apparatus of the present invention is described.Fig. 4 is the summary pie graph of electro-photography apparatus of the present invention.11 is photoreceptor, is in contact with it to be provided with live part 12.In live part, from power supply 13 service voltages.Around photoreceptor, be provided with exposure device 14, developing apparatus 15, transfer device 16, cleaning device 17 and remove electrical equipment 18.Need to prove that 19 is fixing device.Fig. 5 be of the present invention can wiping type electro-photography apparatus, in the electro-photography apparatus that Fig. 4 is not set except that electrical equipment 18, have identical structure.
Next, other examples of the present invention are elaborated.
As mentioned above, the solvent that uses during to the formation photographic layer is not particularly limited, but preferred especially tetrahydrofuran.
In this application, use the compound of following general formula (C1) expression as charge transfer agent.
General formula (C1)
(in the formula, R
1～R
3Expression is selected from hydrogen, halogen atom, carbon number be 1 or more and 6 following alkyl, carbon numbers be 6 or more and 12 below aryl in any one more than substituting group).
Still it should be noted that in the present invention, alkyl is meant and is combined with other substituent substituted alkyls and not in conjunction with other substituent not substituted alkyls on alkyl; Aryl is meant and is combined with other substituent substituted aryls and not in conjunction with other substituent unsubstituting aromatic yls on aryl.
In the compound of general formula (C1) expression, the phasic property of compound shown in the particularly following chemical formula (C1a)～(C1d) and tetrahydrofuran is good, and is therefore preferred.
Below, provide particular compound, but be not limited to these:
Chemical formula (C1a)
Chemical formula (C1b)
Chemical formula (C1c)
Chemical formula (C1d)
By making charge transfer layer 23 contain above-mentioned charge transfer agent, the photostability of photographic layer 25, charging property excellence.
Below, laminate-type Electrophtography photosensor 11 of the present invention is elaborated.
Laminate-type Electrophtography photosensor 11 of the present invention is laminate-type Organophotoreceptors, and wherein the photographic layer 25 on the electric conductivity supporter 21 is laminated charge transfer layers 23 and form on charge generation layer 22 at least.
The formation step of charge generation layer 22 is described.At first, with above-mentioned charge generation material and the dissolving of suitable resinoid bond or be dispersed in the coating solvent and carry out coatingization, obtain charge generation layer coating.
Charge generation layer 22 following formation: utilize common rubbing methods such as dip coated method, method of spin coating, spraying rubbing method, electrostatic applications method that this charge generation layer is coated on coating and carry out drying on the electric conductivity supporter 21, form charge generation layer 22 by number μ m, preferred 0.02 μ m thickness above, below the 2 μ m.
The charge transfer layer coating of Electrophtography photosensor of the present invention obtains being dissolved in the coating solvents tetrahydrofurane as the compound of the sub-property of the power supply of charge carrying substances material-above-mentioned chemical formula (A1a)～(A1d), (C1a)～(C1d) and resinoid bond.
Use above-mentioned coating, utilize common rubbing methods such as dip coated method, method of spin coating, spraying rubbing method, electrostatic applications method on charge generation layer 22, to form charge transfer layer 23.
By the coating solvent of further use tetrahydrofuran described later, reduce the image noise that the reduction of the partial-band electric potential that causes because of the solvent that remains in the charge transfer layer 23 produces as this charge transfer layer 23.
Its result, charge transfer agent is dissolved in the coating solvent, with gained coating fluid coating is dry when forming charge transfer layer 23, needn't heats but carry out drying with the lower temperature short time, even residual tetrahydrofuran in charge transfer layer 23 can not produce image noise yet.
As mentioned above, when forming charge transfer layer 23, do not need high temperature or long-time dry, can easily set suitable drying condition, therefore on the charge transfer layer of making 23, can not crack, can under the image quality good state, stablize and the highly sensitive photoreceptor of high productivity production photostability, charging property excellence.
When using tetrahydrofuran in solvent, with respect to 1 parts by weight resin cementing agent, the content of the charge transfer agent in the charge transfer layer 23 is preferably more than 0.5 weight portion, below 0.8 weight portion.If the content of this compound is less than 0.5 weight portion, then electrical characteristics such as residual electric potential rising worsen.And when the content of this compound during more than 0.8 weight portion, mechanical properties such as mar proof descend.
And, the compound of chemical formula (A1a)～(A1d), (C1a)～(C1d) expression can also be mixed with other charge transfer agents, be used for same charge transfer layer 23.When using tetrahydrofuran in the solvent, the compound a of chemical formula (A1a)～(A1d), (C1a)～(C1d) and other charge transfer agents b contain proportional (a: b, weight ratio) be more than 5: 95, below 50: 50, preferred 5: 95 above, 30: 70 following scopes.
More than, charge generation layer 22 and charge transfer layer 23 are illustrated according to the laminate-type Electrophtography photosensor 11 of sequential laminating on electric conductivity supporter 21 of putting down in writing, but the present invention is not limited to this, put upside down the laminated order of charge generation layer 22 and charge transfer layer 23, charge transfer layer 23 and charge generation layer 22 are also included within the present invention according to the laminate-type Electrophtography photosensor 11 of sequential laminating on electric conductivity supporter 21 of putting down in writing.
And, also applicable to the mono-layer electronic photographic photoreceptor 31 (Fig. 8) that in one deck 35, contains charge generation agent and charge transfer agent.
As the electro-photography apparatus that is equipped with this Electrophtography photosensor, as mentioned above, charged mode can be the contact of brush, roller etc. usually, also can be the contactless of charger (scorotron), charger unit (corotron) etc., can be positive and negative any charged particles.
Exposure mode can be LED, LD etc. any.Visualization way can be any in the two kinds of compositions, a kind of composition, magnetic/non magnetic.The transfer printing mode can be roller, band etc. any.
Next, further describe the electro-photography apparatus of Fig. 5.This electro-photography apparatus 1 has above-mentioned Electrophtography photosensor 11.
Around Electrophtography photosensor 11, Charging system 12, exposure device 14, developing apparatus 15, transfer device 16 and cleaning device 17 are arranged along the sense of rotation of Electrophtography photosensor 11 according to the order of record.
When Electrophtography photosensor 11 is rotated with certain linear velocity, utilize Charging system 12 to make the same charged predetermined potential that reaches in photographic layer 25 surfaces, live part is through exposure device 14 exposures then, eliminate the electric charge of exposed portion, on photographic layer 25, form electrostatic latent image, utilize developing apparatus 15 to make that electrostatic latent image is visual to develop at unexposed portion, gained toner picture is transferred on the recording chart 5 by transfer device 16.
Transfer printing has the recording chart 5 of toner picture to be sent on the fixing device 19 from Electrophtography photosensor 11, and the toner on 19 pairs of recording charts 5 of fixing device heats, pressurizes, with its photographic fixing on recording chart 5.
Still it should be noted that, toner looks like to be transferred to recording chart 5 photographic layer 25 afterwards and utilizes the rotation of Electrophtography photosensor 11 to be sent on the cleaning device 17, be sent to once more on the Charging system 12 after the cleaning, repeat above-mentioned charged, exposure, development, transfer printing step.
At this moment, in electro-photography apparatus of the present invention, making the linear velocity of photoreceptor from the exposure position of Electrophtography photosensor 11 to developing location is to form image in 0.1 second to get off.
The linear velocity of photoreceptor from the exposure position to the developing location, be the linear velocity of photoreceptor, be meant from position that the irradiation of picture exposure light finishes the time of utilizing the position that charge image developing toner begins to adhere to until arrival from the picture step of exposure to development step.
Electrophtography photosensor of the present invention also can be used for the electro-photography apparatus that colored printing is used.The electro-photography apparatus that the symbol 50 expression colored printings of Fig. 9 are used.
This electro-photography apparatus 50 has a plurality of Electrophtography photosensor 51a～51d.Each Electrophtography photosensor 51a～51d is made of the Electrophtography photosensor shown in the symbol 31 of the Electrophtography photosensor shown in the symbol 11 of Fig. 7 or Fig. 8, and the photographic layer 25,35 of Electrophtography photosensor 51a～51d contains the charge transfer agent of locating to have arbitrary kind among the TiOPc of maximum peak and above-mentioned chemical formula (A1a)～(A1d), (C1a)～(C1d) at Bragg angle (2 θ ± 0.2 °) for 27.2 °.
Near each Electrophtography photosensor 51a～51d, dispose Charging system 54a～54d, exposure device 55a～55d and developing apparatus 52a～52d respectively.
In each developing apparatus 52a～52d, respectively dispose a kind of toner of different colours.Dispose four Electrophtography photosensor 51a～51d herein, in developing apparatus 52a～52d nearby of each Electrophtography photosensor 51a～51d, respectively dispose a kind of toner of red, blue, yellow, black four kinds of colors.
Each Electrophtography photosensor 51a～51d has the cylindrical shape supporter and is formed at the photographic layer of the outer surface of above-mentioned supporter.
Near each Electrophtography photosensor 51a～51d, dispose the ring-type transfer belt 65 that hangs on two transfer rollers 63,64.
Ring inboard at the ring of transfer belt 65 disposes a plurality of compression roller 53a～53d, and each Electrophtography photosensor 51a～51d is positioned at the ring outside of transfer belt 65, by the outer surface of compression roller 53a～53d driving fit in transfer belt 65.
The constituted mode of transfer belt 65 is: when transfer roller 63,64 during along the rotation of same direction, the part that contact with transfer roller 63,64 with transfer roller 63,64 skid-resistant directions on rotation move transfer belt 65 whole rotations.
The constituted mode of each Electrophtography photosensor 51a～51d is: with transfer roller 63,64 retrograde rotations, promptly when transfer belt 65 moves with transfer belt 65 skid-resistant directions on rotate.Make transfer roller 63,64 and Electrophtography photosensor 51a～51d rotation, when transfer belt 65 was rotated in a certain direction, the constituted mode of Electrophtography photosensor 51a～51d was: contact with transfer belt 65 behind the position on the opposite by Charging system 54a～54d, exposure device 55a～55d, developing apparatus 52a～52d.
Charging system 54a～54d and exposure device 55a～55d are connected on supply unit and the control device, the constituted mode of Charging system 54a～54d is: the Electrophtography photosensor 51a～51d to rotation applies voltage, makes the surface charging of Electrophtography photosensor 51a～51d; The constituted mode of exposure device 55a～55d is: to each Electrophtography photosensor 51a～51d irradiating laser 56a～56d, form the sub-image corresponding to data content according to the data of controlling device input certainly on the surface of each Electrophtography photosensor 51a～51d.
When each Electrophtography photosensor 51a～51d rotates to the position, opposite of developing apparatus 52a～52d, versicolor toner is respectively attached on each Electrophtography photosensor 51a～51d, when Electrophtography photosensor 51a～51d is further rotated when contacting with transfer belt 65, the toner that adheres to is transferred on the transfer belt 65.
Constituting of versicolor toner: be transferred to the diverse location on the transfer belt 65, in the downstream that transfer belt 65 moves, transfer belt 65 contacts with printed mediums such as paper, and the toner on the transfer belt 65 is transferred on the printed medium.The part contact number of times identical with chromatic number that adheres to different colours on printed medium and the transfer belt 65, the toner of different colours is transferred on the printed medium during contact.
When Electrophtography photosensor 51a～51d moves according to the order opposite of Charging system 54a～54d, exposure device 55a～55d, developing apparatus 52a～52d, the upstream side configuration of moving from the transfer belt 65 that moves together is corresponding to Electrophtography photosensor 51a～51d red, blue, yellow, black toner, on printed medium according to black, yellow, indigo plant, red order repetition transfer printing toner.
The printed medium of having finished each colour toners transfer printing is separated on transfer belt 65, make toner fixing, be discharged to the outside of device afterwards by fixing device 19.
Below, embodiment and experimental example, the comparative example of Electrophtography photosensor of the present invention together is elaborated.
(synthesis example 1 of phthalocyanine)
Flow down at nitrogen, in the potpourri of 64.4 g benzene dinitriles and 150ml α-chloronaphthalene with the titanium tetrachloride that dripped 6.5ml in 5 minutes.After the dropping, finished reaction in 2 hours with mantle heater heating under 200 ℃.Afterwards, filter precipitate, filtration residue is cleaned with α-chloronaphthalene, clean with chloroform afterwards, use washed with methanol again.Afterwards, the hydrolysis reaction that utilizes the mixed liquor of 60 ml strong aquas and 60 ml ion exchange waters under boiling point, to carry out 10 hours, at room temperature attract afterwards to filter, inject ion exchange water and clean in residue, the ion exchange water that continues to clean until isolated by filtration in residue is neutral.
Afterwards, further use the washed with methanol residue, use 90 ℃ heated-air drying 10 hours afterwards, obtain the hepatic crystal type of 64.6g TiOPc (titanyl phthalocyanine, Titanyl phthalocyanine) powder.
Next, in the concentrated sulphuric acid of about 10 times of amounts, taking out anhydrates makes it separate out, filter with this powder dissolution, will wet cake afterwards in ethylene dichloride, at room temperature stirred 1 hour, obtains 40g TiOPc of the present invention.
(synthesis example 2 of phthalocyanine)
Flow down at nitrogen, in the potpourri of 64.4g benzene dinitrile and 150ml α-chloronaphthalene with the titanium tetrachloride that dripped 6.5ml in 5 minutes.After the dropping, finished reaction in 2 hours with mantle heater heating under 200 ℃.
Afterwards, filter precipitate,, clean with chloroform afterwards, use washed with methanol again with α-chloronaphthalene cleaning and filtering residue.Afterwards, the hydrolysis reaction that utilizes the mixed liquor of 60 ml strong aquas and 60 ml ion exchange waters to carry out under boiling point 10 hours at room temperature attracts to filter afterwards, and is same with above-mentioned synthesis example 1, uses ion exchange water to clean.Afterwards, use washed with methanol, use 90 ℃ heated-air drying 10 hours afterwards, obtain the hepatic crystal type of 64.6g TiOPc powder.
Next, in the concentrated sulphuric acid of about 10 times of amounts, washing, drying obtain 40g TiOPc of the present invention with this powder dissolution.
＜embodiment A 1 〉
With alkyd resin (trade name " ベ Star コ ラ イ ト M-6401-50 ", big Japanese ink chemical industry society system) and amino resins (trade name " ス-パ-ベ Star カ ミ Application G-821-60 ", big Japanese ink chemical industry society system) mixes with the ratio of 65:35, make above-mentioned hybrid resin and titanium dioxide (trade name " CR-EL " again, the former industry of stone society system) reaches the ratio of 1:3, be dissolved in the butanone, make coating fluid.It is comprising on the cylindrical drum of not having cutting aluminium of 24mm that this coating fluid is coated on diameter, and forming thickness is the bottom of 1.5 μ m.
Next, in the TiOPc powder that 10g synthesis example 1 obtains, add beaded glass and at 500ml1, be dissolved with 10g polyvinyl butyral resin (trade name " BM-1 " in the 3-dioxolane, ponding chemical industry society system) solution, disperseed 20 hours with the sand milling dispersion machine, filter the gained dispersion liquid, remove beaded glass, make the charge generation layer coating fluid.Its dip coated is carried out drying on above-mentioned bottom, forming thickness is the charge generation layer of 0.2 μ m.
Next, by weight 1.0:1.0:0.05 prepare as resinoid bond polycarbonate resin (gas chemistry society of trade name " Z400 " Mitsubishi system), be the N-phenyl-1-naphthylamine of antioxidant as the compound of formula (Aa1) expression of charge transfer agent with as aromatic amine, be dissolved in the chloroform preparation charge transfer layer coating fluid.
Be formed with this charge transfer layer coating fluid of dip coated on the matrix of charge generation layer, drying is 60 minutes under 120 ℃, and forming thickness is the charge transfer layer of 25.0 μ m, makes Electrophtography photosensor.
The X-ray diffraction making of corpse or other object for laboratory examination and chemical testing sample
Along the circumferential direction and with the Cylindorical rod direction that it intersects cut respectively with scissors with office at the photosensitive surface that embodiment A 1 obtains, form the hole of cutting of the about 2cm in one side.Use pincet to cut the part that the hole enters and peel off light-sensitive surface from this.
15ml4-methoxyl-4-methyl-2-pentanone is packed in the 50ml beaker, above-mentioned stripping film is immersed in wherein, make charge transfer layer dissolve the back fully and fully mix, form gelatinous fine and be dispersed in the solvent.It is attracted to filter with teflon (registered trademark) made membrane filter (aperture is 0.2 μ m), and filtrate is cleaned with 10ml PTX (4-methoxyl-4-methyl-2-pentanone).Next, make membrane filter and the driving fit of no silicon reflecting plate, make filtrate become the inboard.Stripping film filter makes TiOPc attached on the no silicon reflecting plate, and it is air-dry, as the corpse or other object for laboratory examination and chemical testing sample of X-ray diffraction.
X-ray diffraction
When measuring the corpse or other object for laboratory examination and chemical testing sample of as above making, utilize powder method to measure, use CuK α (wavelength 1.54178
) as x-ray source, condition determination is as follows.
System X ' the Pert of X-ray diffraction device Off リ Star プ ス society
Condition determination X-ray tube ball Cu
4 °～29 ° of sweep limits
Tube voltage 45kv
Tube current 40mA
Prague angle 0.01 degree
Be subjected to optical slits, divergent slit changeable type
Irradiating width 20mm
The X-ray diffractogram of corpse or other object for laboratory examination and chemical testing sample is seen Fig. 1.Confirmed by Fig. 1: the TiOPc that extracts from photographic layer has diffraction peak for 9.7 °, 14.2 °, 18.0 °, 24.2 ° and 27.2 ° at Bragg angle (2 θ ± 0.2 °).
The material that is commonly referred to as Y type TiOPc is near 27.2 °, exist maximum peak in ± 0.2 ° error range.
The TiOPc of embodiment A 1 locates to have the maximum diffraction peak at 27.2 °, is Y type TiOPc therefore.
＜embodiment A 2 〉
The charge generation agent that the TiOPc that obtains with 10 g synthesis examples 2 replaces synthesis example 1 to obtain, it is carried out dry type with beaded glass pulverizes, be added in afterwards in the 150 ml methyl alcohol and be dissolved with in the solution of 5g polyvinyl butyral resin, disperseed 30 minutes with sand mill, be added in then in the solution that is dissolved with 5 g polyvinyl butyrals in the 350ml butanone, disperseed 20 hours with sand mill once more, filter the gained dispersion liquid, remove beaded glass, make the charge generation layer coating fluid.To carry out drying after its dip coated, forming thickness is the charge generation layer of 0.2 μ m.
After, carry out and embodiment A 1 identical operations, make Electrophtography photosensor.In addition, utilize the X-ray diffraction identical with embodiment A 1, the X-ray diffractogram of the TiOPc that extracts from photographic layer is seen Fig. 2.
This TiOPc locates to have distinctive diffraction peak (maximum diffraction peak) at 27.2 °, and the diffraction peak intensity of other diffraction peak intensities with respect to 27.2 ° is below 20%.Further specifically, locate to confirm diffraction peak for 7.3 °, 13.5 °, 18.6 °, 24.0 ° and 27.2 ° at Bragg angle (2 θ ± 0.2 °).
＜embodiment A 3 〉
Except the charge transfer agent that uses chemical formula (A1b) expression replaces the charge transfer agent that uses in the embodiment A 2 and is that to replace to phenol be antioxidant 2 to antioxidant with aromatic amine, beyond the 6-di-tert-butyl-4-methy phenol, carry out and embodiment A 2 identical operations, make Electrophtography photosensor.
＜embodiment A 4 〉
Except the charge transfer agent that uses chemical formula (A1c) expression replaces the charge transfer agent that uses in the embodiment A 2 and is that to replace to phenol be antioxidant 2 to antioxidant with aromatic amine, beyond the 6-di-tert-butyl-4-methy phenol, carry out and embodiment A 2 identical operations, make Electrophtography photosensor.
＜embodiment A 5 〉
Except the charge transfer agent that the charge transfer agent that uses above-mentioned chemical formula (A1b) expression replaces using in the embodiment A 1, carry out and embodiment A 1 identical operations, make Electrophtography photosensor.
＜embodiment A 6 〉
Except the charge transfer agent that the charge transfer agent that uses above-mentioned chemical formula (A1c) expression replaces using in the embodiment A 1, carry out and embodiment A 1 identical operations, make Electrophtography photosensor.
＜embodiment A 7 〉
Except the charge transfer agent that the charge transfer agent that uses chemical formula (A1d) expression replaces using in the embodiment A 1, carry out and embodiment A 1 identical operations, make Electrophtography photosensor.
＜Comparative examples A 1 〉
Except the charge transfer agent that the charge transfer agent that uses chemical formula [AA] expression replaces using in the embodiment A 2, carry out and embodiment A 2 identical operations, make Electrophtography photosensor.
Chemical formula (AA)
＜Comparative examples A 2 〉
Except the charge transfer agent that the charge transfer agent that uses chemical formula [AB] expression replaces using in the embodiment A 2, carry out and embodiment A 2 identical operations, make Electrophtography photosensor.
Chemical formula (AB)
＜Comparative examples A 3 〉
Except the charge generation agent that the β type TiOPc that uses Fig. 3 to represent replaces using in the embodiment A 2, carry out and embodiment A 2 identical operations, make Electrophtography photosensor.
＜Comparative examples A 4 〉
Except the charge transfer agent that the charge transfer agent that uses chemical formula [AA] expression replaces using in the embodiment A 1, carry out and embodiment A 1 identical operations, make Electrophtography photosensor.
＜Comparative examples A 5 〉
Except the charge transfer agent that the charge transfer agent that uses chemical formula [AB] expression replaces using in the embodiment A 1, carry out and embodiment A 1 identical operations, make Electrophtography photosensor.
＜evaluation method 〉
Evaluation method is as described below.Use Electrophtography photosensor evaluating apparatus (sorb electronics industry society system), Electrophtography photosensor at experimental example, embodiment and comparative example making, with charged, expose, develop, be transferred as 1 circulation, with the 1st round-robin current potential as the initial stage current potential, further measure 10,000 the circulation after surface potential (V0), residual electric potential (VL), exposure be 0.4 μ J/cm
2Static characteristic, by obtaining variable quantity evaluation.It the results are shown in Table 1.
[table 1] evaluation test result
As shown in Table 1: embodiment A 1～A7 utilizes the combination of charge generation agent of the present invention and charge transfer agent, and charged current potential, residual electric potential after charged current potential of initial stage, residual electric potential, 10,000 circulations all do not have big variation, and the photoreceptor characteristic is good.In addition, with aromatic amine be embodiment A 1, the A2 of antioxidant combination, the fast light fatigue of photoreceptor, the decline of the surface potential (V0) after 10,000 circulations is in 5v, photoreceptor is good.
And, with phenol be embodiment A 3, the A4 of antioxidant combination, though the surface potential of photoreceptor (V0) slightly descends, residual electric potential (VL) does not have big variation, therefore can use in no problem scope in the practicality.
With respect to this, Comparative examples A 1～A5 utilizes the combination of charge transfer agent He other charge transfer agents of the present application, and the residual electric potential after 10,000 circulations changes greatly, can't satisfy the sensitization bulk properties.
And according to the combination of the charge transfer agent of other charge generation agent and the present application, the residual electric potential after 10,000 circulations changes greatly, can't satisfy the sensitization bulk properties.
In addition, with embodiment A 1, A5～A7 and embodiment A 2～A4 more as can be known: even when using identical charge transfer agent, compare during with the TiOPc that uses Fig. 2 to represent, the exposure that reduces by half when using the TiOPc that Fig. 1 represents is little, highly sensitive.
According to the present application, the good photoreceptor that anti-insulation breakdown excellence with respect to contact electrification can be provided, not exist the residual electric potential that causes by the use in can wiping type electro-photography apparatus to rise.
Embodiment
Next, specify the embodiment of the Electrophtography photosensor that uses tetrahydrofuran and form, but the present invention is not limited to the combination shown in following examples.
＜Embodiment C 1 〉
With alkyd resin (trade name " ベ Star コ ラ イ ト M-6401-50 ", big Japanese ink chemical industry (strain) society system) and amino resins (trade name " ス-パ-ベ Star カ ミ Application G-821-60 ", big Japanese ink chemical industry (strain) society system) mixes with the ratio of 65:35 (weight ratio), make above-mentioned hybrid resin and titanium dioxide (trade name " CR-EL " again, the former industry of stone (strain) society system) reaches the ratio of 1:3 (weight ratio), be dissolved in respectively in the butanone, make coating fluid.The cylindrical drum that comprises aluminium alloy that with the diameter is 30mm is as electric conductivity supporter 21, above-mentioned coating fluid is coated on carries out drying on this drum, and forming thickness is the bottom of 1.5 μ m.
Next, use polyvinyl butyral resin (trade name " BM-1 " by the coating of dip coated step, ponding chemical industry (strain) society system) as the Y type TiOPc of resinoid bond (system paper (strain) society of Mitsubishi system) dispersion liquid, carry out drying afterwards, laminated thickness is the charge generation layer 22 of 0.1 μ m on above-mentioned bottom.Still it should be noted that the X-ray diffractogram of the Y type TiOPc that uses in the Embodiment C 1 is identical with the figure that Fig. 1 represents.
Afterwards, with the charge transfer agent of above-mentioned chemical formula (C1a), as the antioxidant (N-phenyl-1-naphthylamine) of adjuvant with as the polycarbonate resin (trade name " Z400 " of resinoid bond, society of Mitsubishi's gas chemistry (strain) system) is dissolved in the tetrahydrofuran, obtains charge transfer layer coating.
This coating of dip coated on above-mentioned charge generation layer 22, heat drying, forming thickness is the charge transfer layer 23 of 18 μ m, obtains the Electrophtography photosensor 11 of Embodiment C 1.
＜Embodiment C 2 〉
Except will replacing to the compound of chemical formula (C1b), make the Electrophtography photosensor 11 of Embodiment C 2 according to the condition identical with Embodiment C 1 as the compound of the chemical formula (C1a) of charge carrying substances.
＜Embodiment C 3 〉
Except will replacing to the compound of chemical formula (C1c), make the Electrophtography photosensor 11 of Embodiment C 3 according to the condition identical with Embodiment C 1 as the compound of the chemical formula (C1a) of charge carrying substances.
＜Embodiment C 4 〉
Except will replacing to the compound of chemical formula (C1d), make the Electrophtography photosensor 11 of Embodiment C 4 according to the condition identical with Embodiment C 1 as the compound of the chemical formula (C1a) of charge carrying substances.
＜Embodiment C 5 〉
Except use phenol is antioxidant as the antioxidant that is used for charge transfer layer, make charge transfer layer with beyond the coating, make the Electrophtography photosensor 11 of Embodiment C 5 according to the condition identical with Embodiment C 1.
Still it should be noted that, on the Electrophtography photosensor of the foregoing description C1～C6, peel off charge transfer layer, utilize thermal decomposition vapor-phase chromatography (GCMS-QP2000GF: when Shimadzu Seisakusho Ltd.'s system) carrying out the qualitative test of the residual THF (tetrahydrofuran) in the charge transfer layer, confirm the residual THF of difference in each charge transfer layer.
＜Embodiment C 1d 〉
Except using methylene chloride to replace tetrahydrofuran as being used for the coating solvent of charge transfer layer with coating, make charge transfer layer with beyond the coating, make the Electrophtography photosensor of Embodiment C 1d according to the condition identical with Embodiment C 1.
＜Embodiment C 2d 〉
Except using chloroform to replace tetrahydrofuran as being used for the coating solvent of charge transfer layer with coating, make charge transfer layer with beyond the coating, make the Electrophtography photosensor of Embodiment C 2d according to the condition identical with Embodiment C 1.
＜comparative example C3 〉
Except will replacing to the compound of following chemical formula (CA), make the Electrophtography photosensor of comparative example C3 according to the condition identical with Embodiment C 1 as the compound of the chemical formula (C1a) of charge carrying substances.
Chemical formula (CA)
＜comparative example C4 〉
Except will replacing to the compound of following chemical formula (CB), make the Electrophtography photosensor of comparative example C4 according to the condition identical with Embodiment C 1 as the compound of the chemical formula (C1a) of charge carrying substances.
Chemical formula (CB)
＜comparative example C5 〉
In Embodiment C 1, except the TiOPc that will be used for charge generation layer replaces to α type TiOPc, carry out and Embodiment C 1 identical operations, on the electric conductivity supporter, form charge generation layer, charge transfer layer.Still it should be noted that the X-ray diffractogram of the α type TiOPc that uses among the comparative example C5 is identical with the figure that Fig. 6 represents.
＜evaluation test 〉
Evaluation method is as described below.
[mensuration of static characteristic]
Go up the Electrophtography photosensor 11 that above-mentioned Embodiment C 1～C5, Embodiment C 1d, C2d, comparative example C3～C5 are installed at Electrophtography photosensor evaluating apparatus (sorb electronics industry (strain) society system), as electro-photography apparatus shown in Figure 51.
With charged, expose, develop, be transferred as 1 circulation, as the initial stage current potential, further measure surface potential (V0), the static characteristic of residual electric potential (VL) after 10,000 circulations, with the 1st round-robin current potential by obtaining variable quantity evaluation.
In addition, the traveling time (linear velocity) from the image exposure step to development step is set at as the record the table 2.It the results are shown in Table 2.
The result of [table 2] evaluation test
Still it should be noted that the Embodiment C 6 in the above-mentioned table 2 is in the electro-photography apparatus 1 of the Electrophtography photosensor that uses Embodiment C 1, will be from as the evaluation result of step of exposure when the traveling time of development step is set at 0.15 second.
By above-mentioned table 2 as can be known: Embodiment C 1～C5 utilizes the compound of general formula (C1) and the combination of tetrahydrofuran, and charged current potential, residual electric potential after charged current potential of initial stage, residual electric potential, 10,000 circulations all do not have big variation, and the photoreceptor characteristic is good.
In addition, the photoreceptor characteristic of Embodiment C 6 is also excellent, and the application's Electrophtography photosensor can use when not only on-line velocity is as short as below 0.1 second, also can use when on-line velocity surpasses 0.1 second.
With respect to this, the result of the solvent of the use of Embodiment C 1d, C2d except that tetrahydrofuran, the charged potential change after 10,000 circulations is big, can't satisfy the sensitization bulk properties.
In addition, the compound of the use of comparative example C3, C4 except that general formula (C1) is as the result of charge transfer agent, and the residual electric potential after initial stage residual electric potential and 10,000 circulations changes greatly, can't satisfy the sensitization bulk properties.
As mentioned above, as can be known: in the making step of photographic layer 25, when using solvent except that tetrahydrofuran or the compound of use except that general formula (C1) as charge transfer agent, particularly on-line velocity can't the satisfaction light characteristic soon to the device below 0.1 second.
In addition, the result of the α type that the charge generation agent is replaced to of comparative example C5, the residual electric potential after initial stage residual electric potential and 10,000 circulations changes greatly, can't satisfy the sensitization bulk properties.Therefore, when using α type TiOPc, even use tetrahydrofuran as solvent, on-line velocity to the device below 0.1 second, can't satisfy the sensitization bulk properties soon.
Claims (8)
1. Electrophtography photosensor, this photoreceptor have the electric conductivity supporter and are configured in photographic layer on the above-mentioned electric conductivity supporter; Contain charge generation agent and charge transfer agent in the above-mentioned photographic layer; Above-mentioned charge generation agent is a TiOPc, and this TiOPc is being to locate to have the Bragg angle (2 θ) that manifests maximum peak at 27.2 ° ± 0.2 ° in the radiogenic X ray diffracting spectrum with CuK α; Above-mentioned charge transfer agent contains any one or two kinds of above compounds of the compound group that is selected from following chemical formula (A1a)～(A1d):
Chemical formula (A1a)
Chemical formula (A1b)
Chemical formula (A1c)
Chemical formula (A1d)
2. the Electrophtography photosensor of claim 1, wherein above-mentioned photographic layer are above-mentioned charge transfer agent to be dissolved in make above-mentioned tetrahydrofuran evaporation behind the tetrahydrofuran and form; Contain above-mentioned tetrahydrofuran in the above-mentioned photographic layer.
3. the Electrophtography photosensor of claim 1, wherein above-mentioned TiOPc has been located diffraction peak for 9.7 °, 14.2 °, 18.0 °, 24.2 ° and 27.2 ° at Bragg angle (2 θ ± 0.2 °).
4. the Electrophtography photosensor of claim 1, it is antioxidant that wherein above-mentioned photographic layer contains aromatic amine.
5. electro-photography apparatus, this device has: Electrophtography photosensor; Make the Charging system of above-mentioned electrophotographic photoreceptor belt electricity; With charged above-mentioned Electrophtography photosensor exposure, form the exposure device of sub-image on above-mentioned Electrophtography photosensor surface; With make toner attached to the developing apparatus on the above-mentioned sub-image on above-mentioned Electrophtography photosensor surface; Wherein, make attached to the above-mentioned toner on the above-mentioned Electrophtography photosensor and be transferred on the printed medium; Above-mentioned Electrophtography photosensor has electric conductivity supporter and the photographic layer that is configured on the above-mentioned electric conductivity supporter; Contain charge generation agent and charge transfer agent in the above-mentioned photographic layer; Above-mentioned charge generation agent is a TiOPc, and this TiOPc is being to locate to have the Bragg angle (2 θ) that manifests maximum peak at 27.2 ° ± 0.2 ° in the radiogenic X ray diffracting spectrum with CuK α; Above-mentioned charge transfer agent contains any one or two kinds of above compounds of the compound group that is selected from following chemical formula (A1a)～(A1d):
Chemical formula (A1a)
Chemical formula (A1b)
Chemical formula (A1c)
Chemical formula (A1d)
6. the electro-photography apparatus of claim 5, this device carry out charged, the formation of above-mentioned sub-image of above-mentioned Electrophtography photosensor, above-mentioned toner adhere to transfer printing with above-mentioned toner after, charged after under above-mentioned Electrophtography photosensor needn't remove the situation of electricity, carrying out.
7. the electro-photography apparatus of claim 5, wherein above-mentioned Electrophtography photosensor is below 0.1 second from the exposure position with above-mentioned Electrophtography photosensor exposure to the linear velocity that makes above-mentioned toner attached to the developing location on the above-mentioned sub-image.
8. the electro-photography apparatus of claim 5, wherein above-mentioned Charging system is the contact electrification device that directly contacts with above-mentioned Electrophtography photosensor.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006022435 | 2006-01-31 | ||
| JP022435/2006 | 2006-01-31 | ||
| JP042292/2006 | 2006-02-20 |
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| Publication Number | Publication Date |
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| CN101416119A true CN101416119A (en) | 2009-04-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800121536A Pending CN101416119A (en) | 2006-01-31 | 2007-01-25 | Electrophotographic photoreceptor and electrophotographic apparatus |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482245A (en) * | 2009-09-11 | 2012-05-30 | 株式会社理光 | Furan Derivative And Electrophotographic Photoconductor |
| CN109240060A (en) * | 2017-07-10 | 2019-01-18 | 柯尼卡美能达株式会社 | Image forming apparatus and image forming method |
-
2007
- 2007-01-25 CN CNA2007800121536A patent/CN101416119A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482245A (en) * | 2009-09-11 | 2012-05-30 | 株式会社理光 | Furan Derivative And Electrophotographic Photoconductor |
| CN102482245B (en) * | 2009-09-11 | 2015-05-13 | 株式会社理光 | Furan derivative and electrophotographic photoconductor |
| CN109240060A (en) * | 2017-07-10 | 2019-01-18 | 柯尼卡美能达株式会社 | Image forming apparatus and image forming method |
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Open date: 20090422 |