CN101930185B - Electrophototgraphic photoreceptor, image forming device and processing box - Google Patents
Electrophototgraphic photoreceptor, image forming device and processing box Download PDFInfo
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- CN101930185B CN101930185B CN201010208873.3A CN201010208873A CN101930185B CN 101930185 B CN101930185 B CN 101930185B CN 201010208873 A CN201010208873 A CN 201010208873A CN 101930185 B CN101930185 B CN 101930185B
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Images
Landscapes
- Photoreceptors In Electrophotography (AREA)
Abstract
The invention relates to an electrophototgraphic photoreceptor, image forming device and processing box. The invention aims at providing an electrophototgraphic photoreceptor with high performance, so as to be capable of using the current polyarylate electrophototgraphic photoreceptor, namely, the abrasion resistance of the current polyarylate electrophototgraphic photoreceptor is improved and the dissolvability and electric characteristics such as residual potential, bright potential and the like in a coating liquid solvent are simultaneously improved, and the electrophototgraphic photoreceptor has high endurance, the good images can be continuously obtained in case of repeated use. In addition, The invention also provides an image forming device using the electrophototgraphic photoreceptor to realize the minitype and high-speed printing, and a processing box for the image forming device. The electrophototgraphic photoreceptor has a photosensitive layer on a conductive support, characterized in that the photosensitive layer contains a binder resin with a specific structure unit.
Description
Technical field
The present invention relates to there is high-durability and realized the Electrophtography photosensor (being designated hereinafter simply as photoreceptor) of long-term higher image quality.In addition, relate to the image processing system and the image processing system processing unit that have used these photoreceptors.
Background technology
Be applied to use in duplicating machine, facsimile recorder, laser printer etc. the image forming method of electrofax of Electrophtography photosensor have: through after making the process of electrophotographic photoreceptor belt electricity, image exposure, development, carry out toner image to various processes such as the surface cleaning of transfer printing, photographic fixing and the Electrophtography photosensor of image holding body (transfer printings of common paper etc.).
But, for this Electrophtography photosensor, being generally at present known is that on electric conductivity supporter, to be provided with Electrophtography photosensor take selenium or selenium alloy as the photoconductive layer of main body, to make zinc paste etc. inorganic be that photoconductive material is dispersed in the Electrophtography photosensor in cementing agent and has used Electrophtography photosensor of amorphous layer material etc., in recent years, Organophotoreceptor is because cost is low, the degree of freedom of photoreceptor design is high, non-pollution etc. is widely used.
As this Organophotoreceptor, photoreceptor excellence aspect the various characteristicses such as sensitivity, permanance, stability of the function divergence type photographic layer structure of had lamination charge generation layer and charge transport layer, is widely used.
But, have in the Organophotoreceptor of above-mentioned functions divergence type layer structure, the charge transport layer that becomes superficial layer usually contains the charge transport material of low molecular compound, so in order to ensure the film forming of this charge transport layer, resin glue and charge transport material are share, but the charge transport layer being formed by resin glues such as low molecular charge transport material and polycarbonate is generally more soft, can enumerate as shortcoming: in electrofax is processed when Reusability because of toning system, the mechanical load at photosensitive surface due to cleaning systems and the low shortcoming of such abrasion performance of easily wearing and tearing.In fact, due to wear of the photosensitive member and the deterioration of sensitivity showed adverse effects, and decreased chargeability, resulting decrease in image density, substrate contamination (dirt in muscle), and other abnormal images sometimes reaches the life of the photosensitive member.
For such problem, the technological development that carried out improving resin glue, can form the charge transport layer that hardness is higher.For example, as the resin glue that improves photoreceptor abrasion performance characteristic, the polycarbonate of bisphenol Z type is disclosed in patent documentation 1.
But will use this polycarbonate in electrofax is at a high speed processed time, present situation is that its abrasion performance, mar resistance etc. are scarcely abundant, expects more high performance resin glue.
On the other hand, in order to improve the physical strength of photoreceptor, also have and use the example of aromatic polyester as resin glue.For example, commercially available polyarylate (aromatic polyester) resin of commodity in use " U-Polymer " by name is disclosed in patent documentation 2 as the technology of the Electrophtography photosensor of cementing agent, wherein, compared with polycarbonate, demonstrate sensitivity excellent especially.In addition, in patent documentation 3, disclose a kind of Electrophtography photosensor, it is characterized in that, polyarylate (aromatic polyester) multipolymer that contains the structure that has used tetramethyl Bisphenol F and bisphenol-A in bisphenol component.And then, a kind of Electrophtography photosensor is disclosed in patent documentation 4, it is characterized in that, contain and used the polyarylate (aromatic polyester) of bisphenol-c as bis-phenol.
But, according to using these aromatic polyesters as the technology of photographic layer cementing agent, there is the shortcoming that the stability of dissolubility in the coating solvent of photographic layer and solution is bad or their electrical specification worsens.The technology that particularly above-mentioned patent documentation 2 is recorded, although seeing aspect abrasion performance, sensitivity that some improve, due to the poor stability of its coating fluid, thus can not be coated with manufacture, or allow to coating manufacture, sliding is also bad.In addition, the technology that above-mentioned patent documentation 3 is recorded although see raising compared with existing polycarbonate aspect abrasion performance, be can't see superiority aspect sliding compared with polycarbonate.And then, the technology that above-mentioned patent documentation 4 is recorded, remains aspect abrasion performance and see raising compared with existing polycarbonate, although have advantages of that the life of photoreceptor is such, but aspect electrical specification, particularly response, than using, the situation of polycarbonate resin is poor.Skeleton for polyarylate changes, also on the books in above-mentioned patent documentation 5, but has still inadequate problem.
Patent documentation 1: Japanese kokai publication sho 59-071057
Patent documentation 2: Japanese kokai publication sho 56-135844
Patent documentation 3: Japanese kokai publication hei 03-006567
Patent documentation 4: Japanese kokai publication hei 07-333911
Patent documentation 5: TOHKEMY 2001-290288
Summary of the invention
The object of the present invention is to provide a kind of high performance Electrophtography photosensor, it has solved the problem of the Electrophtography photosensor of existing use polyarylate,, in improving abrasion performance characteristic, improve dissolubility, the electrical specification (rest potential, bright portion current potential etc.) in coating fluid solvent, there is high-durability, even for Reusability, also sustainablely obtain good image.In addition the object of the present invention is to provide by using above-mentioned Electrophtography photosensor to realize image processing system and the processing box for image forming device of miniaturization and high reliability that can high speed printing.
Object of the present invention can be reached as the resin glue of Electrophtography photosensor by the vibrin with new.
The present invention and optimal way thereof are narrated.
The present invention relates to a kind of Electrophtography photosensor, it has photographic layer on electric conductivity supporter, wherein, and the resin glue that photographic layer contains the structural unit with following general formula (1) expression.
General formula (1)
(in general formula (1), R
1represent to have the divalent group of more than 3 aromatic rings, R
2represent and R
1the different divalent groups with more than 2 aromatic rings, R
3represent divalent organic group.)
R in preferred formula (1)
3by dicarboxylic acid R
3(COOH)
2derivative divalent organic group, R
1by the 1st glycol R
1(OH)
2derivative divalent group, R
2by the 2nd glycol R
2(OH)
2derivative divalent group.
Preferably the 1st glycol R
1(OH)
2for the aromatic diol compound of following general formula (2), and the 2nd glycol R
2(OH)
2for the aromatic diol compound of following general formula (3).
General formula (2)
HO-φ
1-A
1-φ
2-A
2-...-A
j-1-φ
j-OH
In general formula (2), φ
1, φ
2... φ
jrepresent aromatic rings (j is more than 3 integer),
A
1, A
2... A
j-1for be selected from-CR
11r
12-,-R
13-, group (j is more than 3 integer) in-O-,-S-and Direct Bonding.
Wherein, R
11, R
12represent H, alkyl, allyl, aryl, alkoxy, halogen, R
11and R
12can form ring by bonding.R
13represent that carbon number is 2 above alkylidenes.
General formula (3)
HO-φ
1-B
1-φ
2-B
2-...-B
k-1-φ
k-OH
In general formula (3), φ
1, φ
2... φ
krepresent aromatic rings (k is more than 2 integer),
B
1, B
2... B
k-1for be selected from-CR
21r
22-,-R
23-,-O-,-S-,-SO
2-and Direct Bonding in group (k is more than 2 integer).
Wherein, R
21, R
22represent H, alkyl, allyl, aryl, alkoxy, halogen, R
21and R
22can form ring by bonding.R
23represent that carbon number is 2 above alkylidenes.
The 1st glycol R
1(OH)
2be preferably more than one the diol compound being selected from following general formula (2a) and general formula (2b).
General formula (2a)
General formula (2b)
In the compound that general formula (2a) represents, the compound that preferred following general formula (2c) represents.
General formula (2c)
General formula (2a) is to general formula (2c), and R is the group being selected from alkyl, allyl, aryl.
R and R can form other ring by bonding, and whole R can be the same or different.
The 1st glycol R
1(OH)
2be preferably more than one the compound being selected from following d1 to d5.
The 2nd glycol R
2(OH)
2be preferably and be selected from general formula (3a) to more than one the diol compound in general formula (3c).
General formula (3a)
General formula (3b)
General formula (3c)
General formula (3a) is to general formula (3c), and R is the group being selected from alkyl, allyl, aryl.
R and R can form other ring by bonding, and whole R can be the same or different.
General formula (3a) is to the 2nd glycol R of general formula (3b)
2(OH)
2be preferably more than one the compound being selected from following d11 to d16.
The 2nd glycol R
2(OH)
2be preferably be selected from following general formula (3d) and (3e) in more than one aromatic diol compound.
General formula (3d)
General formula (3e)
In the compound that general formula (3d) represents, the compound that preferred following general formula (3f) represents.
General formula (3f)
General formula (3d) is to general formula (3f), and R is the group being selected from alkyl, allyl, aryl.R and R can form other ring by bonding, and whole R can be the same or different.
General formula (3d) is to the 2nd glycol R of general formula (3f)
2(OH)
2be preferably more than one the compound being selected from following d21 to d23.
Derive from the 1st glycol R
1(OH)
2structure (R
1) and derive from the 2nd glycol R
2(OH)
2structure (R
2) mol ratio (R
1/ R
2) be preferably 5/95 to 95/5.
R in general formula (1)
3the dicarboxylic acid compound in source preferably use aromatic dicarboxylic acid or aliphatic dicarboxylic acid.
Above-mentioned dicarboxylic acid compound preferably uses the dicarboxylic acid compound of more than two kinds being selected from aromatic dicarboxylic acid or aliphatic dicarboxylic acid.
The photographic layer of above-mentioned Electrophtography photosensor has charge generation layer and the charge transport layer of lamination on this charge generation layer, and the photographic layer of this Electrophtography photosensor preferably contains the resin glue of the structural unit with general formula (1) expression.
A kind of image processing system, it is at least to have charged elements, exposing unit, developing cell at the periphery of Electrophtography photosensor, repeatedly carries out the image processing system of image formation, wherein, this Electrophtography photosensor is above-mentioned Electrophtography photosensor.
A kind of handle box, integrally there is at least above-mentioned Electrophtography photosensor and be selected from charged elements, cleaning unit, as at least one unit in exposing unit and developing cell, and can be loaded and unloaded on image processing system.
The present invention can provide a kind of high performance Electrophtography photosensor, it has improved dissolubility, the electrical specification (rest potential, bright portion current potential etc.) in coating fluid solvent while manufacture in improving abrasion performance characteristic, there is high-durability, even for the Reusability also good image of sustainable acquisition.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that group has entered the function of image processing system of the present invention.
Fig. 2 is the section constitution figure that represents the color image forming device of an embodiment of the present invention.
Fig. 3 is the formation sectional view that has used the color image forming device of Electrophtography photosensor of the present invention.
Embodiment
Below, describe the present invention in detail.
Electrophtography photosensor of the present invention has photographic layer on electric conductivity supporter, it is characterized in that, this photographic layer contains (1) resin glue of structural unit that represents that has general formula.
This Electrophtography photosensor, photoreceptor has high-durability and for Reusability, image disappearance, the image that sustainable acquisition is good does not occur.
Below the main composition important document that forms this Electrophtography photosensor is described.
The resin glue with the structural unit of general formula (1) can pass through dicarboxylic acid R
3(COOH)
2with the 1st glycol R
1(OH)
2with the 2nd glycol R
2(OH)
2polycondensation and obtain.
The 1st glycol R
1(OH)
2preferably use the aromatic diol of general formula (2).
As the φ in general formula (2)
1, φ
2... φ
jconcrete example, for example, can from following group, select.As φ
1, φ
2... φ
j, needn't be all identical substituting group, φ
1, φ
2... φ
jin part or all can use different substituting groups.
A in general formula (2)
1, A
2... A
j-1substituting group in, as more preferred example, for example, can from following group, select.As A
1, A
2... A
j-1, needn't be all identical substituting group, A
1, A
2... A
j-1in part or all can use different substituting groups.
The 2nd glycol R
2(OH)
2preferably use the aromatic diol compound of general formula (3).
As the φ in general formula (3)
1, φ
2... φ
kconcrete example, can from general formula (2) φ
1, φ
2... φ
jin same compound group, select.As φ
1, φ
2... φ
k, needn't be all identical substituting group, φ
1, φ
2... φ
kin part or all can use different substituting groups.
As the B in general formula (3)
1, B
2... B
k-1substituting group, A that can be from general formula (2)
1, A
2... A
j-1the illustrated substituting group of group in select.As B
1, B
2... B
k-1, needn't be all identical substituting group, B
1, B
2... B
k-1in part or all can use different substituting groups.
The 1st glycol R
1(OH)
2preferably use more than one the compound of selecting from following d1 to d5.
As the 2nd glycol R
2(OH)
2, can from following compound, select.
Two (2-hydroxy phenyl) methane,
Two (4-hydroxy phenyl) methane,
Two (4-hydroxy-3-methyl phenyl) methane,
Two (4-hydroxy-2-methyl phenyl) methane,
Two (3-hydroxy-4-methyl phenyl) methane,
Two (4-hydroxy phenyl) phenylmethane,
1,1 '-bis-(4-hydroxy phenyl)-1-diphenylphosphino ethanes,
1,1 '-bis-(4-hydroxy-2-methyl phenyl) diphenylphosphino ethane,
1,1 '-bis-(4-hydroxy-3-methyl phenyl) diphenylphosphino ethane,
2,2 '-bis-(4-hydroxy phenyl) propane (another name bisphenol-A),
2,2 '-bis-(4-hydroxy phenyl) HFC-236fa (another name bisphenol AF),
2,2 '-bis-(4-hydroxy-3-methyl phenyl) propane (another name bisphenol-c),
2,2 '-bis-(4-hydroxyl-3,5-3,5-dimethylphenyl) propane,
2,2 '-bis-(3-ethyl-4-hydroxy phenyl) propane,
2,2 '-bis-(3-tert-butyl-hydroxy phenyl) propane,
2,2 '-bis-(3-cyclohexyl-4-hydroxy phenyl) propane,
2,2 '-bis-(4-hydroxyl-3-phenyl) propane,
2,2 '-bis-(4-hydroxyl-3,5-3,5-dimethylphenyl) propane,
2,2 '-bis-(3-chloro-4-hydroxyl phenyl) propane,
2,2 '-bis-(the bromo-4-hydroxy phenyl of 3-) propane,
2,2 '-bis-(the bromo-4-hydroxy phenyl of 3,5-bis-) propane,
2,2 '-bis-(4-hydroxy phenyl) butane,
2,2 '-bis-(4-hydroxy phenyl)-3-methylbutanes,
2,2 '-bis-(4-hydroxy phenyls)-3,3 '-dimethylbutane,
2,2 '-bis-(4-hydroxy phenyl)-4-methylpentanes,
1,1 '-bis-(4-hydroxy phenyl) cyclopentane,
1,1 '-bis(4-hydroxyphenyl)cyclohexane (another name bisphenol Z),
Two (4-hydroxy phenyl) phenylmethane,
1,1 '-bis-(4-hydroxy phenyl)-1-diphenylphosphino ethanes (another name bisphenol-ap),
Two (4-hydroxy phenyl) sulfone,
Two (4-hydroxy phenyl) ether,
Two (2-hydroxy phenyl) ether,
2,2 '-dihydroxybiphenyl,
3,3 '-dihydroxybiphenyl,
4,4 '-dihydroxybiphenyl etc.
The 2nd glycol R
2(OH)
2be preferably more than one the compound being selected from following d11 to d16.
The 2nd glycol R
2(OH)
2be preferably more than one the compound being selected from following d21 to d23.
And then, for the structure (R that derives from the 1st glycol
1) with the structure (R of the 2nd glycol that derives from general formula (3a) and general formula (3b)
2) mol ratio (R
1/ R
2), be preferably more than 5/95 below 95/5.
When either party's ratio is very big, although be unlikely to hinder practicality, easily produce problem that the dissolubility when making coating fluid worsens a little or initial stage and durable after the problem that worsens of current potential.
And then, there is the R in general formula (1)
3dicarboxylic acid compound preferably use the dicarboxylic acid compound being selected from aromatic dicarboxylic acid or aliphatic dicarboxylic acid.
As aromatic dicarboxylic acid composition, for example, by m-phthalic acid, terephthalic acid (TPA), tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, methyl m-phthalic acid, methyl terephthalic acid (TPA), biphenyl-4, 4 '-dioctyl phthalate, biphenyl-3, 3 '-dioctyl phthalate, diphenyl methane-4, 4 '-dioctyl phthalate, 1, 1-diphenylethane-4, 4 '-dioctyl phthalate, 2, 2-diphenyl propane-4, 4 '-dioctyl phthalate, UVINUL MS 40, 4 '-dioctyl phthalate, naphthalene-1, 4-dioctyl phthalate, naphthalene-1, 5-dioctyl phthalate, naphthalene-2, 6-dioctyl phthalate, naphthalene-2, 7-dioctyl phthalate, diphenyl ether-4, 4 '-dioctyl phthalate, diphenyl sulfide-4, 4 '-dioctyl phthalate, diphenyl sulfide-4, 4 '-aromatic dicarboxylic acid the compound derivings such as dioctyl phthalate obtain, also can be use mixing two or more.In these aromatic dicarboxylic acid compositions, particularly can effectively use m-phthalic acid, terephthalic acid (TPA) and their potpourri.The potpourri of m-phthalic acid and terephthalic acid (TPA) is effective especially, and preferably the mol ratio of m-phthalic acid/terephthalic acid (TPA) is 10/90 to 95/5, and more preferably mol ratio is 25/75 to 75/25.
In addition, as aliphatic dicarboxylic acid composition, for example, obtain by the aliphatic dicarboxylic acids such as hexane diacid, glutaric acid, methylglutaric acid, succinic acid, methylsuccinic acid, pentane dioctyl phthalate, hexane dicarboxylic acid, heptane dioctyl phthalate, octane dicarboxylic acid, decane dioctyl phthalate, dodecane dioctyl phthalate, cyclohexane cyclohexanedimethanodibasic are derivative.
As the glass transition temperature of the resin glue of general formula (1), be preferably 100 ℃ above below 180 ℃.This resin glue is 2 × 10 by the weight-average molecular weight of polystyrene conversion
4to 5 × 10
6being effectively, is particularly preferably 5 × 10 by the weight-average molecular weight of polystyrene conversion
4to 1 × 10
6.
For the manufacture method of the resin glue of general formula (1)
As the manufacture method of copolymerization polyarylate resin with structural unit of the present invention, can utilize and use the various dicarboxylic acid compounds of derivative polyarylate structure, melt phase polycondensation, solution polymerization process and the interfacial polymerization of diol compound or derivatives thereof, especially can effectively use interfacial polymerization.In addition, can be also the autofrettage of having applied the melting mixing ester exchange reaction of other vibrin.
By by the resin glue of general formula (1) for Electrophtography photosensor, in particular for the superficial layer of Organophotoreceptor, can reach better goal of the invention.
Below recording preferred photoreceptor forms.
So-called Organophotoreceptor, mean that organifying compound has the Electrophtography photosensor that at least one function in the requisite charge generation function of the formation of Electrophtography photosensor and charge transport function is formed, refer to by organic charge and produce photoreceptor that material or organic charge transportation of substances form, complete charge generation function and charge transport function and the Organophotoreceptors such as the photoreceptor that forms with high-molecular complex.
Above-mentioned Organophotoreceptor also can have the formation that the photographic layer of single layer structure is set on electric conductivity supporter; but in the present invention, be preferably at least the photoreceptor that following such layer forms, wherein in the preferred protective seam in the superiors or photographic layer, use the resin glue of general formula (1).
1) on electric conductivity supporter, lamination has middle layer and forms as the charge generation layer of photographic layer and the layer of charge transport layer successively,
2) on electric conductivity supporter, lamination has middle layer, forms as the charge generation layer of photographic layer and the layer of charge transport layer and protective seam successively,
By above-mentioned 1) centered by narrate Organophotoreceptor layer form.
(electric conductivity supporter)
As long as supporter has electric conductivity, can be arbitrary substance, for example can enumerate: be the supporter that drum type or sheet obtain by metal formings such as aluminium, copper, chromium, nickel, zinc and stainless steels; On plastic foil lamination the metal forming such as aluminium, copper and supporter; On plastic foil evaporation aluminium, indium oxide and tin oxide etc. and supporter; By separately coating or be coated with together with resin glue and metal, plastic foil and the paper etc. of conductive layer are set of conductive material.
(middle layer)
The middle layer that possesses barriers function and binding function can be set in the middle of conductive layer and photographic layer.
Middle layer can form in the following way: the resin glues such as casein, polyvinyl alcohol (PVA), nitrocellulose, ethylene-acrylic acid copolymer, polyamide, polyurethane and gelatin are dissolved in solvent, form by dip coated etc.Particularly be preferably dissolvable in water the polyamide of alcohol.
In addition,, for the object of resistance of adjusting middle layer, can make middle layer contain various electrically conductive microparticles, metal oxide.The various metal oxides such as such as aluminium oxide, zinc paste, titanium dioxide, tin oxide, antimony oxide, indium oxide, bismuth oxide.Can use doped with the indium oxide of tin, doped with the ultra micron such as tin oxide and zirconia of antimony.
Can use a kind of these metal oxides, or two or more mixing is used.In the situation of two or more mixing, can adopt the form of solid solution or fusion.The mean grain size of such metal oxide is preferably below 0.3 μ m, more preferably below 0.1 μ m.
The solvent using as middle layer, preferably by inorganic particle fine dispersion and by fat-solvent polyamide resin solvent.Specifically, to be 2 to 4 alcohols aspect the dissolubility of polyamide and coating performance excellent and preferably for the carbon number such as ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, the tert-butyl alcohol, sec-butyl alcohol.In addition, in order to improve the dispersiveness of keeping quality, particle, can share cosolvent with solvent, can enumerate methyl alcohol, benzylalcohol, toluene, methylene chloride, cyclohexanone, tetrahydrofuran etc. as this cosolvent.
The concentration of suitably selecting resin glue conforms to thickness, the speed of production in middle layer making.
Inorganic particle while disperseing inorganic particle etc., with respect to the blending ratio of resin glue, is preferably 20 to 400 mass parts with respect to resin glue 100 mass parts inorganic particles, more preferably 50 to 200 parts.
As the diverting device of inorganic particle, can use ultrasonic dispersing machine, bowl mill, sand mill and homomixer etc.
The drying means in middle layer can suitably be selected according to the kind of solvent, thickness, preferably heated drying.
The thickness in middle layer is preferably 0.1 to 30 μ m, more preferably 0.3 to 20 μ m.
(charge generation layer)
Charge generation layer contains charge generation material and resin glue, preferably charge generation material is dispersed in resin glue solution, is coated with and forms.
Charge generation material can be enumerated indigo pigment, the phthalocyanine colors etc. such as the quinone pigments such as the azo raw material such as tonyred and diamine ble (ダ イ ア Application Block Le one), pyrene quinone (PVC レ Application キ ノ Application) and anthanthrone, quinoline cyanines (quinocyanine) pigment, perylene pigment, indigo and thioindigo.These charge generation materials can use separately or use with the form being dispersed in resin.
As the resin glue of charge generation layer, can enumerate for example polystyrene resin, polyvinyl resin, acrylic resin, acrylic resin, methacrylic resin, vestolit, vinyl acetate resin, polyvinyl butyral resin, epoxy resin, urethane resin, phenolics, vibrin, alkyd resin, polycarbonate resin, organic siliconresin, melamine resin, and (for example contain two or more copolymer resin in these resins, vinyl chloride vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-copolymer-maleic anhydride resin) and Polectron etc.
Charge generation layer is preferably as follows formation: use dissolution with solvents resin glue, utilize dispersion machine to disperse charge generation material in the solution obtaining and prepare coating fluid, with coating machine, with constant thickness coating coating fluid, drying coating film, makes charge generation layer.
The solvent that dissolves and be coated with as the resin glue for charge generation layer is used, can enumerate for example toluene, dimethylbenzene, methylene chloride, 1,2-ethylene dichloride, methyl ethyl ketone, cyclohexane, ethyl acetate, butyl acetate, methyl alcohol, ethanol, propyl alcohol, butanols, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, DOX, pyridine and diethylamine etc.
As the diverting device of charge generation material, can use ultrasonic dispersing machine, bowl mill, sand mill and homomixer etc.
Charge generation material, with respect to the blending ratio of resin glue, is preferably 1 to 600 mass parts with respect to resin glue 100 mass parts charge generation materials, more preferably 50 to 500 parts.The thickness of charge generation layer according to characteristic and the blending ratio etc. of the characteristic of charge generation material, resin glue and different, is preferably 0.01 to 5 μ m, more preferably 0.05 to 3 μ m.The coating fluid that charge generation layer is used can prevent by filter foreign matter and agglutinator before coating the generation of image deflects.Also can form by vacuum evaporation pigment.
(charge transport layer)
Charge transport layer contains charge transport material (CTM) and resin glue, and charge transport substance dissolves, in resin glue solution, is coated with and is formed.
Charge transport material for example can be by carbazole derivates, oxazole derivative, oxadiazole derivative, thiazole, thiadiazoles derivative, triazole derivative, imdazole derivatives, imidazolone derivatives, imidazolidine derivative, two imidazolidine derivatives, compound of styryl, hydrazone compound, pyrazoline compounds, azolactone derivant, benzimidizole derivatives, quinazoline derivant, benzofuran derivatives, acridine derivatives, azophenlyene derivant, amino stilbene derivative, triarylamine derivatives, phenylenediamine derivative, stilbene derivative, benzidine derivative, poly-N-vinyl carbazole, poly--1-vinylpyrene and poly--9-vinyl anthracene, triphenylamine derivatives etc. mix two or more use.
The resin glue that charge transport layer is used preferably uses the resin glue of general formula (1).Also can share other resins together with the resin glue of general formula (1).As the resin glue share, can enumerate polycarbonate resin, polyacrylate resin, other vibrin, polystyrene resin, styrene-acrylonitrile copolymer resin, polymethacrylate resin and styrene-methacrylate co-polymer resin etc.
Charge transport layer is preferably as follows formation: resin glue and charge transport substance dissolves are prepared to coating fluid, and with constant thickness coating coating fluid, coated film is dry with coating machine, make charge transport layer.
As the solvent for the coating fluid of the resin glue that contains charge transport layer and charge transport material is dissolved, can enumerate for example methylene chloride, 1, 2-ethylene dichloride, toluene, dimethylbenzene, benzene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, tetrahydrofuran, 1, 4-dioxane, 1, 3-dioxolanes, N, N '-dimethyl formamide, pyridine etc., wherein, as using all good solvents of the dissolubility of coating fluid of the charge transport layer in the resin glue situation of general formula (1) and the stability of coating fluid, can enumerate tetrahydrofuran, toluene, dimethylbenzene, 1, 4-dioxane, methyl isobutyl ketone, methylene chloride, 1, 2-ethylene dichloride equal solvent.Even if not necessarily use the solvent of halogen-containing element, also can make good coating fluid.
Charge transport material, with respect to the blending ratio of resin glue, is preferably 10 to 500 mass parts with respect to resin glue 100 mass parts charge transport materials, more preferably 20 to 150 mass parts.
The thickness of charge transport layer is according to characteristic and the blending ratio etc. of the characteristic of charge transport material, resin glue and different, but is preferably 5 to 40 μ m, more preferably 10 to 35 μ m.
In charge transport layer, can add antioxidant, electronic conductor, stabilizing agent etc.For antioxidant, can be the antioxidant of recording in TOHKEMY 2000-305291, for electronic conductor, can be the middle electronic conductors of recording such as Japanese kokai publication sho 50-137543.
In addition, in charge transport layer, also can add as required levelling agent.As the levelling agent that can share in charge transport layer, can use the silicone oil such as dimethyl silicon oil, methyl phenyl silicone oil, have polymkeric substance or the oligomer of perfluoroalkyl at side chain, its use amount is that 0 to 1 mass parts left and right is suitable with respect to the resin glue of 100 mass parts.
The electrostatic latent image forming on Organophotoreceptor is development by developing as toner image.Can be crushed toner for the toner developing, can be also polymerization toner, but consider the polymerization toner of preferably making by polymerization from the viewpoint that obtains stable size-grade distribution.
So-called polymerization toner, refers to by toner and uses the generation of resin of cementing agent and toner to be shaped as the polymerization of starting monomer of resin glue and the toner forming by follow-up chemical treatment as required.More particularly, refer to through the polyreaction such as suspension polymerization, emulsion polymerization and the toner forming in the intergranular fusion process of carrying out thereafter as required.
The volume average particle size of toner, above-mentioned 50% particle volume diameter (Dv50) is preferably 2 to 9 μ m, more preferably 3 to 7 μ m.By being made as this mean grain size, can improve resolution.And then, by with the combination of above-mentioned mean grain size, can in becoming small particle size toner, reduce the amount of the toner of fine particle size, can improve for a long time dot image repeatability, form good, the stable image of distinctiveness.
Toner can be monocomponent toner, can be also two-component developing agent.
While use as monocomponent toner, can enumerate non-magnetic mono-component developer or in toner, contain the magnetic single component developer of the magnetic-particle of 0.1 to 0.5 about μ m, these all can use.
In addition, can mix as two-component developing agent and use with carrier.In this case, as the magnetic-particle of carrier, can use the metals such as iron, ferrite, magnetic iron ore, the materials such as the alloy of the metals such as these metals and aluminium, lead.Particularly preferably ferrite particle.Above-mentioned magnetic-particle preferably its volume average particle size is 15 to 100 μ m, more preferably 25 to 80 μ m.
The volume average particle size of carrier can be measured by the laser diffraction formula particle size distribution device " HELOS " (manufacture of SYMPATEC company) that possesses wet type dispersion machine typically.
The preferred magnetic-particle of carrier is further by resin-coated carrier or make magnetic-particle be dispersed in the so-called resin dispersion type carrier in resin.As the resin composition of coating use, can use such as ethylene series resin, phenylethylene resin series, Styrene And Chloroalkyl Acrylates is that resin, silicon-type resin, ester are resin or fluoropolymer system resin etc.In addition,, as the resin for forming resin dispersion type carrier, can use such as Styrene And Chloroalkyl Acrylates is resin, vibrin, fluorine resin, phenolics etc.
Secondly, the image processing system that has used Organophotoreceptor of the present invention is described.
Image processing system 1 shown in Fig. 1 is the image processing system of digital mode, by image reading unit A, image processing part B, image forming part C, form as the transfer printing part transport unit D of transfer printing part conveyer.
Be provided with the auto document supply unit of automatic transmission original copy on the top of image reading unit A, the original copy loading in original copy mounting table 11 is separated transmission one by one by original copy transfer roller 12, carries out reading of image reading position 13a.The original copy that original copy reads after end is discharged on original copy paper discharge tray 14 by original copy transfer roller 12.
The image of the original copy while on the other hand, being placed on contact glass 13 reads by the movement that is v/2 to unidirectional speed of reading action and the 2nd mirror unit 16 (it is made up of the 2nd mirror and the 3rd mirror that form V word shape on position) of the speed v of the 1st mirror unit 15 (it is made up of the illuminating lamp and the 1st mirror that form scanning optics).
The image reading is by the sensitive surface imaging at the imaging apparatus CCD as linear sensor after projecting lens 17.The wire optical image of imaging on imaging apparatus CCD carries out A/D conversion after being become electric signal (luminance signal) by opto-electronic conversion successively, in image processing part B, implement after the processing such as concentration conversion, filtering processing, view data is temporarily stored in storer.
In image forming part C, as image formation unit, dispose as picture and support the drum type photoreceptor 21 of body, and its periphery by the arranged in order of action separately make the charged charged elements of this photoreceptor 21 (charged operation) 22, the potentiometric detection unit 220 that detects the surface potential of charged photoreceptor, developing cell (developing procedure) 23, as the cleaning device (cleaning process) 26 of the transfer printing conveyor-belt apparatus 45 of transfer printing unit (transfer printing process), photoreceptor 21 and as light the PCL (being with in advance electric light) 27 except electric unit (light is except electrician's order).In addition be provided with, the reflection density detecting unit 222 of the reflection density for being determined at the image patch (パ Star チ picture) developing on photoreceptor 21 in the downstream of developing cell 23.Photoreceptor 21 is driven in rotation in illustrated clockwise direction.
Utilize charged elements 22 that the photoreceptor 21 of rotation is brought after identical electricity, by the exposure optical system as picture exposing unit (as exposure process) 30, the picture signal based on recalling from the storer of image processing part B looks like exposure.As writing unit as the exposure optical system of exposing unit 30, take not shown laser diode as illuminating source, after the polygonal mirror 31 of over-rotation, f θ lens 34, cylindrical lens 35, light path is reflected mirror 32 and bends, carry out main sweep, photoreceptor 21 is looked like to exposure in the position of Ao, form electrostatic latent image by the rotation (subscan) of photoreceptor 21.In one example of present embodiment, word segment is exposed, form electrostatic latent image.
In image processing system of the present invention, form electrostatic latent image on photoreceptor time, be preferably that 350 to 800nm semiconductor laser or light emitting diode uses as picture exposure light source using oscillation wavelength.Use these as exposure light source, by the exposure station diameter control of the main scanning direction writing at 10 to 100 μ m, on Organophotoreceptor, carry out digit explosure, can obtain thus the electrophotographic image of the above high resolution to 2500dpi of 400dpi (dpi: every 2.54cm counts).
So-called exposure station diameter, the 1/e that to refer to along the intensity of this exposing light beam be peak intensity
2the length (Ld: length is measured at maximum position) of the exposing light beam of the main scanning direction in above region.
As light beam used, have and applied the scanning optics of semiconductor laser and the solid state scanning instrument of LED etc., for light intensity distributions, there are Gaussian distribution and Lorentz distribution etc., with the 1/e of peak intensity separately
2above region is exposure station diameter.
Electrostatic latent image on photoreceptor 21 utilizes developing cell 23 to carry out discharged-area development, form on the surface of photoreceptor 21 can video toner image.In image forming method of the present invention, preferably use polymerization toner for the developer of this developing cell.By the polymerization toner of shape and even particle size distribution and Organophotoreceptor of the present invention are share, can obtain the better electrophotographic image of distinctiveness.
In transfer printing part transport unit D, below image formation unit, be provided with as the paper supply unit 41 (A) of transfer printing part storage unit of transfer printing part P of depositing different size, 41 (B), 41 (C), and be provided with the manual feed unit 42 that carries out manual feed in side, the transfer printing part P of any selection from these unit is transmitted along transmitting road 40 by guide roller 43, after temporarily stopping by the inclination to the transfer printing part P transmitting and a pair of paper feeding registration roller 44 transfer printing part P that skew is revised, carry out paper feeding again, led and transmitted road 40, transfer printing preliminary roller 43a, paper path 46 and enter guide plate 47, transfer position Bo by the transfer printing utmost point 24 with separate the transfer printing travelling belt 454 of the utmost point 25 at transfer printing conveyor-belt apparatus 45 on the toner image that transmits on photoreceptor 21 of mounting be transferred on transfer printing part P simultaneously, this transfer printing part P is from 21 separation of photoreceptor, be sent to fixation unit 50 by transfer printing conveyor-belt apparatus 45.
The one-sided state that carries out image formation at transfer printing part has more than been described, in the situation of double-sided copying, ADF switching member 170 switches, and transfer printing part guide part 177 is open, transmits transfer printing part P along dotted arrow direction.
And then, below transfer printing part P is sent under the effect of delivery unit 178, making it switchback by transfer printing part inversion portion 179, the rearward end of transfer printing part P becomes leading section, is sent in double-sided copying paper feed unit 130.
Transfer printing part P utilizes the transmission guiding element 131 of being located at double-sided copying paper supply unit 130 to move to paper feeding direction,, by transfer printing part P paper feeding again transfer printing part P is led and transmits road 40 with paper-feed roll 132.
Again transmit transfer printing part P to photoreceptor 21 directions as described above, at the back side transfer printing toner image of transfer printing part P, with after fixation unit 50 photographic fixing, ADF is to paper discharge tray 64.
As image processing system of the present invention, the above-mentioned constitutive requirements such as photoreceptor and developer, clearer can be formed in combination as handle box one, this unit can freely be formed with respect to apparatus main body with loading and unloading.In addition, also can by charged device, as in exposer, developer, transfer printing or separation vessel and clearer one of at least together with photoreceptor one support and form handle box, make the single unit that can freely be loaded and unloaded on device body, the pilot units such as the guide rail of operative installations body form the formation of freely loading and unloading.
Fig. 2 is the section constitution figure that represents the color image forming device of an embodiment of the present invention.
This color image forming device is called as tandem type color image forming device, by 4 groups of image forming parts (image formation unit) 10Y, 10M, 10C, 10Bk, banded middle transfer body unit 7, paper feeding delivery unit 21 and fixation unit 24 form for no reason.Dispose original image reading device SC on the top of the body A of image processing system.
Forming the image forming part 10Y of yellow image has: be disposed at charged elements (charged operation) 2Y, exposing unit (exposure process) 3Y around of drum type photoreceptor 1Y, developing cell (developing procedure) 4Y that support body as the 1st image, primary transfer roller 5Y, cleaning unit 6Y as primary transfer unit (primary transfer operation).Forming the image forming part 10M of magenta color image has: support drum type photoreceptor 1M, charged elements 2M, exposing unit 3M, the developing cell 4M of body, primary transfer roller 5M, cleaning unit 6M as primary transfer unit as the 1st image.Forming the image forming part 10C of cyan image has: support drum type photoreceptor 1C, charged elements 2C, exposing unit 3C, the developing cell 4C of body, primary transfer roller 5C, cleaning unit 6C as primary transfer unit as the 1st image.Forming the image forming part 10Bk of black image has: support drum type photoreceptor 1Bk, charged elements 2Bk, exposing unit 3Bk, the developing cell 4Bk of body, primary transfer roller 5Bk, cleaning unit 6Bk as primary transfer unit as the 1st image.
4 groups of image formation unit 10Y, 10M, 10C, 10Bk, centered by photosensitive drums 1Y, 1M, 1C, 1Bk, are made up of the charged elements 2Y rotating, 2M, 2C, 2Bk, developing cell 4Y, 4M, 4C, 4Bk and clean photosensitive drums 1Y, 1M as exposing unit 3Y, 3M, 3C, 3Bk, rotation, cleaning unit 5Y, the 5M of 1C, 1Bk, 5C, 5Bk.
The color difference of the toner image that image formation unit 10Y, 10M, 10C, 10Bk just form respectively on photoreceptor 1Y, 1M, 1C, 1Bk, but form identically, be elaborated as an example of image formation unit 10Y example.
Charged elements 2Y is the unit of photosensitive drums 1Y being given to same potential, in present embodiment, photosensitive drums 1Y is used to the charged device 2Y of corona discharge type.
To expose, form the unit corresponding to the electrostatic latent image of yellow image based on picture signal (yellow) on the photosensitive drums 1Y that has been given same potential by charged device 2Y as exposing unit 3Y, as this exposing unit 3Y, can use by the axial direction at photosensitive drums 1Y, light-emitting component being arranged in to the LED of array-like and exposing unit or the laser optical system etc. that image-forming component (trade name: SELFOC Lens) forms.
As image processing system, the above-mentioned constitutive requirements such as photoreceptor and developer, clearer can be formed in combination as handle box (image formation unit) one, and this image formation unit can freely be formed with respect to apparatus main body with loading and unloading.In addition, also can by charged device, as in exposer, developer, transfer printing or separation vessel and clearer one of at least together with photoreceptor one support and form handle box (image formation unit), make the single image forming unit that can freely be loaded and unloaded on apparatus main body, the pilot units such as the guide rail of operative installations body form the formation of freely loading and unloading.Herein, so-called " one support ", refers in the time of handling handle box, can carry out installation or removal as 1 block using process cartridge unit.
For no reason conduct the 2nd image that banded middle transfer body unit 7 has a semiconduction ring-band shape supports the banded middle transfer body 70 for no reason of body, describedly quotes body 70 in the middle of for no reason banded and is wound onto on multiple rollers and is supported rotationally.
The each color image being formed by image formation unit 10Y, 10M, 10C, 10Bk is successively transferred to by primary transfer roller 5Y, 5M, 5C, 5Bk as primary transfer unit on the banded middle transfer body 70 for no reason of rotation, the coloured image that formation will be synthetic.Such as, the transfer printing part P as transfer printing part (support the supporter of the final image after photographic fixing: common paper, slide etc.) leaving in paper feeding cassette 20 is transmitted by paper feed unit 21, through multiple intermediate calender rolls 22A, 22B, 22C, 22D, registration roller 23, be sent to the secondary transfer roller 5b as secondary transfer printing unit, on transfer printing part P, carry out secondary transfer printing and by coloured image without exception transfer printing.The transfer printing part P of transfer printing chromatic colour image utilizes fixation unit 24 to carry out photographic fixing processing, is seized on both sides by the arms and loads on the paper discharge tray 26 outside machine by exit roller 25.The transfer printing supporter of the toner image herein, middle transfer body and transfer printing part etc. being formed on photoreceptor is referred to as offset medium.
On the other hand, the secondary transfer roller 5b that is used as secondary transfer printing unit is transferred to coloured image after transfer printing part P, and the banded middle transfer body 70 for no reason that transfer printing part P curvature is separated is removed remaining toner by cleaning unit 6b.
In image formation processing, primary transfer roller 5Bk always with photoreceptor 1Bk butt.Other primary transfer roller 5Y, 5M, 5C are only in the time that coloured image forms and each self-corresponding photoreceptor 1Y, 1M, 1C butt.
In addition, be situated between and can from apparatus main body A, pull out framework 8 by supporting guide 82L, 82R.
Framework 8 by image forming part 10Y, 10M, 10C, 10Bk and for no reason banded middle transfer body unit 7 form.
Fig. 3 is the formation sectional view of the color image forming device (at least having duplicating machine or the laser beam printer of charged elements, exposing unit, multiple developing cell, transfer printing unit, cleaning unit and middle transfer body at the periphery of Organophotoreceptor) that used Organophotoreceptor of the present invention.It is moderate elastic body that banded middle transfer body 70 uses resistance.
The 1st,, be driven in rotation with the peripheral speed of regulation in the counter clockwise direction shown in arrow by the Barrate type photoreceptor of Reusability as picture organizator.
Photoreceptor 1 is processed into polarity and the current potential equally with regulation by charged elements (charged operation) 2 in rotary course, next, by not shown picture exposing unit (as exposure process) 3, be subject to image exposure, thereby the electrostatic latent image that formation is corresponding with the color component picture (colouring information) of the yellow (Y) of target coloured image, this image exposure utilization adopts the scan exposure of laser beam to use up etc. to carry out, and wherein said laser beam is modulated corresponding to the time dependent electric digital pixel signal of image information.
Then, this electrostatic latent image is the Yellow toner development that developing procedure (yellow developer) 4Y is used as the 1st color by the developing cell of yellow (Y).Now, the the 2nd to the 4th developing cell (magenta developer, cyan developer, black toner developer) 4M, 4C, the each developer of 4Bk are not worked, do not act on photoreceptor 1, and the yellow toner image of above-mentioned the 1st color is not subject to above-mentioned the 2nd impact to the 4th developer.
On photoreceptor 1, form and support the 1st color yellow toner image thereon in the process of the impression portion by between photoreceptor 1 and middle transfer body 70, utilize from primary transfer roller 5a and be applied to the electric field that the primary transfer bias voltage of middle transfer body 70 forms, by intermediate transfer (primary transfer) to the outer peripheral face of middle transfer body 70.
Complete the surface cleaned device 6a cleaning of the photoreceptor 1 of the transfer printing of the 1st color yellow toner image corresponding with middle transfer body 70.
Next similarly on middle transfer body 70, superpose successively transfer printing the 2nd color magenta toner image, the 3rd color cyan toner image, the 4th color black toner image, form the stack color toner image corresponding with target coloured image.
With the parallel bearing of the relative secondary transfer printing subtend of secondary transfer roller 5b roller 79b be configured to the state that can leave from middle transfer body 70 lower faces.
For being the polarity contrary with toner from photoreceptor 1 to the primary transfer bias voltage of middle transfer body 70 successively overlapping transfer printing the 1st to the 4th color toner image, applied by grid bias power supply.It applies voltage.
The primary transfer operation of the 1st to the 3rd color toner image from photoreceptor 1 to middle transfer body 70, secondary transfer roller 5b and middle transfer body cleaning unit 6b also can leave from middle transfer body 70.
The stack color toner image being transferred on banded middle transfer body 70 carries out as follows to the transfer printing that supports the transfer printing part P of body as the 2nd image,, secondary transfer roller 5b and middle transfer body 70 be with butt in, transfer printing part P by transfer printing part guiding element, is sent to bringing and the nip of secondary transfer roller 5b butt of middle transfer body 70 from a pair of paper feeding registration roller 23 on the opportunity of regulation.Apply secondary transfer printing bias voltage by grid bias power supply to secondary transfer roller 5b.Utilize this secondary transfer printing bias voltage, the color toner image that will superpose is from middle transfer body 70 transfer printings (secondary transfer printing) to supporting the transfer printing part P of body as the 2nd image.The transfer printing part P that has accepted toner image transfer printing is imported to fixation unit 24, carry out heat fixer.
Image processing system of the present invention is generally applicable to the electro-photography apparatus such as electrophotographic copier, laser printer, LED printer and liquid crystal photic gate formula printer, and then, also can be widely used for having applied the devices such as the display, record of Electronic Photographing Technology, light printing, plate-making and facsimile recorder.
[embodiment]
Then, illustrate in greater detail the present invention by embodiment." part " of in embodiment, using all represents mass parts.
Embodiment 1
Make as follows photoreceptor 1.
Cut is carried out in the surface of cylindrical shape aluminium support body, and preparation surface roughness Rz is the electric conductivity supporter of 1.5 μ m.
< middle layer >
Make the middle layer coating fluid of following composition.
1 part of polyamide X1010 (manufacture of Daicel Degussa Co., Ltd.)
1.1 parts of titania SMT500SAS (manufacture of TAYCA company)
20 parts of ethanol
Use sand mill as dispersion machine, carry out the dispersion of 10 hours with batch-type.
Use above-mentioned coating fluid to be coated with on supporter with dip coated method, so that be 2 μ m at 110 ℃ of thickness that are dried after 20 minutes.
< charge generation layer >
Charge generation material: 20 parts of titanyl phthalocyanine pigment (Cu-K α characteristic X-ray diffraction spectrum at least has the titanyl phthalocyanine pigment at maximum diffraction peak the position of 27.3 ° in measuring)
10 parts of polyvinyl butyral resins (#6000-C: Denki Kagaku Kogyo kabushiki manufactures)
700 parts of tert-butyl acetates
300 parts of 4-methoxyl-4-methyl-2 pentanones
Above-mentioned substance is mixed, use sand mill to disperse 10 hours, prepare charge generation layer coating fluid.This coating fluid is coated on middle layer by dip coated method, forming dry film thickness is the charge generation layer of 0.3 μ m.
< charge transport layer >
150 parts of charge transport material: CTM (following compd A)
Cementing agent: there is 300 parts of the potpourri of copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.5/0.5 that the No.1 of table 1～table 6 records (mole) of following structural unit and m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri)
6 parts of antioxidants (Irganox1010: Japanese Ciba-Geigy company manufactures)
2000 parts of solvent: toluene/tetrahydrofuran=1.5/8.5 (part)
1 part of silicone oil (KF-54: chemical company of SHIN-ETSU HANTOTAI manufactures)
Above-mentioned substance is mixed, dissolve, prepare charge transport layer coating fluid.Use dip coated method on charge generation layer, to be coated with this coating fluid, form the charge transport layer that thickness is 25 μ m at 110 ℃ after dry 60 minutes, be made into photoreceptor 1.
The weight-average molecular weight of polystyrene conversion: 230,000
The making of photoreceptor 2
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with to the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.5/0.5 that the No.2 of table 1～table 6 records (mole) with following structural unit and m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri), similarly operation, makes photoreceptor 2 in addition.
The weight-average molecular weight of polystyrene conversion: 220,000
Embodiment 3
The making of photoreceptor 3
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with to the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.95/0.05 that the No.3 of table 1～table 6 records (mole) with following structural unit and m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri), similarly operation, makes photoreceptor 3 in addition.
The weight-average molecular weight of polystyrene conversion: 210,000
The making of photoreceptor 4
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with to the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.05/0.95 that the No.4 of table 1～table 6 records (mole) with following structural unit and m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri), by more 4000 parts of the quantitative changes of solvent, similarly operation, makes photoreceptor 4 in addition.
The weight-average molecular weight of polystyrene conversion: 220,000
Embodiment 5
The making of photoreceptor 5
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with to the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.6/0.4 that the No.5 of table 1～table 6 records (mole) with following structural unit and m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri), similarly operation, makes photoreceptor 5 in addition.
The weight-average molecular weight of polystyrene conversion: 200,000
Embodiment 6
The making of photoreceptor 6
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with to the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.65/0.35 that the No.6 of table 1～table 6 records (mole) with following structural unit and m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri), similarly operation, makes photoreceptor 6 in addition.
The weight-average molecular weight of polystyrene conversion: 230,000
Embodiment 7
The making of photoreceptor 7
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with to the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.5/0.5 that the No.7 of table 1～table 6 records (mole) with following structural unit and m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri), similarly operation, makes photoreceptor 7 in addition.
The weight-average molecular weight of polystyrene conversion: 210,000
Embodiment 8
The making of photoreceptor 8
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with to the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.5/0.5 that the No.8 of table 1～table 6 records (mole) with following structural unit and m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri), similarly operation, makes photoreceptor 8 in addition.
The weight-average molecular weight of polystyrene conversion: 220,000
Embodiment 9
The making of photoreceptor 9
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with to the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.6/0.4 that the No.9 of table 1～table 6 records (mole) with following structural unit and m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri), similarly operation, makes photoreceptor 9 in addition.
The weight-average molecular weight of polystyrene conversion: 230,000
Embodiment 10
The making of photoreceptor 10
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with to the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.5/0.5 that the No.10 of table 1～table 6 records (mole) with following structural unit and m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri), similarly operation, makes photoreceptor 10 in addition.
The weight-average molecular weight of polystyrene conversion: 220,000
The making of photoreceptor 11
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with to the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.6/0.4 that the No.11 of table 1～table 6 records (mole) with following structural unit and m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri), similarly operation, makes photoreceptor 11 in addition.
The weight-average molecular weight of polystyrene conversion: 220,000
The making of photoreceptor 12
In the making of photoreceptor 1, by the cementing agent of charge transport layer replace with the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.6/0.4 that the No.12 of table 1～table 6 records (mole) with following structural unit, with dicarboxylic acid compound=diphenyl ether-4,4 '-dioctyl phthalate (a3)=1.0 (mole) copolymerization), similarly operation, makes photoreceptor 12 in addition.
The weight-average molecular weight of polystyrene conversion: 210,000
The making of photoreceptor 13
In the making of photoreceptor 1, by the cementing agent of charge transport layer replace with the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.5/0.5 that the No.13 of table 1～table 6 records (mole) with following structural unit, with dicarboxylic acid compound=diphenyl ether-4,4 '-dioctyl phthalate (a3)=1.0 (mole) copolymerization), similarly operation, makes photoreceptor 13 in addition.
The weight-average molecular weight of polystyrene conversion: 240,000
The making of photoreceptor 14
In the making of photoreceptor 1, by the cementing agent of charge transport layer replace with the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.4/0.6 that the No.14 of table 1～table 6 records (mole) with following structural unit, with dicarboxylic acid compound=diphenyl ether-4, the copolymerization of 4 '-dioctyl phthalate (a3)), similarly operation, makes photoreceptor 14 in addition.
The weight-average molecular weight of polystyrene conversion: 230,000
The making of photoreceptor 15
In the making of photoreceptor 1, by the cementing agent of charge transport layer replace with the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.5/0.5 that the No.15 of table 1～table 6 records (mole) with following structural unit, with dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)/diphenyl ether-4,4 '-dioctyl phthalate (a3)=0.333/0.333/0.333 (mole) the copolymerization of potpourri), similarly operation, makes photoreceptor 15 in addition.
The weight-average molecular weight of polystyrene conversion: 220,000
Embodiment 16
The making of photoreceptor 16
In the making of photoreceptor 1, by the cementing agent of charge transport layer replace with the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.5/0.5 that the No.16 of table 1～table 6 records (mole) with following structural unit, with dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)/2,6-naphthalenedicarboxylic acid (a4)=0.4/0.4/0.2 (mole) the copolymerization of potpourri), similarly operation, makes photoreceptor 16 in addition.
The weight-average molecular weight of polystyrene conversion: 240,000
The making of photoreceptor 17
In the making of photoreceptor 1, by the cementing agent of charge transport layer replace with the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.6/0.4 that the No.17 of table 1～table 6 records (mole) with following structural unit, with dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)/hexane diacid (a5)=0.333/0.333/0.333 (mole) the copolymerization of potpourri), similarly operation, makes photoreceptor 17 in addition.
The weight-average molecular weight of polystyrene conversion: 250,000
Embodiment 18
The making of photoreceptor 18
In the making of photoreceptor 1, by the cementing agent of charge transport layer replace with the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.5/0.5 that the No.18 of table 1～table 6 records (mole) with following structural unit, with dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri), similarly operation, makes photoreceptor 18 in addition.
The weight-average molecular weight of polystyrene conversion: 220,000
Embodiment 19
The making of photoreceptor 19
In the making of photoreceptor 1, by the cementing agent of charge transport layer replace with the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.4/0.6 that the No.19 of table 1～table 6 records (mole) with following structural unit, with dicarboxylic acid compound=diphenyl ether-4, the copolymerization of 4 '-dioctyl phthalate (a3)), similarly operation, makes photoreceptor 19 in addition.
The weight-average molecular weight of polystyrene conversion: 220,000
The making of photoreceptor 20
In the making of photoreceptor 1, by the cementing agent of charge transport layer replace with the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.7/0.3 that the No.20 of table 1～table 6 records (mole) with following structural unit, with dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri), similarly operation, makes photoreceptor 20 in addition.
The weight-average molecular weight of polystyrene conversion: 230,000
The making of photoreceptor 21 (comparative example 1)
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with to the copolymerization polyarylate resin with following structural unit (as the No.21 of table 1～table 6 records, remove the 1st glycol, be the 2nd glycol 1.0 (mole) with m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri), solvent is changed to the tetrahydrofuran of 4000 parts, similarly operation, makes photoreceptor 21 in addition.
The weight-average molecular weight of polystyrene conversion: 200,000
The making of photoreceptor 22 (comparative example 2)
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with to the polycarbonate (Z300: gas chemical company of Mitsubishi manufactures) of following structural unit, similarly operation, makes photoreceptor 22 in addition.
The making of photoreceptor 23
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with to the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.03/0.97 that the No.23 of table 1～table 6 records (mole) with following structural unit and dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri), solvent is changed to the tetrahydrofuran of 4000 parts, similarly operation, makes photoreceptor 23 in addition.
The weight-average molecular weight of polystyrene conversion: 220,000
The making of photoreceptor 24
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with to the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.97/0.03 that the No.23 of table 1～table 6 records (mole) with following structural unit and dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri), similarly operation, makes photoreceptor 24 in addition.
The weight-average molecular weight of polystyrene conversion: 220,000
The making of photoreceptor 25
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with to the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.03/0.97 that the No.25 of table 1～table 6 records (mole) with following structural unit and dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri), similarly operation, makes photoreceptor 25 in addition.
The weight-average molecular weight of polystyrene conversion: 230,000
The making of photoreceptor 26
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with to the potpourri of the copolymerization polyarylate resin (the 1st glycol/2nd glycol=0.97/0.03 that the No.26 of table 1～table 6 records (mole) with following structural unit and dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole) the copolymerization of potpourri), similarly operation, makes photoreceptor 26 in addition.
The weight-average molecular weight of polystyrene conversion: 230,000
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
[table 6]
(evaluation of photoreceptor)
As above the photoreceptor obtaining is used to the commercially available full color compounding machine bizhub PRO C6500 that has Fig. 2 and form substantially, and (Konica Minolta Business Technology Co manufactures; Use the exposure light of the semiconductor laser of 600dpi, 780nm) evaluate.Above-mentioned full color compounding machine is owing to having 4 groups of image formation units, for example, so the unified photoreceptor (,, in the situation of photoreceptor 1, preparing 4 photoreceptors 1) with one species of the photoreceptor of each image formation unit is evaluated.In each evaluation, under 30 ℃, the condition of 80%RH, the A4 image of Y, M, C, Bk lettering rate 2.5% of all kinds is imprinted on neutralized paper A4 paper, prints 100,000, carry out resistance to printing test, thereafter, under each following different environmental baseline, evaluate.
(potential property)
In above-mentioned evaluation, carry out 100,000 printings, use the transformation apparatus that is provided with surface potential meter in the position of the developing cell of bizhub PRO C6500 to evaluate the surface potential after initial stage and 100,000.
Measure surface potential VL (V), the surface potential VH (V) of unexposed portion of exposure portion, utilize the absolute value of variation to evaluate potential change, Δ VL (V), the Δ VH (V) after initial stage and 100,000.
Photoreceptor belt electric potential (unexposed portion current potential): be-700V by initial stage potential setting.
(evaluation of coloured image)
Under 30 ℃, the environmental baseline of 80%RH, printing 100,000 carries out after resistance to printing test, under 20 ℃, the environmental baseline of 50%RH, place 12 hours, make 4 groups of image formation unit work of full color compounding machine bizhub PRO C6500, the half tone image that comprises human face photo is printed on A4 paper, evaluates with following benchmark.
A: reproduce smoothly the coloured image of half toning, do not find to produce image blurring and image inequality
B: part produces image blurring or image is uneven on the coloured image of half toning, but and not obvious, reproduce smoothly on the whole (no problem in practicality)
C: in the coloured image of half toning, part comprise significantly image blurring, image is uneven, there is no repeatability (having problem in practicality)
D: whole of the coloured image of half toning be upper produce significantly image blurring or image is uneven (in practicality, having problem).
(losing quantity of photoreceptor)
In above-mentioned evaluation, carry out 100,000 printings, use the film thickness difference after initial stage thickness and 100,000 to evaluate.For the thickness of photographic layer, measure homogeneous thickness parts (because the thickness at the two ends of photoreceptor is easily inhomogeneous, so at least remove two ends 5cm), the thickness using its mean value as photographic layer with being intended to 10 places.Determining film thickness device uses the determining film thickness device EDDY560C (manufacture of HELMUTFISCHER GMBTE CO company) of vortex flow mode to measure, and calculates apart from initial stage thickness (27.3 μ losing quantity m).
(solvent solubility, coating fluid keeping quality)
The cementing agent of the charge transport layer to photoreceptor 1 to 26, evaluates the solvent solubility of coating fluid and the keeping quality of coating fluid.For solvent solubility, make coating fluid under following 3 condition time, evaluate the dissolubility of resin glue etc.
Condition 1:
150 parts of charge transport material: CTM (above-claimed cpd A)
Cementing agent: 300 parts of the cementing agents of the charge transport layer of each photoreceptor
6 parts of antioxidants (Irganox1010: Japanese Ciba-Geigy company manufactures)
2000 parts of toluene/tetrahydrofuran=1.5/8.5 (portion)
1 part of silicone oil (KF-54: chemical company of SHIN-ETSU HANTOTAI manufactures)
Condition 2:
150 parts of charge transport material: CTM (above-claimed cpd A)
Cementing agent: 300 parts of the cementing agents of the charge transport layer of each photoreceptor
6 parts of antioxidants (Irganox1010: Japanese Ciba-Geigy company manufactures)
2000 parts of tetrahydrofurans
1 part of silicone oil (KF-54: chemical company of SHIN-ETSU HANTOTAI manufactures)
Condition 3:
150 parts of charge transport material: CTM (above-claimed cpd A)
Cementing agent: 300 parts of the cementing agents of the charge transport layer of each photoreceptor
6 parts of antioxidants (Irganox1010: Japanese Ciba-Geigy company manufactures)
Methyl isobutyl ketone/dimethylbenzene/tetrahydrofuran=3/,3/4 2000 part
1 part of silicone oil (KF-54: chemical company of SHIN-ETSU HANTOTAI manufactures)
For coating fluid keeping quality, the coating fluid of condition 1, condition 2, condition 3 is carried out preserving for 5 ℃, 48 hours (low temperature preservations) and 30 ℃, 48 hours and preserves (High temperature storage), evaluate have after each coating fluid preservation unchanged.
The metewand of solvent solubility
A: easily uniform dissolution is completely no problem.
B: it is slightly difficult to dissolve, and is the level of qualified lower limit.
C a: part is not dissolved, produces precipitation, but after dilution, just can dissolve a little.But because the concentration of coating fluid is slightly low, so be disadvantageous for the manufacture of photoreceptor.
D: solubleness is obviously not enough, needs 5 times of above dilutions to dissolve, and does not have practicality.
The conservatory metewand of coating fluid
A: completely no problem.
B: low temperature has the tendency of gelation slightly while preservation, but is spendable level.
C: separate out when low temperature is preserved.
D: have separating out of defective level under any preservation condition.
Evaluation result is summarized in following table 7.
As shown in Table 7, in photoreceptor of the present invention, derive from the structure (R of the 1st glycol
1) with derive from the structure (R of the 2nd glycol
2) mol ratio (R
1/ R
2) be that 5/95 to 95/5 photoreceptor 1 to 20 has obtained than having the better result of practicality in each assessment item, but greatly deteriorated in the photoreceptor 21 of comparative example at least one project in the evaluation of current potential evaluation, coloured image, solvent solubility, coating fluid keeping quality, the photoreceptor losing quantity of photoreceptor 22 is large, potential change after 100000 is also large, the evaluation of coloured image is deteriorated, and result is existing problems aspect practicality all.In addition, although be the structure (R that photoreceptor of the present invention derives from the 1st glycol
1) with derive from the structure (R of the 2nd glycol
2) mol ratio (R
1/ R
2) at 5/95 to 95/5 extraneous photoreceptor 23 to 26, although in the evaluation of current potential evaluation, coloured image, can guarantee sufficient practicality, slightly poorer than photoreceptor 1 to 20 aspect solvent solubility, coating fluid keeping quality.
Claims (5)
1. an Electrophtography photosensor has photographic layer on electric conductivity supporter, and photographic layer contains (1) resin glue of structural unit that represents that has general formula,
R in general formula (1)
3by dicarboxylic acid R
3(COOH)
2derivative divalent organic group, R
1by the 1st glycol R
1(OH)
2derivative divalent group, R
2by the 2nd glycol R
2(OH)
2derivative divalent group,
R
2be and R
1the different divalent groups with more than 2 aromatic rings,
Described Electrophtography photosensor is characterised in that, the 1st glycol R
1(OH)
2for be selected from general formula (2a) and (2b) in more than one diol compound,
In general formula (2a), general formula (2b), R is alkyl, and whole R can be the same or different;
The 2nd glycol R
2(OH)
2for being selected from more than one the diol compound in following general formula (3a)～general formula (3c),
In general formula (3a)～general formula (3c), R is alkyl,
R and R can form other ring by bonding, and whole R can be the same or different.
2. an Electrophtography photosensor has photographic layer on electric conductivity supporter, and photographic layer contains (1) resin glue of structural unit that represents that has general formula,
R in general formula (1)
3by dicarboxylic acid R
3(COOH)
2derivative divalent organic group, R
1by the 1st glycol R
1(OH)
2derivative divalent group, R
2by the 2nd glycol R
2(OH)
2derivative divalent group,
R
2be and R
1the different divalent groups with more than 2 aromatic rings,
Described Electrophtography photosensor is characterised in that, the 1st glycol R
1(OH)
2for be selected from general formula (2a) and (2b) in more than one diol compound,
In general formula (2a), general formula (2b), R is alkyl, and whole R can be the same or different;
The 2nd glycol R
2(OH)
2for be selected from following general formula (3d) and (3e) in more than one aromatic diol compound,
In general formula (3d), (3e), R is alkyl,
R and R can form other ring by bonding, and whole R can be identical functional group, can be also different functional groups.
3. Electrophtography photosensor as claimed in claim 1 or 2, is characterized in that, the structure R1 that derives from the 1st glycol is 5/95～95/5 with the mol ratio R1/R2 of the structure R2 that derives from the 2nd glycol.
4. an image processing system, at least has charged elements, exposing unit and developing cell at the periphery of Electrophtography photosensor, repeatedly carries out image formation, it is characterized in that, this Electrophtography photosensor is the Electrophtography photosensor described in claim 1 or 2.
5. a handle box, is characterized in that, integrally there is the Electrophtography photosensor described in claim 1 or 2 and be selected from charged elements, cleaning unit, as at least one unit in exposing unit and developing cell, and can be loaded and unloaded on image processing system.
Applications Claiming Priority (2)
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|---|---|---|---|
| JP2009149681A JP2011007914A (en) | 2009-06-24 | 2009-06-24 | Electrophotographic photoreceptor, image forming apparatus, and process cartridge |
| JP2009-149681 | 2009-06-24 |
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| CN101930185B true CN101930185B (en) | 2014-05-14 |
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| CN (1) | CN101930185B (en) |
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| JP6408772B2 (en) * | 2014-03-14 | 2018-10-17 | ユニチカ株式会社 | Varnish and production method thereof |
| JP6380124B2 (en) * | 2015-01-22 | 2018-08-29 | 三菱ケミカル株式会社 | Electrophotographic photoreceptor, image forming apparatus, and polyester resin |
| JP6387974B2 (en) * | 2016-01-28 | 2018-09-12 | 京セラドキュメントソリューションズ株式会社 | Electrophotographic photoreceptor |
| JP6833549B2 (en) | 2016-02-19 | 2021-02-24 | キヤノン株式会社 | Electrophotographic photosensitive members, process cartridges and electrophotographic equipment |
| JP6664234B2 (en) | 2016-02-19 | 2020-03-13 | キヤノン株式会社 | Electrophotographic photoreceptor, process cartridge and electrophotographic apparatus |
| CN109415499A (en) * | 2016-05-27 | 2019-03-01 | 尤尼吉可株式会社 | Polyarylate resin, the film and laminated body formed by polyarylate resin |
| EP3249471B1 (en) * | 2016-05-27 | 2019-03-20 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
| WO2018100813A1 (en) * | 2016-11-30 | 2018-06-07 | 京セラドキュメントソリューションズ株式会社 | Electrophotographic photoreceptor |
| JP6949619B2 (en) * | 2017-08-18 | 2021-10-13 | キヤノン株式会社 | Electrophotographic photosensitive members, process cartridges and electrophotographic equipment |
| JP6995583B2 (en) * | 2017-11-24 | 2022-01-14 | キヤノン株式会社 | Electrophotographic photosensitive members, process cartridges and electrophotographic equipment |
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| CN1605944A (en) * | 2003-10-08 | 2005-04-13 | 富士电机影像器材有限公司 | Electrophotographic photoconductor and methods therefor |
| CN1742236A (en) * | 2002-12-06 | 2006-03-01 | 三菱化学株式会社 | electrophotographic photoreceptor |
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| JP3397592B2 (en) * | 1996-07-29 | 2003-04-14 | キヤノン株式会社 | Electrophotographic photoreceptor, process cartridge and electrophotographic apparatus |
| JPH10123741A (en) * | 1996-10-16 | 1998-05-15 | Canon Inc | Electrophotographic photoreceptor, process cartridge and electrophotographic device |
| JP3402960B2 (en) * | 1996-10-25 | 2003-05-06 | キヤノン株式会社 | Electrophotographic photoreceptor, process cartridge and electrophotographic apparatus |
| JP3740310B2 (en) * | 1999-02-04 | 2006-02-01 | キヤノン株式会社 | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
| JP3679641B2 (en) * | 1999-02-05 | 2005-08-03 | キヤノン株式会社 | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
| JP4228511B2 (en) * | 2000-04-04 | 2009-02-25 | 三菱化学株式会社 | Electrophotographic photoreceptor |
| JP2003195540A (en) * | 2001-12-27 | 2003-07-09 | Canon Inc | Manufacturing method for electrophotographic photoreceptor, electrophotographic photoreceptor, process cartridge and electrophotographic device |
| JP2004093862A (en) * | 2002-08-30 | 2004-03-25 | Canon Inc | Electrophotographic device, electrophotographic sensitive body and process cartridge |
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| CN1742236A (en) * | 2002-12-06 | 2006-03-01 | 三菱化学株式会社 | electrophotographic photoreceptor |
| CN1605944A (en) * | 2003-10-08 | 2005-04-13 | 富士电机影像器材有限公司 | Electrophotographic photoconductor and methods therefor |
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