CN101930185A - Electrophtography photosensor, image processing system and handle box - Google Patents
Electrophtography photosensor, image processing system and handle box Download PDFInfo
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- CN101930185A CN101930185A CN 201010208873 CN201010208873A CN101930185A CN 101930185 A CN101930185 A CN 101930185A CN 201010208873 CN201010208873 CN 201010208873 CN 201010208873 A CN201010208873 A CN 201010208873A CN 101930185 A CN101930185 A CN 101930185A
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- photoreceptor
- glycol
- electrophtography photosensor
- image
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Images
Landscapes
- Photoreceptors In Electrophotography (AREA)
Abstract
The present invention relates to Electrophtography photosensor, image processing system and handle box.The object of the present invention is to provide a kind of high performance electronic photosensitive body, it has solved the problem of using the Electrophtography photosensor of existing polyarylate, promptly, dissolubility, electrology characteristic (rest potential, bright current potential etc.) in the coating fluid solvent when improving the abrasion performance characteristic, have been improved, has high-durability, even for using the also sustainable preferable image that obtains repeatedly.In addition, the object of the present invention is to provide by using above-mentioned Electrophtography photosensor to realize the image processing system and the image processing system handle box of the high reliability of small-sized and energy high speed printing.Described Electrophtography photosensor has photographic layer on the electric conductivity supporter, it is characterized in that, this photographic layer contains the resin glue with specific structure unit.
Description
Technical field
The present invention relates to have high-durability and realized the Electrophtography photosensor (being designated hereinafter simply as photoreceptor) of long-term high image qualityization.In addition, relate to image processing system and the image processing system processing unit that has used these photoreceptors.
Background technology
Be applied in duplicating machine, facsimile recorder, the laser printer etc. use 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 the various processes such as cleaning surfaces of toner image to transfer printing, photographic fixing and the Electrophtography photosensor of image holding body (transfer printings of common paper etc.).
Yet, for this Electrophtography photosensor, being generally known at present be that the electric conductivity supporter is provided with Electrophtography photosensor based on the photoconductive layer of selenium or selenium alloy, makes zinc paste etc. inorganic is that photoconductive material is dispersed in the Electrophtography photosensor in the cementing agent and has used Electrophtography photosensor of amorphous layer material etc., in recent years, the degree of freedom height that Organophotoreceptor is low owing to cost, photoreceptor designs, non-pollution etc. are widely used.
As this Organophotoreceptor, photoreceptor excellence aspect 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 film forming in order to ensure this charge transport layer, resin glue and charge transport material are share, but the charge transport layer that is formed by resin glues such as low molecular charge transport material and polycarbonate is generally soft, can enumerate as shortcoming:when in electrofax is handled, using repeatedly because of toning system, due to the cleaning systems at the mechanical load of photosensitive surface and the low shortcoming of such abrasion performance of wearing and tearing easily.In fact, owing to the wearing and tearing of photoreceptor present harmful effects such as sensitivity deterioration, charging property reduction, produce that image color reduces, the dirty (Di in end Ji れ) etc. abnormal image, photoreceptor reaches the life-span sometimes.
At such problem, the technological development that carried out improving resin glue, can form the higher charge transport layer of hardness.For example, as the resin glue that improves photoreceptor abrasion performance characteristic, the polycarbonate of bisphenol Z type is disclosed in the patent documentation 1.
But in the time of will using this polycarbonate in electrofax is at a high speed handled, 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, disclose the technology of commercially available polyarylate (aromatic polyester) resin of commodity in use " U-Polymer " by name as the Electrophtography photosensor of cementing agent in patent documentation 2, wherein compared with polycarbonate, it is excellent especially to demonstrate sensitivity.In addition, disclose a kind of Electrophtography photosensor in the patent documentation 3, it is characterized in that, contained polyarylate (aromatic polyester) multipolymer of the structure of having used tetramethyl Bisphenol F and bisphenol-A in the bisphenol component.And then, a kind of Electrophtography photosensor is disclosed in the patent documentation 4, it is characterized in that, contain and used the polyarylate (aromatic polyester) of bisphenol-c as bis-phenol.
But,, exist in the shortcoming of the stable bad of dissolubility in the coating solvent of photographic layer and solution or their electrical specification deterioration according to the technology of using these aromatic polyesters as the photographic layer cementing agent.The technology of particularly above-mentioned patent documentation 2 records, though seeing aspect abrasion performance, the sensitivity that some improve, because the poor stability of its coating fluid, so can not be coated with manufacturing, or promptly allow to coating manufacturing, sliding is also bad.In addition, the technology of above-mentioned patent documentation 3 records is seen raising though compare with existing polycarbonate aspect abrasion performance, compares with polycarbonate aspect sliding and can't see superiority.And then, the technology of above-mentioned patent documentation 4 records remains aspect abrasion performance to compare with existing polycarbonate and sees raising, prolongs such advantage though have the life-span of photoreceptor, but it is aspect electrical specification, particularly response, poorer than the situation of using polycarbonate resin.Skeleton for polyarylate changes, and is also on the books in the 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 electronic photosensitive body, it has solved the problem of the Electrophtography photosensor of existing use polyarylate, promptly, when improving the abrasion performance characteristic, improve dissolubility, electrical specification (rest potential, bright current potential etc.) in the coating fluid solvent, has high-durability, even for using the also sustainable preferable image that obtains repeatedly.In addition, the object of the present invention is to provide by using above-mentioned Electrophtography photosensor to realize the image processing system and the image processing system handle box of miniaturization and high reliability that can high speed printing.
Purpose of the present invention can be reached as the resin glue of Electrophtography photosensor by using new vibrin.
The present invention and optimal way thereof are narrated.
The present invention relates to a kind of Electrophtography photosensor, it has photographic layer on the electric conductivity supporter, and wherein, photographic layer contains the resin glue of the structural unit with following general formula (1) expression.
General formula (1)
(in the general formula (1), R
1Expression has the divalent group of 3 above aromatic rings, R
2Expression and R
1Different divalent groups with 2 above aromatic rings, R
3Expression divalent organic group.)
R in the preferred formula (1)
3Be by dicarboxylic acid R
3(COOH)
2The divalent organic group, the R that derive
1Be by the 1st glycol R
1(OH)
2The divalent group, the R that derive
2Be by the 2nd glycol R
2(OH)
2The divalent group of deriving.
Preferred the 1st glycol R
1(OH)
2Be the aromatic diol compound of following general formula (2), and the 2nd glycol R
2(OH)
2Aromatic diol compound for following general formula (3).
General formula (2)
HO-φ
1-A
1-φ
2-A
2-...-A
j-1-φ
j-OH
In the general formula (2), φ
1, φ
2... φ
jExpression aromatic rings (j is the integer more than 3),
A
1, A
2... A
J-1For being selected from-CR
11R
12-,-R
13-,-O-,-group (j is the integer more than 3) in S-and the Direct Bonding.
Wherein, R
11, R
12Expression H, alkyl, allyl, aryl, alkoxy, halogen, R
11And R
12Can form ring by bonding.R
13The expression carbon number is the alkylidene more than 2.
General formula (3)
HO-φ
1-B
1-φ
2-B
2-...-B
k-1-φ
k-OH
In the general formula (3), φ
1, φ
2... φ
kExpression aromatic rings (k is the integer more than 2),
B
1, B
2... B
K-1For being selected from-CR
21R
22-,-R
23-,-O-,-S-,-SO
2-and Direct Bonding in group (k is the integer more than 2).
Wherein, R
21, R
22Expression H, alkyl, allyl, aryl, alkoxy, halogen, R
21And R
22Can form ring by bonding.R
23The expression carbon number is the alkylidene more than 2.
The 1st glycol R
1(OH)
2Be preferably more than one the diol compound that is selected from following general formula (2a) and the general formula (2b).
General formula (2a)
General formula (2b)
In the compound of general formula (2a) expression, the compound of preferred following general formula (2c) expression.
General formula (2c)
General formula (2a) is to general formula (2c), and R is the group that is selected from alkyl, allyl, the 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 that is selected among the following d1 to d5.
The 2nd glycol R
2(OH)
2Be preferably and be selected from more than one the diol compound of general formula (3a) to the 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 that is selected from alkyl, allyl, the 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 that is selected among the 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 of general formula (3d) expression, the compound of preferred following general formula (3f) expression.
General formula (3f)
General formula (3d) is to general formula (3f), and R is the group that is selected from alkyl, allyl, the 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 that is selected among the 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 the 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 more than 2 kinds that is selected from aromatic dicarboxylic acid or the 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 that periphery at Electrophtography photosensor has charged elements, exposing unit, developing cell at least, carries out the image processing system that image forms repeatedly, wherein, this Electrophtography photosensor is above-mentioned Electrophtography photosensor.
A kind of handle box, have above-mentioned at least Electrophtography photosensor integratedly and be selected from charged elements, cleaning unit, as at least one unit in exposing unit and the developing cell, and can be loaded and unloaded on image processing system.
The present invention can provide a kind of high performance electronic photosensitive body, it has improved dissolubility, the electrical specification (rest potential, bright current potential etc.) in the coating fluid solvent when making when improving the abrasion performance characteristic, has high-durability, even for using also sustainable acquisition preferable image repeatedly.
Description of drawings
Fig. 1 is the synoptic diagram that group has been gone into the function of image processing system of the present invention.
Fig. 2 is the section constitution figure that the coloured image of expression an embodiment of the present invention forms device.
Fig. 3 has been to use the coloured image of Electrophtography photosensor of the present invention to form the formation sectional view of device.
Embodiment
Below, describe the present invention in detail.
Electrophtography photosensor of the present invention has photographic layer on the electric conductivity supporter, it is characterized in that, this photographic layer contains the resin glue of structural unit of (1) expression that has general formula.
This Electrophtography photosensor, photoreceptor have high-durability and for using repeatedly image disappearance, sustainable acquisition preferable image do not take place.
Below the main composition important document that constitutes this Electrophtography photosensor is described.
Resin glue with 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)
2The preferred aromatic diol that uses general formula (2).
As the φ in the 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 all be identical substituting group, φ
1, φ
2... φ
jIn part or all can use different substituting groups.
A in the 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 all be identical substituting group, A
1, A
2... A
J-1In part or all can use different substituting groups.
The 2nd glycol R
2(OH)
2The preferred aromatic diol compound that uses general formula (3).
As the φ in the general formula (3)
1, φ
2... φ
kConcrete example, can from general formula (2) φ
1, φ
2... φ
jSelect in the same compound group.As φ
1, φ
2... φ
k, needn't all be identical substituting group, φ
1, φ
2... φ
kIn part or all can use different substituting groups.
As the B in the general formula (3)
1, B
2... B
K-1Substituting group, can be from the A the 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 all be identical substituting group, B
1, B
2... B
K-1In part or all can use different substituting groups.
The 1st glycol R
1(OH)
2The compound of more than one that preferred use is selected 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 '-two (4-hydroxy phenyl)-1-diphenylphosphino ethanes,
1,1 '-two (4-hydroxy-2-methyl phenyl) diphenylphosphino ethane,
1,1 '-two (4-hydroxy-3-methyl phenyl) diphenylphosphino ethane,
2,2 '-two (4-hydroxy phenyl) propane (another name bisphenol-A),
2,2 '-two (4-hydroxy phenyl) HFC-236fa (another name bisphenol AF),
2,2 '-two (4-hydroxy-3-methyl phenyl) propane (another name bisphenol-c),
2,2 '-two (4-hydroxyl-3,5-3,5-dimethylphenyl) propane,
2,2 '-two (3-ethyl-4-hydroxy phenyl) propane,
2,2 '-two (3-tert-butyl-hydroxy phenyl) propane,
2,2 '-two (3-cyclohexyl-4-hydroxy phenyl) propane,
2,2 '-two (4-hydroxyl-3-phenyl) propane,
2,2 '-two (4-hydroxyl-3,5-3,5-dimethylphenyl) propane,
2,2 '-two (3-chloro-4-hydroxy phenyl) propane,
2,2 '-two (3-bromo-4-hydroxy phenyl) propane,
2,2 '-two (3,5-two bromo-4-hydroxy phenyls) propane,
2,2 '-two (4-hydroxy phenyl) butane,
2,2 '-two (4-hydroxy phenyl)-3-methylbutanes,
2,2 '-two (4-hydroxy phenyls)-3,3 '-dimethylbutane,
2,2 '-two (4-hydroxy phenyl)-4-methylpentanes,
1,1 '-two (4-hydroxy phenyl) cyclopentane,
1,1 '-bis(4-hydroxyphenyl)cyclohexane (another name bisphenol Z),
Two (4-hydroxy phenyl) phenylmethane,
1,1 '-two (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 that is selected among the following d11 to d16.
The 2nd glycol R
2(OH)
2Be preferably more than one the compound that is selected among the following d21 to d23.
And then, for the structure (R that derives from the 1st glycol
1) with derive from the structure (R of the 2nd glycol of 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, though be unlikely to hinder practicality, be easy to generate problem that the dissolubility when being used to make coating fluid worsens a little or initial stage and durable after the problem that worsens of current potential.
And then, have the R in the general formula (1)
3Dicarboxylic acid compound preferably use the dicarboxylic acid compound that is selected from aromatic dicarboxylic acid or the aliphatic dicarboxylic acid.
As the aromatic dicarboxylic acid composition, for example by m-phthalic acid, terephthalic acid (TPA), tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, the methyl m-phthalic acid, the 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, benzophenone-4,4 '-dioctyl phthalate, naphthalene-1, the 4-dioctyl phthalate, naphthalene-1, the 5-dioctyl phthalate, naphthalene-2, the 6-dioctyl phthalate, naphthalene-2, the 7-dioctyl phthalate, diphenyl ether-4,4 '-dioctyl phthalate, diphenyl sulfide-4,4 '-dioctyl phthalate, diphenyl sulfide-4,4 '-aromatic dicarboxylic acid 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 the mol ratio of preferred 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 the aliphatic dicarboxylic acid composition, for example being derived by 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 cyclohexanedimethanodibasics obtains.
As the glass transition temperature of the resin glue of general formula (1), be preferably more than 100 ℃ below 180 ℃.This resin glue is 2 * 10 by the weight-average molecular weight of polystyrene conversion
4To 5 * 10
6Be effectively, especially preferably the weight-average molecular weight by polystyrene conversion is 5 * 10
4To 1 * 10
6
Manufacture method for the resin glue of general formula (1)
Manufacture method as copolymerization polyarylate resin with structural unit of the present invention, the various dicarboxylic acid compounds that used the polyarylate structure of deriving, melt phase polycondensation, solution polymerization process and the interfacial polymerization of diol compound or derivatives thereof can be utilized, especially interfacial polymerization can be effectively used.In addition, also can be the autofrettage of having used the melting mixing ester exchange reaction of other vibrin.
By the resin glue with general formula (1) be used for Electrophtography photosensor, in particular for the superficial layer of Organophotoreceptor, can reach goal of the invention better.
Below the preferred photoreceptor of record constitutes.
So-called Organophotoreceptor, mean that the organifying compound has the Electrophtography photosensor that at least a function in requisite charge generation function of the formation of Electrophtography photosensor and the charge transport function is constituted, be meant by organic charge to produce photoreceptor that material or organic charge transportation of substances constitute, finish charge generation function and charge transport function and the Organophotoreceptors such as photoreceptor that constitute with high-molecular complex.
Above-mentioned Organophotoreceptor also can have the formation that the photographic layer of single layer structure is set on the electric conductivity supporter; but preferably be at least the photoreceptor that following such layer constitutes among the present invention, wherein preferably in the protective seam of the superiors or photographic layer, use the resin glue of general formula (1).
1) on the electric conductivity supporter successively lamination the middle layer is arranged and constitutes as the layer of the charge generation layer of photographic layer and charge transport layer,
2) on the electric conductivity supporter successively lamination the middle layer is arranged, constitutes as the layer of the charge generation layer of photographic layer and charge transport layer and protective seam,
With above-mentioned 1) be the layer formation of center narration Organophotoreceptor.
(electric conductivity supporter)
As long as supporter has electric conductivity, then can be arbitrary substance, for example can enumerate: with metal formings such as aluminium, copper, chromium, nickel, zinc and stainless steels is the supporter that drum type or sheet obtain; On plastic foil lamination metal forming such as aluminium, copper and supporter; On plastic foil evaporation aluminium, indium oxide and tin oxide etc. and supporter; With separately coating or be coated with and metal, plastic foil and the paper etc. of conductive layer are set of conductive material with resin glue.
(middle layer)
The middle layer that possesses barriers function and binding function can be set in the middle of conductive layer and photographic layer.
The middle layer can form in the following way: resin glues such as casein, polyvinyl alcohol (PVA), nitrocellulose, ethylene-acrylic acid copolymer, polyamide, polyurethane and gelatin are dissolved in the solvent, form by dip coated etc.Particularly preferably be dissolvable in water the polyamide of alcohol.
In addition, the purpose for the resistance of adjusting the middle layer can make the middle layer contain various electrically conductive microparticles, metal oxide.Various metal oxides such as aluminium oxide, zinc paste, titanium dioxide, tin oxide, antimony oxide, indium oxide, bismuth oxide for example.Can use ultra microns such as the indium oxide that is doped with tin, the tin oxide that is doped with antimony and zirconia.
Can use a kind of these metal oxides, or two or more mixing is used.Under 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 the 0.3 μ m, more preferably below the 0.1 μ m.
As the solvent of middle layer use, preferably with the inorganic particle fine dispersion and with the fat-solvent solvent of polyamide resin.Specifically, to be 2 to 4 alcohols excellent and preferred aspect the dissolubility of polyamide and coating performance for carbon numbers such as ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, the tert-butyl alcohol, sec-butyl alcohol.In addition,, can share cosolvent, can enumerate methyl alcohol, benzylalcohol, toluene, methylene chloride, cyclohexanone, tetrahydrofuran etc. as this cosolvent with solvent in order to improve the dispersiveness of keeping quality, particle.
Suitably select the concentration of resin glue so that conform to thickness, the speed of production in middle layer.
Inorganic particle when disperseing inorganic particle etc. is 20 to 400 mass parts with respect to resin glue 100 mass parts inorganic particles preferably with respect to the blending ratio of resin glue, 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 solvent types, thickness, preferred 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 the charge generation material is dispersed in the resin glue solution, is coated with and forms.
The charge generation material can be enumerated indigo pigment, phthalocyanine colors etc. such as tonyred and quinone pigments such as diamine ble azo raw materials such as (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 that is dispersed in the resin.
Resin glue as 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 contain two or more copolymer resins (for example, vinyl chloride vinyl acetate copolymer resin in these resins, vinyl chloride-vinyl acetate-copolymer-maleic anhydride resin) and Polectron etc.
Charge generation layer is preferably as follows formation: use the dissolution with solvents resin glue, utilize dispersion machine to disperse the charge generation material in the solution that obtains and prepare coating fluid, with constant thickness coating coating fluid, drying coating film is made charge generation layer with coating machine.
As the resin glue dissolving that is used for charge generation layer is used and the solvent of coating, 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, 1,3-dioxolanes, pyridine and diethylamine etc.
As the diverting device of charge generation material, can use ultrasonic dispersing machine, bowl mill, sand mill and homomixer etc.
The charge generation material is 1 to 600 mass parts with respect to resin glue 100 mass parts charge generation materials preferably with respect to the blending ratio of resin glue, more preferably 50 to 500 parts.The thickness of charge generation layer with blending ratio etc. and different, is preferably 0.01 to 5 μ m, more preferably 0.05 to 3 μ m according to the characteristic of the characteristic of charge generation material, resin glue.The coating fluid that charge generation layer is used can prevent the generation of image deflects by filtration foreign matter and agglutinator before coating.Also can form by vacuum evaporation pigment.
(charge transport layer)
Charge transport layer contains charge transport material (CTM) and resin glue, and the charge transport substance dissolves in resin glue solution, is coated with and forms.
The charge transport material for example can be with carbazole derivates oxazole derivant oxadiazole derivant, 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, the azophenlyene derivant, amino stilbene derivative, the triarylamine derivant, phenylenediamine derivative, stilbene derivative, benzidine derivative, the poly-N-vinyl carbazole, poly--1-vinylpyrene and poly--9-vinyl anthracene, triphenylamine derivatives etc. mix use more than 2 kinds.
The resin glue that charge transport layer is used preferably uses the resin glue of general formula (1).Also can share other resins with the resin glue of general formula (1).As the resin glue that 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 coating fluid, with constant thickness coating coating fluid, with the coated film drying, make charge transport layer with coating machine.
The solvent of the coating fluid dissolving of the resin glue of charge transport layer and charge transport material will be contained as being used for, can enumerate for example methylene chloride, 1, the 2-ethylene dichloride, toluene, dimethylbenzene, benzene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, tetrahydrofuran, 1, the 4-dioxane, 1, the 3-dioxolanes, N, N '-dimethyl formamide, pyridine etc., wherein, as the dissolubility of the coating fluid of the charge transport layer under the resin glue situation of using general formula (1) and all good solvent of stability of coating fluid, can enumerate tetrahydrofuran, toluene, dimethylbenzene, 1, the 4-dioxane, methyl isobutyl ketone, methylene chloride, 1,2-ethylene dichloride equal solvent.Even not necessarily use the solvent of halogen-containing element, also can make good coating fluid.
The charge transport material is 10 to 500 mass parts with respect to resin glue 100 mass parts charge transport materials preferably with respect to the blending ratio of resin glue, more preferably 20 to 150 mass parts.
The thickness of charge transport layer with blending ratio etc. and different, but is preferably 5 to 40 μ m according to the characteristic of the characteristic of charge transport material, resin glue, more preferably 10 to 35 μ m.
In charge transport layer, can add antioxidant, electronic conduction agent, stabilizing agent etc.For antioxidant, can be the antioxidant of putting down in writing among the TOHKEMY 2000-305291, for the electronic conduction agent, can be the middle electronic conduction agent of putting down in writing such as Japanese kokai publication sho 50-137543.
In addition, in charge transport layer, also can add levelling agent as required.As the levelling agent that can in charge transport layer, share, can use silicone oils such as dimethyl silicon oil, methyl phenyl silicone oil, have the polymkeric substance or the oligomer of perfluoroalkyl at side chain, its use amount is to suit about 0 to 1 mass parts with respect to the resin glue of 100 mass parts.
The electrostatic latent image that forms on Organophotoreceptor is by developing as the toner picture and development.The toner that is used to develop can be a crushed toner, also can be polymerization toner, but considers from the viewpoint that obtains stable size-grade distribution, preferably the polymerization toner of making of polymerization.
So-called polymerization toner is meant the polymerization of the starting monomer that is shaped as resin glue with the generation and the toner of the resin of cementing agent by toner and the toner that forms by follow-up chemical treatment as required.More particularly, be meant through polyreactions such as suspension polymerization, emulsion polymerization and the toner that forms in the intergranular fusion process of carrying out thereafter as required.
The volume average particle size of toner, be that above-mentioned 50% particle volume diameter (Dv50) is preferably 2 to 9 μ m, 3 to 7 μ m more preferably.By being made as this mean grain size, can improve resolution.And then, by with the combination of above-mentioned mean grain size, can when becoming small particle size toner, reduce the amount of the toner of fine particle size, can improve for a long time dot image repeatability, good, the stable image of formation distinctiveness.
Toner can be monocomponent toner, also can be two-component developing agent.
When using as monocomponent toner, can enumerate the non-magnetic mono-component developer or contain the magnetic single component developer of the magnetic-particle about 0.1 to 0.5 μ m in toner, these all can use.
In addition, can mix as two-component developing agent with carrier and use.In this case, as the magnetic-particle of carrier, can use metals such as iron, ferrite, magnetic iron ore, the materials such as alloy of metals such as these metals and aluminium, lead.Preferred especially ferrite particle.Preferred its volume average particle size of above-mentioned magnetic-particle 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 " (manufacturing of SYMPATEC company) that possesses the wet type dispersion machine typically.
The preferred magnetic-particle of carrier is further by resin-coated carrier or make magnetic-particle be dispersed in so-called resin dispersion type carrier in the resin.Resin as coating usefulness is formed, and can use for example ethylene series resin, phenylethylene resin series, styrene-propene acid is that resin, silicon-type resin, ester are resin or fluoropolymer system resin etc.In addition, as the resin that is used to constitute resin dispersion type carrier, can use for example styrene-propene acid 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 Figure 1 is the image processing system of digital mode, by image reading unit A, image processing part B, image forming part C, constitute as the transfer transport unit D of transfer 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 of mounting on original copy mounting table 11 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 the end is discharged on the original copy paper discharge tray 14 by original copy transfer roller 12.
The speed v of the image of the original copy when on the other hand, placing on the contact glass 13 by the 1st mirror unit 15 (it is made up of illuminating lamp that constitutes scanning optics and the 1st mirror) what read action and the 2nd mirror unit 16 (it is made up of the 2nd mirror that forms V word shape on the position and the 3rd mirror) is that moving of v/2 read to unidirectional speed.
The image that reads by projecting lens 17 back in sensitive surface imaging as the imaging apparatus CCD of linear sensor.Carry out the A/D conversion the wire optical image of imaging on the imaging apparatus CCD is become electric signal (luminance signal) successively by opto-electronic conversion after, after the conversion of enforcement concentration, Filtering Processing etc. were handled in image processing part B, view data temporarily was stored in the storer.
Among the 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 (charged operation) 22 of this photoreceptor 21, the current potential detecting 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 with remove the PCL (pre-charged lamp) 27 of electric unit (light removes electrician's preface) as light.In addition, be provided with the reflection density detecting unit 222 of the reflection density that is used to be determined at the image patch (パ Star チ picture) that develops on the photoreceptor 21 in the downstream of developing cell 23.Photoreceptor 21 is driven in rotation in illustrated clockwise direction.
Utilize photoreceptor 21 that charged elements 22 makes rotation with after going up identical electricity,, look like to expose based on the picture signal that from the storer of image processing part B, accesses by as exposure optical system as exposing unit (as exposure process) 30.As writing unit promptly as the exposure optical system of exposing unit 30, with not shown laser diode is illuminating source, behind the polygonal mirror 31 of process rotation, f θ lens 34, the cylindrical lens 35, light path mirror 32 bending that is reflected, carry out main sweep, photoreceptor 21 is looked like exposure in the position of Ao, by rotation (subscan) the formation electrostatic latent image of photoreceptor 21.In one example of present embodiment word segment is exposed, form electrostatic latent image.
In the image processing system of the present invention, when on photoreceptor, forming electrostatic latent image, preferably be that 350 to 800nm semiconductor laser or light emitting diode are as using as exposure light source with oscillation wavelength.Use these as exposure light source, the exposure station diameter of the main scanning direction that writes is controlled at 10 to 100 μ m, in the exposure of the enterprising line number word of Organophotoreceptor, can access the electrophotographic image of the above high resolution to 2500dpi of 400dpi (dpi: every 2.54cm counts) thus.
So-called exposure station diameter is meant that along the intensity of this exposing light beam be the 1/e of peak intensity
2The length (Ld: length is measured at maximum position) of the exposing light beam of the main scanning direction in above zone.
As used light beam, the scanning optics of having used semiconductor laser and solid state scanning instrument of LED etc. are arranged, for light intensity distributions, Gaussian distribution and Lorentz distribution etc. are arranged, with the 1/e of separately peak intensity
2Above zone is the exposure station diameter.
Electrostatic latent image on the photoreceptor 21 utilizes developing cell 23 to carry out discharged-area development, but forms the toner picture of video on the surface of photoreceptor 21.In the image forming method of the present invention, the developer that is used for this developing cell preferably uses polymerization toner.Share by polymerization toner and Organophotoreceptor of the present invention, can access distinctiveness good electron photographic image more shape and even particle size distribution.
Among the transfer transport unit D, below image formation unit, be provided with paper supply unit 41 (A) as the transfer storage unit of the transfer P that deposits different size, 41 (B), 41 (C), and be provided with the manual feed unit 42 that carries out manual feed in the side, the transfer P of any selection from these unit is transmitted along transmitting road 40 by guide roller 43, after temporarily being stopped, the inclination of the transfer P that transmitting and a pair of paper feeding registration roller 44 transfer 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 the photoreceptor 21 of mounting be transferred to simultaneously on the transfer P, this transfer P is sent to fixation unit 50 from 21 separation of photoreceptor by transfer printing conveyor-belt apparatus 45.
The one-sided state that carries out image formation in transfer more than has been described, under the situation of double-sided copying, row's paper switching member 170 switches, and transfer guide part 177 is open, transmits transfer P along the dotted arrow direction.
And then transfer P makes it switchback by transfer counter-rotating portion 179 below being sent under the effect of delivery unit 178, and the rearward end of transfer P becomes leading section, is sent to double-sided copying with in the paper feed unit 130.
Transfer P utilizes and to be located at double-sided copying and to move to paper feeding direction with the transmission guiding element 131 of paper supply unit 130, with transfer P paper feeding again, transfer P is led transmission road 40 with paper-feed roll 132.
Transmit transfer P to photoreceptor 21 directions as described above once more, at the back side of transfer P transfer printing toner image, after fixation unit 50 photographic fixing, row's paper is to paper discharge tray 64.
As image processing system of the present invention, above-mentioned photoreceptor and constitutive requirements such as developer, clearer can be constituted in combination as the handle box one, this unit can freely be constituted with respect to apparatus main body with loading and unloading.In addition, also can be with charged device, as one of at least supporting ground and form handle box in exposer, developer, transfer printing or separation vessel and the clearer with the photoreceptor one, make the single unit that can freely be loaded and unloaded on device body, the pilot units such as guide rail of operative installations body form the formation of freely loading and unloading.
Fig. 2 is the section constitution figure that the coloured image of expression an embodiment of the present invention forms device.
This coloured image forms device and is called as the tandem type coloured image and forms device, by 4 groups of image forming parts (image formation unit) 10Y, 10M, 10C, 10Bk, banded intermediate transfer body unit 7, paper feeding delivery unit 21 and fixation unit 24 constitute for no reason.Top at the body A of image processing system disposes original image reading device SC.
The image forming part 10Y that forms yellow image has: be disposed at as the 1st image support charged elements (charged operation) 2Y, exposing unit (exposure process) 3Y around the drum type photoreceptor 1Y of body, developing cell (developing procedure) 4Y, as primary transfer roller 5Y, the cleaning unit 6Y of primary transfer unit (primary transfer operation).The image forming part 10M that forms magenta color image has: as the 1st image support drum type photoreceptor 1M, charged elements 2M, exposing unit 3M, the developing cell 4M of body, as primary transfer roller 5M, the cleaning unit 6M of primary transfer unit.The image forming part 10C that forms cyan image has: as the 1st image support drum type photoreceptor 1C, charged elements 2C, exposing unit 3C, the developing cell 4C of body, as primary transfer roller 5C, the cleaning unit 6C of primary transfer unit.The image forming part 10Bk that forms black image has: as the 1st image support drum type photoreceptor 1Bk, charged elements 2Bk, exposing unit 3Bk, the developing cell 4Bk of body, as primary transfer roller 5Bk, the cleaning unit 6Bk of primary transfer unit.
4 groups of image formation unit 10Y, 10M, 10C, 10Bk are the center with photosensitive drums 1Y, 1M, 1C, 1Bk, are made of the charged elements 2Y, the 2M that rotate, 2C, 2Bk, developing cell 4Y, 4M, 4C, 4Bk and cleaning photosensitive drums 1Y as exposing unit 3Y, 3M, 3C, 3Bk, rotation, 1M, 1C, cleaning unit 5Y, the 5M of 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 constitute identically, be that example is elaborated with image formation unit 10Y.
Charged elements 2Y is the unit of photosensitive drums 1Y being given same potential, in the present embodiment, photosensitive drums 1Y is used the charged device 2Y of corona discharge type.
As exposing unit 3Y is 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 this exposing unit 3Y, can use by photosensitive drums 1Y axially on light-emitting component is arranged in the LED and the image-forming component (trade name: SELFOC Lens) exposing unit of Gou Chenging or laser optical system etc. of array-like.
As image processing system, above-mentioned photoreceptor and constitutive requirements such as developer, clearer can be constituted in combination as handle box (image formation unit) one, and this image formation unit can freely be constituted with respect to apparatus main body with loading and unloading.In addition, also can be with charged device, as one of at least supporting ground and form handle box (image formation unit) in exposer, developer, transfer printing or separation vessel and the clearer with the photoreceptor one, make the single image formation unit that can freely be loaded and unloaded on apparatus main body, the pilot units such as guide rail of operative installations body form the formation of freely loading and unloading.Herein, so-called " one support " is meant when the loading and unloading handle box, can carry out installation or removal as 1 block with process cartridge unit.
For no reason conduct the 2nd image that banded intermediate transfer body unit 7 has a semiconduction ring-band shape supports the banded for no reason intermediate transfer body 70 of body, and the described body 70 of quoting in the middle of banded for no reason is wound onto on a plurality of rollers and is supported rotationally.
Each color image that is formed by image formation unit 10Y, 10M, 10C, 10Bk is transferred on the banded for no reason intermediate transfer body 70 of rotation the coloured image that formation will be synthesized one by one by primary transfer roller 5Y, 5M, 5C, 5Bk as the primary transfer unit.The transfer P as transfer (support the supporter of the final image after the photographic fixing: for example common paper, slide etc.) that leaves in the paper feeding cassette 20 is transmitted by paper feed unit 21, through a plurality of intermediate calender rolls 22A, 22B, 22C, 22D, registration roller 23, be sent to secondary transfer roller 5b, on transfer P, carry out secondary transfer printing and coloured image transfer printing without exception as the secondary transfer printing unit.The transfer P of transfer printing chromatic colour image utilizes fixation unit 24 to carry out photographic fixing and handles, and is seized on both sides by the arms by exit roller 25 and on the paper discharge tray 26 of mounting outside machine.Herein, the transfer printing supporter of the toner image that intermediate transfer body and transfer etc. are formed on photoreceptor is referred to as offset medium.
On the other hand, after the secondary transfer roller 5b that is used as the secondary transfer printing unit is transferred to transfer P with coloured image, the banded for no reason intermediate transfer body 70 that transfer P curvature is separated is removed remaining toner by cleaning unit 6b.
In image form to be handled, primary transfer roller 5Bk always with photoreceptor 1Bk butt.Other primary transfer roller 5Y, 5M, 5C are only when coloured image forms and each self-corresponding photoreceptor 1Y, 1M, 1C butt.
In addition, Jie can pull out framework 8 by supporting guide 82L, 82R from apparatus main body A.
Framework 8 is made of image forming part 10Y, 10M, 10C, 10Bk and banded for no reason intermediate transfer body unit 7.
Fig. 3 has been to use the coloured image of Organophotoreceptor of the present invention to form the formation sectional view of device (duplicating machine or the laser beam printer that have charged elements, exposing unit, a plurality of developing cell, transfer printing unit, cleaning unit and intermediate transfer body at least at the periphery of Organophotoreceptor).It is moderate elastic body that banded intermediate transfer body 70 uses resistance.
The 1st, the Barrate type photoreceptor as being used repeatedly as organizator is driven in rotation with predetermined circumference speed in the counter clockwise direction shown in the arrow.
Photoreceptor 1 is processed into polarity and the current potential that has regulation equally by charged elements (charged operation) 2 in rotary course, next, by not shown picture exposing unit (as exposure process) 3, be subjected to image exposure, thereby the corresponding electrostatic latent image of color component picture (colouring information) of the yellow (Y) of formation and target coloured image, this image exposure utilization is adopted that the scan exposure of laser beam is used up etc. and is carried 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).At this moment, the the 2nd to the 4th developing cell (magenta developer, cyan developer, black toner developer) 4M, 4C, 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 subjected to the influence of above-mentioned the 2nd to the 4th developer.
Passing through in the process of the impression portion between photoreceptor 1 and the intermediate transfer body 70 at the 1st color yellow toner image that forms on the photoreceptor 1 and support thereon, utilization is applied to the formed electric field of primary transfer bias voltage of intermediate transfer body 70 from primary transfer roller 5a, by intermediate transfer (primary transfer) to the outer peripheral face of intermediate transfer body 70.
Finished the device 6a cleaning that is cleaned of surface with the photoreceptor 1 of the transfer printing of intermediate transfer body 70 corresponding the 1st color yellow toner images.
Next similarly stack transfer printing the 2nd color magenta toner image, the 3rd color cyan toner image, the 4th color black toner image on intermediate transfer body 70 successively form and the corresponding stack color toner of target coloured image 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 article 70 lower faces.
Being used for from photoreceptor 1 is the polarity opposite with toner to the primary transfer bias voltage of overlapping successively transfer printing the 1st to the 4th color toner image of intermediate transfer body 70, is applied by grid bias power supply.Its apply voltage for example for+100V～+ 2kV.
From photoreceptor 1 to the primary transfer operation of the 1st to the 3rd color toner image of intermediate transfer body 70, secondary transfer roller 5b and intermediate transfer body cleaning unit 6b also can leave from middle transfer article 70.
The stack color toner image that is transferred on the banded intermediate transfer body 70 carries out to the transfer printing of the transfer P that supports body as the 2nd image is following, promptly, in the band butt of secondary transfer roller 5b and intermediate transfer body 70, transfer P from a pair of paper feeding registration roller 23 by the transfer guiding element, the opportunity of regulation be sent to intermediate transfer body 70 with on the nip of secondary transfer roller 5b butt.Apply the 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 from middle transfer article 70 transfer printings (secondary transfer printing) to supporting on the transfer P of body as the 2nd image.The transfer P that has accepted the toner image transfer printing is imported fixation unit 24, carry out heat fixer.
Image processing system of the present invention generally is applicable to 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 used 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 using among the embodiment all represents mass parts.
Embodiment 1
Make photoreceptor 1 as follows.
Cut is carried out on surface to the 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 (manufacturing of Daicel Degussa Co., Ltd.)
1.1 parts of titania SMT500SAS (manufacturing of TAYCA company)
20 parts of ethanol
Use sand mill as dispersion machine, carry out 10 hours dispersion with batch-type.
Use above-mentioned coating fluid on supporter, to be coated with, so that be 2 μ m at the thickness of 110 ℃ of dryings after 20 minutes with the dip coated method.
＜charge generation layer 〉
Charge generation material: 20 parts of titanyl phthalocyanine pigment (the titanyl phthalocyanine pigment that has the maximum diffraction peak in the Cu-K α characteristic X-ray diffraction spectrum mensuration at least 27.3 ° position)
10 parts of polyvinyl butyral resins (#6000-C: Denki Kagaku Kogyo kabushiki makes)
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, preparation charge generation layer coating fluid.With the dip coated method this coating fluid is coated on the middle layer, 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: 300 parts of copolymerization polyarylate resin (copolymerization of the potpourri of the 1st glycol/the 2nd glycol=0.5/0.5 (mole) of the No.1 of table 1～table 6 record and the potpourri of m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)) with following structural unit
6 parts of antioxidants (Irganox1010: Japanese Ciba-Geigy company makes)
Solvent: 2000 parts of toluene/tetrahydrofurans=1.5/8.5 (part)
1 part of silicone oil (KF-54: chemical company of SHIN-ETSU HANTOTAI makes)
Above-mentioned substance is mixed dissolving, preparation charge transport layer coating fluid.Use the dip coated method to be coated with this coating fluid on charge generation layer, forming thickness 110 ℃ of dryings after 60 minutes is the charge transport layer of 25 μ m, is 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 the copolymerization polyarylate resin (copolymerization of the potpourri of the 1st glycol/the 2nd glycol=0.5/0.5 (mole) of the No.2 record of table 1～table 6 and the potpourri of m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)) with following structural unit, photoreceptor 2 is made in operation similarly in addition.
The weight-average molecular weight of polystyrene conversion: 220,000
The making of photoreceptor 3
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with the copolymerization polyarylate resin (copolymerization of the potpourri of the 1st glycol/the 2nd glycol=0.95/0.05 (mole) of the No.3 record of table 1～table 6 and the potpourri of m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)) with following structural unit, photoreceptor 3 is made in operation similarly in addition.
The weight-average molecular weight of polystyrene conversion: 210,000
Embodiment 4
The making of photoreceptor 4
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with the copolymerization polyarylate resin (copolymerization of the potpourri of the 1st glycol/the 2nd glycol=0.05/0.95 (mole) of the No.4 record of table 1～table 6 and the potpourri of m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)) with following structural unit, with more 4000 parts of the quantitative changes of solvent, photoreceptor 4 is made in operation similarly 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 the copolymerization polyarylate resin (copolymerization of the potpourri of the 1st glycol/the 2nd glycol=0.6/0.4 (mole) of the No.5 record of table 1～table 6 and the potpourri of m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)) with following structural unit, photoreceptor 5 is made in operation similarly 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 the copolymerization polyarylate resin (copolymerization of the potpourri of the 1st glycol/the 2nd glycol=0.65/0.35 (mole) of the No.6 record of table 1～table 6 and the potpourri of m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)) with following structural unit, photoreceptor 6 is made in operation similarly in addition.
The weight-average molecular weight of polystyrene conversion: 230,000
The making of photoreceptor 7
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with the copolymerization polyarylate resin (copolymerization of the potpourri of the 1st glycol/the 2nd glycol=0.5/0.5 (mole) of the No.7 record of table 1～table 6 and the potpourri of m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)) with following structural unit, photoreceptor 7 is made in operation similarly 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 the copolymerization polyarylate resin (copolymerization of the potpourri of the 1st glycol/the 2nd glycol=0.5/0.5 (mole) of the No.8 record of table 1～table 6 and the potpourri of m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)) with following structural unit, photoreceptor 8 is made in operation similarly 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 the copolymerization polyarylate resin (copolymerization of the potpourri of the 1st glycol/the 2nd glycol=0.6/0.4 (mole) of the No.9 record of table 1～table 6 and the potpourri of m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)) with following structural unit, photoreceptor 9 is made in operation similarly 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 the copolymerization polyarylate resin (copolymerization of the potpourri of the 1st glycol/the 2nd glycol=0.5/0.5 (mole) of the No.10 record of table 1～table 6 and the potpourri of m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)) with following structural unit, photoreceptor 10 is made in operation similarly 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 the copolymerization polyarylate resin (copolymerization of the potpourri of the 1st glycol/the 2nd glycol=0.6/0.4 (mole) of the No.11 record of table 1～table 6 and the potpourri of m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)) with following structural unit, photoreceptor 11 is made in operation similarly in addition.
The weight-average molecular weight of polystyrene conversion: 220,000
The making of photoreceptor 12
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with copolymerization polyarylate resin with following structural unit (potpourri of the 1st glycol/the 2nd glycol=0.6/0.4 (mole) of the No.12 record of table 1～table 6, and dicarboxylic acid compound=diphenyl ether-4, the copolymerization of 4 '-dioctyl phthalate (a3)=1.0 (mole)), photoreceptor 12 is made in operation similarly in addition.
The weight-average molecular weight of polystyrene conversion: 210,000
The making of photoreceptor 13
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with copolymerization polyarylate resin with following structural unit (potpourri of the 1st glycol/the 2nd glycol=0.5/0.5 (mole) of the No.13 record of table 1～table 6, and dicarboxylic acid compound=diphenyl ether-4, the copolymerization of 4 '-dioctyl phthalate (a3)=1.0 (mole)), photoreceptor 13 is made in operation similarly in addition.
The weight-average molecular weight of polystyrene conversion: 240,000
The making of photoreceptor 14
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with copolymerization polyarylate resin with following structural unit (potpourri of the 1st glycol/the 2nd glycol=0.4/0.6 (mole) of the No.14 record of table 1～table 6, and dicarboxylic acid compound=diphenyl ether-4, the copolymerization of 4 '-dioctyl phthalate (a3)), photoreceptor 14 is made in operation similarly in addition.
The weight-average molecular weight of polystyrene conversion: 230,000
Embodiment 15
The making of photoreceptor 15
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with copolymerization polyarylate resin with following structural unit (potpourri of the 1st glycol/the 2nd glycol=0.5/0.5 (mole) of the No.15 record of table 1～table 6, and dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)/diphenyl ether-4, the copolymerization of the potpourri of 4 '-dioctyl phthalate (a3)=0.333/0.333/0.333 (mole)), photoreceptor 15 is made in operation similarly 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, the cementing agent of charge transport layer is replaced with copolymerization polyarylate resin with following structural unit (potpourri of the 1st glycol/the 2nd glycol=0.5/0.5 (mole) of the No.16 record of table 1～table 6, and dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)/2, the copolymerization of the potpourri of 6-naphthalenedicarboxylic acid (a4)=0.4/0.4/0.2 (mole)), photoreceptor 16 is made in operation similarly in addition.
The weight-average molecular weight of polystyrene conversion: 240,000
The making of photoreceptor 17
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with copolymerization polyarylate resin with following structural unit (potpourri of the 1st glycol/the 2nd glycol=0.6/0.4 (mole) of the No.17 record of table 1～table 6, and the copolymerization of the potpourri of dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)/hexane diacid (a5)=0.333/0.333/0.333 (mole)), photoreceptor 17 is made in operation similarly 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, the cementing agent of charge transport layer is replaced with copolymerization polyarylate resin with following structural unit (potpourri of the 1st glycol/the 2nd glycol=0.5/0.5 (mole) of the No.18 record of table 1～table 6, and the copolymerization of the potpourri of dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)), photoreceptor 18 is made in operation similarly 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, the cementing agent of charge transport layer is replaced with copolymerization polyarylate resin with following structural unit (potpourri of the 1st glycol/the 2nd glycol=0.4/0.6 (mole) of the No.19 record of table 1～table 6, and dicarboxylic acid compound=diphenyl ether-4, the copolymerization of 4 '-dioctyl phthalate (a3)), photoreceptor 19 is made in operation similarly in addition.
The weight-average molecular weight of polystyrene conversion: 220,000
The making of photoreceptor 20
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with copolymerization polyarylate resin with following structural unit (potpourri of the 1st glycol/the 2nd glycol=0.7/0.3 (mole) of the No.20 record of table 1～table 6, and the copolymerization of the potpourri of dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)), photoreceptor 20 is made in operation similarly 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 the copolymerization polyarylate resin with following structural unit, and (No.21 as table 1～table 6 puts down in writing, remove the 1st glycol, be the copolymerization of the potpourri of the 2nd glycol 1.0 (mole) and m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)), solvent changed to 4000 parts tetrahydrofuran, photoreceptor 21 is made in operation similarly 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 the polycarbonate (Z300: the manufacturing of gas chemical company of Mitsubishi), similarly operate in addition, make photoreceptor 22 of following structural unit.
The making of photoreceptor 23
In the making of photoreceptor 1, the cementing agent of charge transport layer is replaced with the copolymerization polyarylate resin (copolymerization of the potpourri of the 1st glycol/the 2nd glycol=0.03/0.97 (mole) of the No.23 record of table 1～table 6 and the potpourri of dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)) with following structural unit, solvent changed to 4000 parts tetrahydrofuran, photoreceptor 23 is made in operation similarly 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 the copolymerization polyarylate resin (copolymerization of the potpourri of the 1st glycol/the 2nd glycol=0.97/0.03 (mole) of the No.23 record of table 1～table 6 and the potpourri of dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)) with following structural unit, photoreceptor 24 is made in operation similarly 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 the copolymerization polyarylate resin (copolymerization of the potpourri of the 1st glycol/the 2nd glycol=0.03/0.97 (mole) of the No.25 record of table 1～table 6 and the potpourri of dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)) with following structural unit, photoreceptor 25 is made in operation similarly 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 the copolymerization polyarylate resin (copolymerization of the potpourri of the 1st glycol/the 2nd glycol=0.97/0.03 (mole) of the No.26 record of table 1～table 6 and the potpourri of dicarboxylic acid compound=m-phthalic acid (a1)/terephthalic acid (TPA) (a2)=0.5/0.5 (mole)) with following structural unit, photoreceptor 26 is made in operation similarly 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)
The photoreceptor that as above obtains is used the commercially available full color compounding machine bizhub PRO C6500 that has Fig. 2 and constitute basically, and (Konica Minolta Business Technology Co makes; Use the exposure light of the semiconductor laser of 600dpi, 780nm) estimate.Above-mentioned full color compounding machine is owing to having 4 groups of image formation units, so the photoreceptor unification of each image formation unit is estimated with the photoreceptor (for example, under the situation of photoreceptor 1, preparing 4 photoreceptors 1) of same kind.During each is estimated, 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 the neutralized paper A4 paper, prints 100,000, carry out anti-printing test, thereafter, under each following different environmental baseline, estimate.
(potential property)
Carry out 100,000 printings in the above-mentioned evaluation, use the surface potential after the transformation apparatus that is provided with the surface potential meter in the position of the developing cell of bizhub PRO C6500 is estimated initial stage and 100,000.
Measure surface potential VL (V), the surface potential VH (V) of unexposed portion of exposure portion, utilize potential change, Δ VL (V), Δ VH (V) after the absolute value of change is estimated initial stage and 100,000.
Photoreceptor belt electric potential (unexposed current potential): be-700V with the initial stage potential setting.
(evaluation of coloured image)
After anti-printing test is carried out in 100,000 of printings under 30 ℃, the environmental baseline of 80%RH, under 20 ℃, the environmental baseline of 50%RH, placed 12 hours, make 4 groups of images of full color compounding machine bizhub PRO C6500 form cell operation, the half tone image that will comprise human face photo is printed on the A4 paper, estimates with following benchmark.
A: reproduce the coloured image of half toning smoothly, do not find to produce image blurring and image inequality
B: produce image blurring on the coloured image top of half toning or image is uneven, but and not obvious, reproduce smoothly on the whole (no problem in the practicality)
C: in the coloured image of half toning, that the part comprises is significantly image blurring, image is uneven, does not have repeatability (problem is arranged in the practicality)
D: whole of the coloured image of half toning goes up and produces significantly image blurring or image is uneven (problem is arranged in the practicality).
(losing quantity of photoreceptor)
Carry out 100,000 printings in the above-mentioned evaluation, use the film thickness difference behind initial stage thickness and 100,000 to estimate.For the thickness of photographic layer, measure homogeneous thickness part (because the thickness at the two ends of photoreceptor is inhomogeneous easily, so remove two ends 5cm at least) with being intended to 10 places, with the thickness of its mean value as photographic layer.The determining film thickness device uses the determining film thickness device EDDY560C (manufacturing of HELMUTFISCHER GMBTE CO company) of vortex flow mode to measure, and calculates apart from the losing quantity of initial stage thickness (27.3 μ m).
(solvent solubility, coating fluid keeping quality)
To the cementing agent of the charge transport layer of photoreceptor 1 to 26, estimate the solvent solubility of coating fluid and the keeping quality of coating fluid.For solvent solubility, estimate the dissolubility of resin glue etc. when under following 3 condition, making coating fluid.
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 makes)
2000 parts of toluene/tetrahydrofurans=1.5/8.5 (portion)
1 part of silicone oil (KF-54: chemical company of SHIN-ETSU HANTOTAI makes)
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 makes)
2000 parts of tetrahydrofurans
1 part of silicone oil (KF-54: chemical company of SHIN-ETSU HANTOTAI makes)
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 makes)
Methyl isobutyl ketone/dimethylbenzene/tetrahydrofuran=3/,3/4 2000 part
1 part of silicone oil (KF-54: chemical company of SHIN-ETSU HANTOTAI makes)
For the coating fluid keeping quality, the coating fluid of condition 1, condition 2, condition 3 is carried out preserving in 5 ℃, 48 hours (cryopreservation) and preserved (high temperature preservations) in 30 ℃, 48 hours, no change is arranged after estimating each coating fluid preservation.
The metewand of solvent solubility
A: uniform dissolution easily is no problem fully.
B: dissolving is difficult slightly, is the level of qualified lower limit.
C: a part is dissolving not, produces precipitation, but the dilution back just can be dissolved a little.But because the concentration of coating fluid is low slightly, so be disadvantageous for the manufacturing of photoreceptor.
D: solubleness is obviously not enough, needs the dilution more than 5 times to dissolve, and does not have practicality.
The conservatory metewand of coating fluid
A: no problem fully.
B: have the tendency of gelation slightly during cryopreservation, but be spendable level.
C: separate out during cryopreservation.
D: separating out of defective level all arranged under any preservation condition.
Evaluation result is summarized in the following table 7.
As shown in Table 7, in the 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 in each assessment item than having the better result of practicality, but deterioration greatly 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 big, potential change after 100,000 is also big, the evaluation deterioration of coloured image, result be existing problems aspect practicality all.In addition, though 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, though in the evaluation of current potential evaluation, coloured image, can guarantee sufficient practicality, poorer slightly than photoreceptor 1 to 20 aspect solvent solubility, coating fluid keeping quality.
Claims (8)
1. an Electrophtography photosensor has photographic layer on the electric conductivity supporter, it is characterized in that, photographic layer contains the resin glue of structural unit of (1) expression that has general formula,
General formula (1)
In the general formula (1), R
1Expression has the divalent group of 3 above aromatic rings, R
2Expression and R
1Different divalent groups with 2 above aromatic rings, R
3Expression divalent organic group.
2. Electrophtography photosensor as claimed in claim 1 is characterized in that, the R in the general formula (1)
3Be by dicarboxylic acid R
3(COOH)
2The divalent organic group of deriving, R
1Be by the 1st glycol R
1(OH)
2The divalent group of deriving, R
2Be by the 2nd glycol R
2(OH)
2The divalent group of deriving.
3. Electrophtography photosensor as claimed in claim 2 is characterized in that, the 1st glycol R
1(OH)
2Be the aromatic diol compound of following general formula (2),
General formula (2)
HO-φ
1-A
1-φ
2-A
2-...-A
j-1-φ
j-OH
φ
1, φ
2... φ
jThe expression aromatic rings, j is the integer more than 3,
A
1, A
2... A
J-1For being selected from-CR
11R
12-,-R
13,-O-,-group in S-and the Direct Bonding, j is the integer more than 3,
Wherein, R
11, R
12Expression alkyl, allyl, aryl, alkoxy, halogen, R
11And R
12Can form ring, R by bonding
13The expression carbon number is the alkylidene more than 2,
The 2nd glycol R
2(OH)
2Be the aromatic diol compound of general formula (3),
General formula (3)
HO-φ
1-B
1-φ
2-B
2-...-B
k-1-φ
k-OH
φ
1, φ
2... φ
kThe expression aromatic rings, k is the integer more than 2,
B
1, B
2... B
K-1For being selected from-CR
21R
22-,-R
23-,-O-,-S-,-SO
2-and Direct Bonding in group, k is the integer more than 2,
Wherein, R
21, R
22Expression alkyl, allyl, aryl, alkoxy, halogen, R
21And R
22Can form ring, R by bonding
23The expression carbon number is the alkylidene more than 2.
4. Electrophtography photosensor as claimed in claim 3 is characterized in that, the 1st glycol R
1(OH)
2For be selected from general formula (2a) and (2b) in more than one diol compound,
General formula (2a)
General formula (2b)
In general formula (2a), the general formula (2b), R is the group that is selected from alkyl, allyl and the aryl,
R and R can form other ring by bonding, and whole R can be the same or different.
5. Electrophtography photosensor as claimed in claim 3 is characterized in that, the 2nd glycol R
2(OH)
2For being selected from more than one the diol compound in following general formula (3a)～general formula (3c),
General formula (3a)
General formula (3b)
General formula (3c)
In general formula (3a)～general formula (3c), R is the group that is selected from alkyl, allyl and the aryl,
R and R can form other ring by bonding, and whole R can be the same or different.
6. Electrophtography photosensor as claimed in claim 3 is characterized in that, the 2nd glycol R
2(OH)
2For be selected from following general formula (3d) and (3e) in more than one aromatic diol compound,
General formula (3d)
General formula (3e)
Among general formula (3d), (3e), R is the group that is selected from alkyl, allyl and the aryl,
R and R can form other ring by bonding, and whole R can be identical functional group, also can be slightly different functional group.
7. image processing system has charged elements, exposing unit and developing cell at least at the periphery of Electrophtography photosensor, carries out image repeatedly and forms, and it is characterized in that this Electrophtography photosensor is the described Electrophtography photosensor of claim 1.
8. a handle box is characterized in that, have the described Electrophtography photosensor of claim 1 integratedly and be selected from charged elements, cleaning unit, as at least one unit in exposing unit and the developing cell, and can be loaded and unloaded on image processing system.
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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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|---|---|
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|---|---|---|---|
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| CN (1) | CN101930185B (en) |
Cited By (2)
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| 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 |
| CN109690420A (en) * | 2016-11-30 | 2019-04-26 | 京瓷办公信息系统株式会社 | Electrophotographic Photoreceptor |
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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 |
| EP3249471B1 (en) * | 2016-05-27 | 2019-03-20 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
| 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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| JP2001290288A (en) * | 2000-04-04 | 2001-10-19 | Mitsubishi Chemicals Corp | Electrophotographic photoreceptor |
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| JP2011007914A (en) | 2011-01-13 |
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