CN1912751A

CN1912751A - Electrophotographic photoreceptor and method of preparing the photoreceptor, and image forming method, image forming apparatus and process cartridge therefor using the photoreceptor

Info

Publication number: CN1912751A
Application number: CN 200610105428
Authority: CN
Inventors: 梁川宜辉; 河崎佳明; 铃木哲郎
Original assignee: Ricoh Co Ltd
Current assignee: Ricoh Co Ltd
Priority date: 2005-07-06
Filing date: 2006-07-06
Publication date: 2007-02-14
Anticipated expiration: 2026-07-06
Also published as: JP4440175B2; CN1912751B; JP2007017633A

Abstract

An electrophotographic photoreceptor, includes at lest an electroconductive substrate and a photosensitive layer including at least a tri- or more functional radical polymerizing monomer having no charge transport structure and a monofunctional radical polymerizing compound having a charge transport structure, wherein the photosensitive layer includes radical polymerizing functional groups in an amount of from 2.55*10<21> to 7.50*10<21> in 1g of solid contents thereof, and has a peel strength not less than 0.1 N/mm when measured by the SAICAS method.

Description

Electrophtography photosensor, method for making, the imaging method that uses it, device and handle box

Technical field

The present invention relates to the method for a kind of Electrophtography photosensor and this photoreceptor of preparation, and formation method, imaging device and the handle box (process cartridge) that use this photoreceptor.

Background technology

Recently, Organophotoreceptor (OPCs) is because its superperformance and advantage have replaced inorganic photoreceptor to be widely used in duplicating machine, fax, laser printer and their composite set.The performance that it is good and the object lesson of advantage comprise: (1) optical property, for example the absorbing light wavelength of wide region and a large amount of absorbing light; (2) electrical property, for example high sensitivity and stable polarizability; (3) material is selected; (4) good manufacturability; (5) low cost; (6) avirulence, or the like.

On the other hand, recently along with imaging device is more and more littler, the diameter of photoreceptor is also more and more littler.In addition, because imaging device forms image and service free at a relatively high speed, thereby require photoreceptor to have high durability.In this respect, Organophotoreceptor generally has the soft top layer that is formed by low-molecular-weight charge transporting material and inactive polymkeric substance, therefore Organophotoreceptor generally has when reusing in electrophotographic processes, is easy to produce the shortcoming of abrasion with image developer and with clearer.In addition, owing to require high-quality image, the particle diameter of toner-particle is more and more littler, and thereupon, for improving cleanability, cleaning blade (cleaning blade) must have higher rubber hardness and contact pressure, and it has also accelerated the abrasion to photoreceptor.The abrasion of this photoreceptor has damaged its electrical property, for example light sensitivity and polarizability, and generation abnormal image, for example image density deterioration and background fouling.When the local abrasion of photoreceptor, because defective cleaning can produce the image with blackstreak.At present, because this abrasion and infringement need to change photoreceptor.

Therefore, the essential wear extent of Organophotoreceptor that reduces is so that obtain high durability.This is the problem that presses for solution in this field most.

The method that is used to improve the photoreceptor wearing quality comprises: (1) Japanese publication 56-48637 discloses the photoreceptor that uses the bonding agent of sclerosis on the top layer; (2) Japanese publication 64-1728 discloses the photoreceptor that uses charge transfer polymerization thing material; (3) Japanese publication 4-281461 discloses the photoreceptor that the inorganic filler of dispersion is arranged in the top layer.(1) use the photoreceptor of the bonding agent of sclerosis in, it helps to improve rest potential, and because the bad solubleness of bonding agent and charge transporting material and impurity (for example polymerization initiator and unreacted residue) has reduced image density.(2) use the photoreceptor and the top layer in (3) of charge transfer polymerization thing material to have the photoreceptor that disperses inorganic filler in, the two has wearing quality to a certain extent, but all can not be fully satisfactory.In addition, there is the photoreceptor that disperses inorganic filler on the top layer in (3), and it helps to improve rest potential, and owing to there is capture on inorganic filler surface, image density reduces.(1) any photoreceptor in (3) does not have the comprehensive durability that is entirely satisfactory, for example electric durability and mechanical robustness.

For improving the wearing quality of photoreceptor in (1), Jap.P. 3262488 discloses a kind of photoreceptor that contains the hardening polyurethane acrylate.Yet although Jap.P. 3262488 discloses the photosensitive layer that comprises the hardening polyurethane acrylate, it only discloses wherein can comprise charge transporting material, and does not have to disclose its concrete example.When only comprising the low-molecular-weight charge transporting material in the photosensitive layer, low-molecular-weight charge transporting material and hardening polyurethane acrylate are immiscible, and the low-molecular-weight charge transporting material is separated, and these can cause the physical strength deterioration of the photoreceptor that makes, for example cracking.In addition, Jap.P. 3262488 discloses to improving solubleness and comprised polycarbonate resin in photosensitive layer.Yet the reduction of hardening polyurethane acrylate content has caused the not enough of photoreceptor wearing quality.The photoreceptor that does not comprise charge transporting material in the top layer is thin for the current potential deterioration of radiation component, thereby has than short life.In addition, the charging potential of this photoreceptor has bad stability for environment.

As the wear-proof technique of the alternative a kind of photosensitive layer of above-mentioned technology, Jap.P. 3194392 discloses and has used the coating fluid that is formed by the monomer with carbon-to-carbon double bond, the charge transporting material with carbon-to-carbon double bond and adhesive resin to prepare the method for electric charge migrating layer.Adhesive resin comprises: contain carbon-to-carbon double bond, and can with the adhesive resin of charge transporting material reaction, and neither contain carbon-to-carbon double bond also not with the adhesive resin of charge transporting material reaction.This photoreceptor has good wearing quality and electrical property.Yet, when adhesive resin do not have with charge transporting material (for example, acrylic polymers, styrene polymer, acrylate styrol copolymer (acrylic styrene copolymer), vibrin, polycarbonate resin and epoxy resin) reactive the time, the bonded amount that contains the monomer of carbon-to-carbon double bond and contain between the charge transporting material of carbon-to-carbon double bond reduces, and causes the photosensitive layer cross-linking density not enough.In addition, because adhesive resin itself does not have toughness, thereby the photosensitive layer that obtains does not have gratifying wearing quality.

Japan publication 2000-66425 discloses a kind of photosensitive layer that comprises sclerosis hole (positive hole) migration compound, and this compound contains two or more chain polymerization functional group in same molecule.Yet because photosensitive layer includes the loose hole transporting material that contains two or more chain polymerization functional group, hardening compound distortion can occur and internal stress increases, thereby makes the top layer become coarse and cracking takes place, and causes the photoreceptor poor durability of gained.

Japan publication 2004-302450,2004-302451 and 2004-302452 disclose a kind of crosslinked electric charge migrating layer, the simple function radical polymerization compound sclerosis that will not have three or polyfunctional free yl polymerizating monomer of charge migration structure and have the charge migration structure in this electric charge migrating layer, this simple function radical polymerization compound with charge migration structure have improved the permanance of the machinery of electric charge migrating layer and electricity and have prevented this slabbingization.Yet, when the crosslinked top layer of preparation, in order to obtain high-wearing feature, containing the acrylic monomer sclerosis that a large amount of acrylic functional are rolled into a ball.Because the acrylic material of sclerosis has big volumetric contraction, make top layer and following photosensitive layer adhesiveness deficiency.When this type of photoreceptor is used for when it has applied very the imaging device of great machinery stress, separate with photosensitive layer on crosslinked top layer, causes keeping enough wearing qualities for a long time.

Japan publication 2001-183857 and 2001-183858 disclose the preparation method who prepares the coating fluid that is used for photoreceptor, this coating fluid comprises the structural unit with the transportable property of electric charge, can form the resin bed that combines with organopolysiloxane resins on its crosslinked top layer.The coating fluid per unit weight contains many polymer functional groups, and can form harder crosslinked top layer.Yet the volumetric contraction of this hardened material is so significantly, to such an extent as to crosslinked top layer and lower floor's adhesion are relatively poor.That is, crosslinked top layer is easy to separate with photosensitive layer, causes keeping long-term enough wearing qualities.In addition, according to electrostatic stabilization, this crosslinked top layer can not thicken, thereby causes obtaining gratifying wearing quality.

Owing to these reasons, need to obtain a kind of photoreceptor, and obtain long-term high quality graphic with excellent durability and stable electrical character.

Summary of the invention

Therefore, an object of the present invention is to provide a kind of photoreceptor, and obtain long-term high quality graphic with excellent durability and stable electrical.

Another object of the present invention provides the method for this photoreceptor of preparation.

Another object of the present invention provides the formation method that uses this photoreceptor.

Another object of the present invention provides the imaging device that uses this photoreceptor.

Another object of the present invention provides the handle box that uses this photoreceptor.

These purposes of the present invention and other purpose, each all or jointly is met by the invention of Electrophtography photosensor respectively, and this Electrophtography photosensor comprises:

The base material of electric conductivity and

Photosensitive layer, this photosensitive layer comprise three or polyfunctional free yl polymerizating monomer with charge migration structure and the simple function radical polymerization compound with charge migration structure at least;

Wherein the amount of the contained free radical polymerization of this photosensitive layer functional group is 2.55 * 10 ²¹-7.50 * 10 ²¹/ 1g photosensitive layer solid constituent, and the peel strength of photosensitive layer is no less than 0.1N/mm when measuring by the SAICAS method.

To further specify these purposes of the present invention and other purpose, characteristic and advantage by elaboration the preferred embodiments of the invention and corresponding accompanying drawing below.

Description of drawings

Further describe various purpose of the present invention, characteristic and corresponding advantages with accompanying drawing below, make it be understanded better and to understand.In the present invention, the part that identical Reference numeral is corresponding identical, and wherein

Figure 1A and 1B are the synoptic diagram of xsect of first embodiment of explanation Electrophtography photosensor of the present invention.

Fig. 2 A and 2B are the synoptic diagram of xsect of second embodiment of explanation Electrophtography photosensor of the present invention.

Fig. 3 is the synoptic diagram of the embodiment of explanation imaging device of the present invention.

Fig. 4 is the synoptic diagram of the embodiment of explanation handle box of the present invention.

Fig. 5 is the synoptic diagram of xsect of the 4th embodiment of explanation Electrophtography photosensor of the present invention.

Fig. 6 is the synoptic diagram of xsect of the 5th embodiment of explanation Electrophtography photosensor of the present invention.

Fig. 7 is the titanyl phthalocyanine X-ray diffraction in crystals spectrum that is used for the embodiment of the invention.

Fig. 8 is cross section scanning electron microscope (SEM) photo of the Electrophtography photosensor among the embodiment 17; And

Fig. 9 is cross section scanning electron microscope (SEM) photo of the Electrophtography photosensor in the Comparative Examples 13.

Embodiment

The invention provides a kind of photoreceptor, and obtain long-term high quality graphic with excellent durability and stable electrical.

Photoreceptor of the present invention comprises three in top layer or multifunctional free yl polymerizating monomer, and this monomer forms three-dimensional network, thereby makes the top layer become very hard cross-linked layer, and this cross-linked layer has high crosslink density and high-wearing feature.And when only using the monomer that contains less free radical polymerization functional group, the bad and crosslinked top layer that becomes of crosslink bond does not wherein have significant wearing quality.When containing polymeric material in the photoreceptor, can damage the formation of three-dimensional network, and can reduce wherein crosslinked, thereby it is relatively poor to cause this photoreceptor and the photoreceptor among the present invention to compare wearing quality.In addition, because polymeric material and hardened material compatibility are relatively poor, this hardened material is by polymeric material and free radical polymerization component (promptly, free yl polymerizating monomer and radical polymerization compound with the transportable structure of electric charge) reaction obtains, thus cause the separation of layer and produce the damage on local wearing and tearing and surface.Crosslinked top layer of the present invention has the permanance of improvement, it comprises: do not have three or polyfunctional free yl polymerizating monomer of charge migration structure and the simple function radical polymerization compound with charge migration structure, these two kinds of components are sclerosis simultaneously at short notice, has the crosslinked of high rigidity with formation.In addition, the improvement of setting rate can form smooth layer, and its good cleanability (cleanability) can keep for a long time.In addition, can form uniform cross linking membrane in the top layer with less distortion.In addition, owing to contain the simple function radical polymerization compound with charge migration structure, this cross-linked layer has electrical property steady in a long-term.When the low-molecular-weight charge transporting material with functional group was contained on crosslinked top layer, cloud form decorative pattern (clouded) is separated and formed to this low-molecular-weight charge transporting material, and the physical strength deterioration on crosslinked top layer.When two or polyfunctional charge migration compound is contained on crosslinked top layer,, thereby cause the top layer that cracking and breakage often take place to such an extent as to the charge migration structure is that so the internal stress in the huge crosslinked top layer increases.In addition, when charge migration, intermediate structure (cation group) can not stably keep, and owing to the increase of trap-charge and rest potential, causes the deterioration of sensitivity (sensitivity).The deterioration of these electrical properties causes the deterioration of image density and the shoaling of character image that obtain.Therefore, the invention provides and a kind ofly for a long time the wearing quality with improvement of cracking and the photoreceptor of stable electrical do not take place, and obtain long-term high quality graphic.

Crosslinked top layer of the present invention has higher cross-linking density, and this top layer comprises that content is 2.55 * 10 ²¹-7.50 * 10 ²¹The free radical polymerization functional group of/1g solid constituent.That is, wherein highly form three-dimensional network, and crosslinked top layer has significant high-wearing feature, high rigidity and elasticity.

The amount of the free radical polymerization functional group in the 1g solid constituent can be measured by following method:

(1) weight/molecular weight=mol;

(2) mol * avogadros constant (6.02 * 10 ²³Mol ^-1)=molecular amounts;

(3) number of the number=functional group of functional group of molecular amounts * per molecule; And

(4) all contain the general assembly (TW) of the sum of functional group in the material of free radical polymerization functional group divided by solid constituent, thereby have measured the number of free radical polymerization functional group in the 1g solid constituent.

In addition, crosslinked top layer of the present invention is no less than 0.1Nmm by its peel strength that the SAICAS method measures, and it has enough adhesivenesses and do not produce with lower floor and separates.

Next will set forth the coating fluid on crosslinked top layer of the present invention.

The object lesson that does not have three or polyfunctional free yl polymerizating monomer of charge migration structure comprises the free yl polymerizating monomer with three or more free radical polymerization functional group, for example acryloxy and methacryloxy.

Compound with three or more acryloxy can prepare by the following method: for example the compound with three or more hydroxyl and acrylic acid (salt), halogenide acrylate (halide acrylate) or ester acrylate (ester acrylate) are carried out esterification or ester exchange reaction.The compound that can have three or more methacryloxy according to similar method preparation.The free radical polymerization functional group that has in the monomer of three or more free radical polymerization functional group can be identical or different.

The concrete example that does not have three or polyfunctional free yl polymerizating monomer of charge migration structure comprises following material, but is not limited only to this.

Promptly, can use trimethylolpropane triacrylate (TMPTA), trimethylol-propane trimethacrylate, HPA-modification trimethylolpropane triacrylate, EO-modification trimethylolpropane triacrylate, PO-modification trimethylolpropane triacrylate, caprolactone-modification trimethylolpropane triacrylate, HPA-modification trimethylol-propane trimethacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate (PETTA), three acrylic acid glyceride, ECH-modification three acrylic acid glyceride, EO-modification three acrylic acid glyceride, PO-modification three acrylic acid glyceride, three (acryloxy ethyl) isocyanuric acid ester, dipentaerythritol acrylate (DPHA), caprolactone-modification dipentaerythritol acrylate, dipentaerythritol hydroxyl five acrylate, alkyl-modification dipentaerythritol five acrylate, alkyl-modification dipentaerythritol tetraacrylate, alkyl-modification dipentaerythritol triacrylate, dihydroxy methylpropane tetraacrylate (DTMPTA), pentaerythrite ethoxy tetraacrylate, 2,2,5,5-tetrakis hydroxymethyl phosphonium cyclopentanone tetraacrylate, or the like.These compounds can be used alone or in combination.These modified monomers have lower viscosity makes its easy processing.

The ratio (molecular weight/number of functional groups) that is used for the number of functional groups of preferred its molecular weight of three or the polyfunctional free yl polymerizating monomer that does not have a charge migration structure of the present invention and monomer is not more than 250.When ratio greater than 250 the time, soft and its wearing quality in the crosslinked top layer that obtains slightly reduces.Therefore, HPA-, the EO-or the preferred use separately of PO-modified monomer that have very long modification group.

Three or the polyfunctional free yl polymerizating monomer that do not have the charge migration structure of 20-80 weight %, more preferably 30-70 weight % are preferably contained in crosslinked top layer.When the content of this monomer was less than 20 weight %, the three-dimensional cross-linked bonding density on crosslinked top layer was not enough, and its wearing quality is not compared and significantly improved with the layer that contains the traditional hot plastic resin.When the content of this monomer during greater than 80 weight %, the content of charge migration compound reduces and the electrical property of the photoreceptor that obtains reduces.

Being used for the radical polymerization compound with simple function of charge migration structure of the present invention is to have hole (positive hole) migration structure, for example triarylamine, hydrazone, dihydropyazolo and carbazole, perhaps electron transfer structure, for example fused polycycle quinone, phenoquinone, cyano group and have the electrophilic aromatic ring of nitro and the compound of free radical polymerization functional group.Can use arbitrary free radical polymerization functional group, as long as these functional groups have carbon-to-carbon double bond and can carry out free radical polymerization.The object lesson of free radical polymerization functional group comprises: 1-substituted ethylene (1-substituted ethylene) functional group, and 1, ethene (1, the 1-substituted ethylene) functional group that 1-replaces, or the like.In these free radical polymerization functional groups, use acryloxy and methacryloxy effectively.In addition, the triarylamine structure can be used as the charge migration structure effectively.

In addition, when compound had following formula (1) or (2), electrical property (for example sensitivity (sensitivity) and rest potential) can preferably be maintained.

Wherein, R ₁Expression hydrogen atom, halogen atom, alkyl replacement or non-replacement, aralkyl replacement or non-replacement, aryl replacement or non-replacement, cyano group, nitro, alkoxy ,-COOR ₂(R wherein ₂Expression hydrogen atom, halogen atom, alkyl replacement or non-replacement, aralkyl replacement or non-replacement, aryl replacement or non-replacement, carbonyl halide) or CONR ₃R ₄(R wherein ₃And R ₄Represent hydrogen atom, halogen atom, alkyl replacement or non-replacement, aralkyl replacement or non-replacement, aryl replacement or non-replacement independently);

Ar ₁And Ar ₂Represent arlydene that replace or non-replacement independently;

Ar ₃And Ar ₄Represent aryl that replace or non-replacement independently;

X represents alkylidene singly-bound, replacement or non-replacement, ring alkylidene replacement or non-replacement, alkylene ether replacement or non-replacement (alkyleneether) group, oxygen atom, sulphur atom and ethenylidene;

Z represents the alkylidene of that replace or non-replacement, alkylene ether group replacement or non-replacement, alkylene oxide group carbonyl (alkyleneoxycarbonyl);

M and n represent 0 and the integer of 1-3.

At formula (1) and (2) lining, R ₁Substituted radical in, alkyl comprises methyl, ethyl, propyl group, butyl, or the like; Aryl comprises phenyl, naphthyl (naphtyl), or the like; Aralkyl comprises benzyl, phenethyl, naphthyl methyl, or the like; And alkoxy comprises methoxyl, ethoxy, propoxyl group, or the like.These can be replaced by following group: alkyl, as halogen atom, nitro, cyano group, methyl and ethyl; Alkoxy is as methoxyl and ethoxy; Aryloxy group is as the phenoxy group group; Aryl is as phenyl and naphthyl; Aralkyl is as benzyl and phenethyl.

R ₁Substituted radical preferably hydrogen atom and methyl.

Ar ₃And Ar ₄Represent aryl that replace or non-replacement independently, its concrete example comprises: fused polycycle hydrocarbyl group, non--fused rings hydrocarbyl group and heterocyclic group.

The fused polycycle hydrocarbyl group preferably has 18 or the still less group of carbon atom, for example fentanyl group, indenyl, naphthyl, Azulene base (azulenyl), heptalene base, biphenylene, As-benzo two indenyls (indacenyl), fluorenyl, acenaphthylene base, praadenyl, acenaphthenyl, phenalenyl, luxuriant and rich with fragrance tolyl (phenantolyl), anthryl, fluoranthene base, the luxuriant and rich with fragrance thiazolinyl (acephenantolylenyl) of vinegar, benzo acenaphthylene base (aceanthrylenyl), triphenylel, pyrenyl,  base (crycenyl) and the naphtho-naphthyl (naphthacenyl) that forms ring.

The concrete example of non--fused rings hydrocarbyl group and heterocyclic group comprises: the monoradical of monocyclic hydrocarbon compound, for example benzene, diphenyl ether, poly-ethylene phenyl ether, diphenylsulfide and diphenyl sulfone; The monoradical of non--hydrocarbon compound of condensing, for example biphenyl, polyphenyl, hexichol alkane, hexichol alkene, two benzynes, triphenyl methane, diphenylethyllene benzene, 1,1-hexichol naphthenic hydrocarbon, polyphenylene alkane and polyphenylene alkene; And ring set hydrocarbon (ring gathering hydrocarbon) compound, for example 9,9-hexichol fluorenes.

The concrete example of heterocyclic group comprises univalent perssad, for example carbazole, dibenzofuran, dibenzothiophen,  diazole and thiadiazoles.

Ar ₃And Ar ₄The concrete example of aryl replacement or non-replacement of representative comprises following groups:

(1) halogen atom, cyano group and nitro;

(2) have 1-12 carbon atom, preferred 1-8 carbon atom, the more preferably straight or branched alkyl of 1-4 carbon atom, and these alkyl can further contain fluorine atom, hydroxyl, cyano group, the alkoxy with 1-4 carbon atom, phenyl or halogen atom, have the alkyl of 1-4 carbon atom or the phenyl that is replaced by the alkoxy with 1-4 carbon atom.The concrete example of alkyl comprises: methyl, ethyl, normal-butyl, isopropyl, the tert-butyl group, sec-butyl (s-butyl), n-pro-pyl, trifluoromethyl, 2-hydroxyethyl, 2-ethoxyethyl group, 2-cyano ethyl, 2-methoxy ethyl (methocyethyl), benzyl, 4-benzyl chloride base, 4-methyl-benzyl, 4-phenylbenzyl etc.

(3) alkoxy (OR2), R wherein ₂The alkyl that limits in the expression (2).Its concrete example comprises: methoxyl, ethoxy, positive propoxy, isopropoxy, tert-butoxy, sec-butoxy (s-butoxy), isobutoxy, 2-hydroxyl-oxethyl, benzyloxy, trifluoromethoxy, or the like.

(4) aryloxy group, and the concrete example of this aryl comprises phenyl and naphthyl.These aryl can comprise: have 1-4 carbon atom alkoxy, have the alkyl of 1-4 carbon atom, perhaps halogen atom is as substituting group.The object lesson of aryloxy group comprises: phenoxy group, 1-naphthoxy, 2-naphthoxy, 4-methoxyl phenoxy group, 4-methylphenoxy, or the like.

(5) alkyl thiol or aryl sulfydryl, for example methyl mercapto, ethylmercapto group, thiophenyl and right-methylbenzene sulfenyl.

(6)

R wherein ₁₀And R ₁₁Alkyl and the aryl of representing qualification in hydrogen atom, (2) independently, and the concrete example of aryl comprises phenyl, xenyl and naphthyl, and these groups can comprise that the alkoxy with 1-4 carbon atom, the alkyl with 1-4 carbon atom or halogen atom are as substituting group.In addition, R ₁₀And R ₁₁Can form ring together.Concrete example with group of this formula comprises: amino, diethylamino, N-methyl-N-phenyl amino, N, and N-diphenyl amino, N-N-two (tolyl) amino, dibenzyl amino, piperidyl, morpholinyl, pyrrolidinyl, or the like.

(7) methylenedioxy group, alkylenedioxy group group, for example methylene disulfide group or alkylidene disulfide group.

(8) styryl that replace or non-replacement, beta-phenyl styryl, diphenyl amino phenyl, the xylyl aminophenyl of replacement or non-replacement, or the like.

Ar ₁And Ar ₂The arylene group of expression is Ar ₃And Ar ₄The divalent group of deriving of the aryl of expression.

The above-mentioned X that mentions represents alkylidene singly-bound, replacement or non-replacement, ring alkylidene replacement or non-replacement, alkylene ether group replacement or non-replacement, oxygen atom, sulphur atom and ethenylidene.

Alkylidene that replace or non-replacement is to have 1-12 carbon atom, preferred 1-8 carbon atom, the more preferably straight or branched alkylidene of 1-4 carbon atom, and these alkylidenes may further include fluorine atom, hydroxyl, cyano group, the alkoxy with 1-4 carbon atom, phenyl or halogen atom, have the alkyl of 1-4 carbon atom or had the phenyl that the alkoxy of 1-4 carbon atom replaces.The concrete example of alkylidene comprises: methylene, ethylidene, just-butylidene, different-propylidene, uncle-butylidene, the second month in a season-butylidene, just-propylidene, trifluoro methylene, 2-hydroxy ethylene, 2-ethoxy ethylidene, 2-cyano group ethylidene (cyanoethylene), 2-methoxyl ethylidene (methocyethylene), benzylidene, phenylethylene, 4-chlorobenzene ethylidene, 4-methylbenzene ethylidene, 4-xenyl ethylidene, or the like.

Ring alkylidene that replace or non-replacement is the cyclic alkylidene with 5-7 carbon atom, and these alkylidenes can comprise fluorine atom, hydroxyl, cyano group, have the alkoxy of 1-4 carbon atom.Its concrete example comprises: ring hexylidyne (cyclohexylidine), cyclohexylidene and 3, and 3-diformazan basic ring hexylidyne, or the like.

The object lesson of alkylene ether group replacement or non-replacement comprises: ethyleneoxy, propenyloxy group (propylene oxy), ethylene glycol, propylene glycol, diglycol, tetraethylene glycol and tripropylene glycol.Alkylidene in the alkylene ether group can comprise the substituting group as hydroxyl, methyl and ethyl.

Ethenylidene has following formula:

Or

R wherein ₁₂Expression hydrogen atom, alkyl (with (2) middle limit identical), aryl are (with Ar ₃And Ar ₄Those of expression are identical); A represents 1 or 2; B represents 1,2 or 3.Z represents the alkylidene of that replace or non-replacement, divalent alkyl ether group replacement or non-replacement and divalence alkylene oxide group carbonyl.The object lesson of alkylidene replacement or non-replacement comprises those that X represents.The object lesson of divalent alkyl ether group replacement or non-replacement comprises those that X represents.The object lesson of divalence alkylene oxide group carbonyl comprises caprolactone-modification group.

In addition, the simple function radical polymerization compound that has the charge migration structure among the present invention more preferably has the compound of following formula (3).

Wherein o, p, q represent 0 or 1 independently; R ₅Expression hydrogen atom or methyl; Each R ₆And R ₇Expression hydrogen atom and alkyl and other substituting group with 1-6 carbon atom, when the two has a plurality of carbon atom, R ₆And R ₇Can differ from one another; S and t represent 0 or the integer of 1-3; Z _aExpression singly-bound, methylene, ethylidene,

-CH ₂CH ₂O-、

Or

Compound with formula (3) preferably has methyl or ethyl as R ₆And R ₇Substituent compound.

Be used for of the present invention, have formula (1), simple function radical polymerization compound (2) and particularly (3), that have the charge migration structure because carbon-carbon double bond is in polymerization when open both sides, therefore do not form end structure and form chain polymer.With the cross-linked polymer of free yl polymerizating monomer polymerization with three or more functional group in, this compound is present in the main chain and is present in that (cross linked chain is included in intermolecular cross-linking chain and the intramolecular crosslinking chain between polymkeric substance and another polymkeric substance in the cross linked chain between main chain, wherein, have the part of folding main chain and derive from monomer another partly carry out polymerization, this monomer with main chain on its away from the position phase-polymerization).Even when compound is present in main chain or the cross linked chain, the triarylamine structure that poises on the chain has at least three radially from the aryl of nitrogen-atoms location, its directly with chain bonding mutually, and dangle by carbonyl or similar group.But though triarylamine structure ground, huge space and fixing flexibly.The triarylamine structure can space orientation (spatially be located), makes it moderately lean on mutually each other in polymkeric substance, and have less malformation in molecule.Therefore, think that the simple function radical polymerization compound with charge migration structure in the top layer of Electrophtography photosensor can have intramolecular structure, wherein can relatively prevent the obstruction of charge migration route.

Concrete example with simple function radical polymerization compound of charge migration structure comprises the compound with following formula, but is not limited only to this.

In addition, in the present invention, also preferably specific (methyl) acrylate compounds with following formula (4) is used as the simple function radical polymerization compound with charge migration structure:

B ₁-Ar ₅-CH＝CH-Ar ₆-B ₂ …(4)

Ar wherein ₅Univalent perssad replacement or non-replacement or divalent group that expression is formed by the aromatic hydrocarbon skeleton.The univalent perssad that is formed by the aromatic hydrocarbon skeleton or the concrete example of divalent group comprise: monovalence or divalent group, for example benzene, naphthalene, phenanthrene, biphenyl and 1,2,3,4-tetrahydro-naphthalene.

The substituent concrete example of aromatic hydrocarbon skeleton comprises: have the alkyl of 1-12 carbon atom, the alkoxy with 1-12 carbon atom, benzyl and halogen atom.Further, can be halogen atom or phenyl as substituting group substituted alkyl and alkoxy.

Ar ₆Expression is by the aromatic hydrocarbon skeleton or have univalent perssad or the divalent group that the heterogeneous ring compound skeleton of one or more uncle's amino forms.The aromatic hydrocarbon skeleton that contains uncle's amino has the structure of following formula (A):

R wherein ₁₃And R ₁₄Expression acyl group, alkyl replacement or non-replacement, aryl replacement or non-replacement or alkenyl that replace or non-replacement; Ar ₇The expression aryl; W represents the integer of 1-3.

The object lesson of acyl group comprises acetyl group, propiono, benzoyl, or the like.The object lesson of alkyl replacement or non-replacement comprises the alkyl with 1-12 carbon atom.The object lesson of the aryl of that replace or non-replacement comprises: phenyl, naphthyl, xenyl, terphenyl, pyrenyl, fluorenyl, 9, and 9-dimethyl-fluorenyl, Azulene base, anthryl, Sanya phenyl,  base and have the group of following formula:

Wherein B represent-O-,-S-,-SO-,-SO ₂-,-CO-and following divalent group; R ²¹Expression hydrogen atom, alkyl, alkoxy, halogen atom, aryl above-mentioned replacement or non-replacement, amino, nitro and cyano group with 1-12 carbon atom;

R wherein ²²Represent aryl hydrogen atom, alkyl and above-mentioned replacement or non-replacement with 1-12 carbon atom; I represents the integer of 1-12; J represents the integer of 1-3.

The object lesson of alkoxy comprises: methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, isobutoxy, the second month in a season-butoxy, tert-butoxy, 2-hydroxyl-oxethyl, 2-cyano group ethoxy, benzyloxy, 4-methyl benzyloxy, trifluoromethoxy, or the like.

The object lesson of halogen atom comprises fluorine atom, chlorine atom, bromine atoms and iodine atom.

Amino object lesson comprises diphenyl amino, xylyl amino, dibenzyl amino, 4-methyl-benzyl, or the like.

The object lesson of aryl comprises: phenyl, naphthyl, xenyl, terphenyl, pyrenyl, fluorenyl, 9,9-dimethyl-fluorenyl, Azulene base, anthryl, Sanya phenyl and  base.

Can replace Ar to the alkyl with 1-12 carbon atom, alkoxy and halogen atom as substituting group ₇, R ₁₃And R ₁₄

Object lesson with heterogeneous ring compound skeleton of one or more uncle's amino comprises: have the heterogeneous ring compound of amine structure, for example pyrroles, pyrazoles, imidazoles, triazole, two  azoles, indoles, iso-indoles, indoline, benzimidazole, benzotriazole, benzoisoxadine, carbazole and phenoxadine.These groups can be the alkyl with 1-12 carbon atom, alkoxy and halogen atom as substituting group.

At least B ₁Or B ₂Be hydrogen atom, and another is an acryloxy; Methacryloxy; Vinyl; Alkyl with acryloxy, methacryloxy or vinyl; Or has an alkoxy of acryloxy, methacryloxy or vinyl.

(methyl) acrylate compounds with formula (4) is preferably the have following formula compound of (5):

R wherein ₈And R ₉That expression replaces or the alkyl of non-replacement, alkoxy replacement or non-replacement and halogen atom; Ar ₇And Ar ₈Expression aryl that replace or non-replacement or arlydene and benzyl that replace or non-replacement; B ₁-B ₄Be and the middle B of formula (1) ₁And B ₂Identical group, and only have one of them; U represents 0 or the integer of 1-5; V represents 0 or the integer of 1-4.

(methyl) acrylate compounds with formula (5) has following performance.(methyl) acrylate compounds is the tertiary amine compound with (developed) stilbene conjugated structure of formation.The electric charge that this type of charge migration compound with conjugated structure of formation has improved cross-linked layer interphase place well injects.In addition, even when being fixed between the crosslink bond, intermolecular interaction still is difficult to weaken and has a transportable property of excellent electric charge.Owing to have content high free radical polymerization acryloxy or a methacryloxy, when radical polymerization fashionable, the gelling and do not produce excessive crosslinked distortion soon of ester (methyl) acrylate compounds.Two keys of stilbene conjugated structure partly participate in polymerization, and to compare polymerization less with acryloxy or methacryloxy, and this has caused the time difference and the not maximization of strain in the cross-linking reaction.In addition, the two keys that participate in polymerization can increase the cross-linking reaction number of per molecule amount, cause higher cross-linking density.In addition, two keys can be controlled polymerization by crosslinked condition, and can easily form optimal cross linking membrane.This type of reaction can realize by ester of the present invention (methyl) acrylate compounds, but can not realize by the two keys of for example α-phenyl stilbene.

Have free radical polymerization functional group and formula (4), the charge migration compound of formula (5) particularly, can form the good electrical property of maintenance and not produce the highly cross-linked film of cracking, this can prevent that particulate material (for example silica) from adhering on the photoreceptor, and can reduce defective white dot image.

Object lesson with charge migration compound of free radical polymerization functional group and formula (4) comprises the compound with following formula I-XVII, but is not limited thereto.

Being used for the simple function radical polymerization compound with charge migration structure of the present invention is indispensable to giving the transportable property of crosslinked top layer electric charge, and its preferred content is 20-80 weight %, and more preferably 30-70 weight % is in general assembly (TW).When content during less than 20 weight %, crosslinked top layer can not keep the transportable property of electric charge, and the sensitivity of the photoreceptor that makes reduces, and the rest potential of photoreceptor increases in repeated use.When content during greater than 80 weight %, the content that does not have three or polyfunctional monomer of charge migration structure reduces, and cross-linking density reduces, thereby the photoreceptor that makes does not have high-wearing feature.Though consumption depends on the wearing quality and the electrical property of needs, consider the balance of the two, have the content 30-70 weight % most preferably of radical polymerization compound of the simple function of charge migration structure.

Crosslinked top layer of the present invention has the peel strength that is no less than 0.1N/mm.Peel strength is to lead under ultralow speed, employing has the single-crystal diamond cutting blade of the grinding undercut angle (grinding undercut angle) of 60 ℃ nose angle degree, 20 ℃ anterior angle and 10 °, cuts with the method for stripper surface and measures.Specifically, measure the transverse force, vertical force and the perpendicular displacement that put on cutting blade, and peel strength is decided by the transverse force that puts on the cutting blade width.Under the constant temperature and humidity state, measure peel strength.In the present invention, peel strength is measured under 22 ℃ and 55%Rh.

In the present invention, use the SAICAS DN-20 of DAIPLA WINTES company limited, its cutting blade is that 0.5mm is wide.Here can use any device with similar effect.In the present invention, photoreceptor of the present invention can suitably cutting on aluminium cylinder (cylinder).The crosslinked top layer that peel strength is no less than 0.1N/mm has with the enough adhesiveness of lower floor and do not produce peels off.

In order to improve the adhesiveness on crosslinked top layer, preferably use saturation vapour pressure to be not more than 100mmHg/25 ℃ solvent in the present invention.When crosslinked top layer was applied, this kind solvent reduced except that the surperficial swelling of (de-solvent) amount and lower floor or the slightly dissolving of desolvating.Therefore, can infer that having successional zone is that interphase near top layer and lower floor forms, it does not have fast physical change.Therefore, crosslinked top layer has enough adhesivenesses.In addition, in the present invention, the solvent that exists slightly in the crosslinked top layer promotes free radical reaction wherein, thereby improves the uniform rigidity on crosslinked top layer.Saturation vapour pressure is not more than 100mmHg/25 ℃ solvent can not accumulate internal stress locally in crosslinked top layer, and forms uniformly and the crosslinked top layer of distortion not.Residual solvent amount when forming crosslinked top layer in the crosslinked top layer, more preferably saturation vapour pressure is not more than 50mmHg/25 ℃ solvent, and further preferred saturation vapour pressure is not more than 20mmHg/25 ℃ solvent.

Because can form good interphase between crosslinked top layer and lower floor, preferred boiling point is 60-150 ℃ a solvent, and this can make crosslinked top layer produce enough adhesivenesses.Consider the process of desolvating of removing, for example by heat drying, more preferably boiling point is 100-130 ℃ a solvent.In addition, because have higher affinity with lower floor principal ingredient-polycarbonate, preferred solubility parameters is the solvent of 8.5-11.0, and more preferably solubility parameters is the solvent of 9.0-9.7, thereby makes crosslinked top layer produce enough adhesivenesses.

The solvent object lesson comprises: hydro carbons, for example heptane, octane, trimethylpentane, isooctane, nonane, 2,2,5-trimethyl cyclohexane, decane, benzene,toluene,xylene, ethylbenzene, cumene, styrene, ethyl cyclohexanone and cyclohexanone; Alcohols, for example methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, isobutyl alcohol, uncle-butanols, 1-amylalcohol (penatnol), 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, uncle-amylalcohol, 3-methyl isophthalic acid-butanols, 3-methyl-2-butanols, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 2-ethyl-1-butanols, 3-enanthol, allyl alcohol, propargyl alcohol (propalgyl alcohol), benzylalcohol, cyclohexanol, 1,2-ethylene glycol (ethanodiol) and 1, the 2-propylene glycol; Phenols, for example phenol and cresols; Ethers, for example dipropyl ether, Di Iso Propyl Ether, dibutyl ethers, butyl vinyl ether, benzyl ether, two  alkane, anisole, phenetol and 1,2-epoxy butane; Acetals, acetal, 1 for example, 2-dimethoxy-ethane and 1,2-diethoxyethane; Ketone, for example methyl ethyl ketone, 2 pentanone, methyl-n-butyl ketone, 2-heptanone, diisobutyl ketone, oxidation methyl (methyloxide), cyclohexanone, methyl cyclohexanone, 4-methyl-2 pentanone, diacetone and acetonyl acetone; The ester class, for example ethyl acetate, propyl acetate, butyl acetate, amyl acetate, acetic acid 3-methoxyl butyl ester, diethyl carbonate and acetic acid 2-methoxyl ethyl ester; Halogen, for example chlorobenzene; Sulphur compound, for example thiophane; Compound with a plurality of functional groups, for example 2-methyl cellosolve, cellosolvo, furfuryl alcohol, tetrahydrofurfuryl alcohol, 1-methoxyl-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, diacetone alcohol, furfural, acetic acid 2-methoxyl ethyl ester, acetic acid 2-ethoxy ethyl ester, propylene glycol propyl ether and propylene glycol-1-monomethyl ether-2-acetate; Or the like.Among these solvents,, preferably use butyl acetate, chlorobenzene, diacetone, dimethylbenzene, acetic acid 2-methoxyl ethyl ester, propylene glycol-1-monomethyl ether-2-acetic acid esters and cyclohexanone according to adhesiveness.These solvents may be used singly or in combin.

The dilution rate of solvent arbitrarily determines according to the thickness of solubleness, coating method and the layer of component.Yet, to keep the amount of residual solvent in the crosslinked top layer and give crosslinked top layer enough adhesivenesses in order to form on crosslinked top layer, the solids content of coating fluid preferably is not more than 25 weight %, more preferably 3-15 weight %.

Crosslinked top layer of the present invention forms by preparation solution (coating fluid), coating, drying solution and polymerization and this solution of sclerosis (crosslinked), and this coating fluid comprises three or polyfunctional free yl polymerizating monomer with charge migration structure and the radical polymerization compound with simple function of charge migration structure at least.In addition, coating fluid can comprise simple function with dual functional free yl polymerizating monomer, functional monomer and free radical polymerization oligomer, with the viscosity of control table layer when applying, the friction factor that reduces skin stress, gives its low surface free energy and reduce the top layer.Can use known free yl polymerizating monomer and oligomer.

The object lesson of the free radical monomer of simple function comprises: 2-ethylhexyl acrylate, acrylic acid 2-hydroxyethyl ester, acrylic acid 2-hydroxy-propyl ester, tetrahydrofurfuryl acrylate, acrylic acid 2-ethylhexyl carbitol ester, acrylic acid 3-methoxyl butyl ester, acrylic acid benzene methyl, cyclohexyl acrylate, acrylic acid isopentyl ester, isobutyl acrylate, acrylic acid methoxyl triethyleneglycol ester, acrylic acid phenoxy group tetraethylene glycol ester, Process Conditions of Cetane Acrylate, acrylic acid iso stearyl ester, stearyl acrylate base ester, styrene monomer, or the like.

The object lesson of difunctionality free radical monomer comprises: acrylic acid 1,3-butanediol ester, diacrylate 1,4-butanediol ester, dimethacrylate 1,4-butanediol ester, diacrylate 1,6-hexanediol ester, dimethacrylate 1,6-hexanediol ester, diacrylate diglycol ester, diacrylic acid pentyl diol ester, EO-modified bisphenol A diacrylate, EO-modified bisphenol F diacrylate, or the like.

Functional monomer's object lesson comprises: acrylic acid octafluoro amyl group ester, acrylic acid 2-perfluoro capryl ethyl ester, methacrylic acid 2-perfluoro capryl ethyl ester, the different nonyl ethyl ester of acrylic acid 2-perfluor, or the like, wherein, fluorine atom can be substituted; Vinyl monomer with polysiloxane group, wherein this polysiloxane group has 20-70 siloxane repeat unit (open in open 5-60503 of Jap.P. and 6-45770), for example acryloyl group dimethyl silicone polymer ethyl, methacryl dimethyl silicone polymer ethyl, acryloyl group dimethyl silicone polymer propyl group, acryloyl group dimethyl silicone polymer butyl and two acryloyl group dimethyl silicone polymer diethyl; Acrylate; And methacrylate.

The object lesson of free radical polymerization oligomer comprises epoxy acrylate oligomer, urethane acrylate oligomer and polyoxyalkylene acrylate ester oligomer (polyetseracrylate oligomers).

Yet when crosslinked top layer was contained a large amount of free yl polymerizating monomers and had the free radical polymerization oligomer of one or two functional group, the three-dimensional cross-linked bonding density on crosslinked top layer reduced (deteriorate) basically, causes the wearing quality deterioration on crosslinked top layer.Therefore, the monomer that contains in the top layer of the present invention and the amount of oligomer preferably are not more than 50 weight portions, more preferably no more than 30 weight portions, have three or polyfunctional free yl polymerizating monomer in 100 weight portions.

Crosslinked top layer of the present invention forms by preparation solution (coating fluid), coating, drying solution and polymerization and this solution of sclerosis (crosslinked).This coating fluid comprises three or polyfunctional free yl polymerizating monomer with charge migration structure and the radical polymerization compound with simple function of charge migration structure at least.Coating fluid can be chosen (optionally) wantonly and adopt polymerization initiator (for example thermal polymerization and Photoepolymerizationinitiater initiater) that cross-linking reaction is carried out effectively.

The object lesson of thermal polymerization comprises peroxide initiator, for example 2,5-dimethylhexane-2,5-diperoxy thing (dihydrooxide), cumyl peroxide, benzoyl peroxide, peroxide tert-butyl isopropyl benzene, 2,5-dimethyl-2,5-two (benzoyl peroxide) hexin-3, peroxidating two-tert-butyl group (butylbeloxide), tert butyl hydroperoxide (t-butylhydrobeloxide), cumene hydroperoxide (cumenehydobeloxide) and lauroyl peroxide; And azo initiator, for example azoisobutyronitrile, azo bicyclohexane nitrile (azobiscyclohexanecarbonitrile), azo two different methylbutyrates, azo diisobutyl amidine hydrochloride and 4,4 '-azo is two-the 4-cyanovaleric acid.

The object lesson of Photoepolymerizationinitiater initiater comprises: acetone or ketal Photoepolymerizationinitiater initiater, diethoxy acetophenone, 2 for example, 2-dimethoxy-1,2-diphenylethane-1-ketone, 1-hydroxyl-cyclohexyl-phenyl-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl (molpholinophenyl)) butanone-1,2-hydroxy-2-methyl-1-phenylpropyl alcohol alkane-1-ketone and 1-phenyl-1,2-propanedione (propanedion)-2-(neighbour-ethoxy carbonyl) oxime; Benzoin ether Photoepolymerizationinitiater initiater, for example styrax, styrax methyl ether, styrax ethylether, benzoin isobutyl butyl ether and benzoin isobutyl propyl group ether; The benzophenone Photoepolymerizationinitiater initiater, for example benzophenone, 4-dihydroxy benaophenonel, neighbour-phenacyl benzoic ether, 2-benzoyl naphthalene, 4-benzoyl biphenyl (benzoylviphenyl), 4-benzoyloxy phenyl ether, acroleic acid esterification benzophenone and 1,4-benzoyl benzene (benzoylbenzene); The thioxanthones Photoepolymerizationinitiater initiater, for example 2-isopropyl thioxanthone, 2-clopenthixal ketone, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone and 2,4-two clopenthixal ketones; With other Photoepolymerizationinitiater initiater; EAQ, 2,4 for example, 6-trimethylbenzene formyl diphenyl phosphine oxide, 2; 4; 6-trimethylbenzene formyl diphenyl ethoxy phosphine oxide, two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide, two (2; 4-dimethoxy benzoyl)-2; 4,4-tri-methyl-amyl phosphine oxide, aminomethyl phenyl glyoxylic ester (methylphenylglyoxyester), 9,10-phenanthrene, acridine compound, triaizine compounds and imidazolium compounds.In addition, can use material separately, or itself and above-mentioned Photoepolymerizationinitiater initiater are used in combination with photopolymerization.Object lesson with material of photopolymerization comprises: triethanolamine, methyldiethanolamine, 4-dimethyl aminoethyl benzoic ether, 4-dimethylamino isoamyl benzene formic ether, ethyl (2-dimethylamino) benzoic ether and 4,4-dimethylamino benzophenone.

These polymerization initiators can be used alone or in combination.The polymerization initiator of 0.5-40 weight portion is preferably contained on crosslinked top layer of the present invention, and more preferably 1-20 weight portion is in 100 weight portion radical polymerization compounds.

In addition, coating fluid can randomly comprise various adjuvants, for example plastifier (for reducing skin stress and improving adhesiveness), levelling agent and do not have the low-molecular-weight charge transporting material of free radical reaction.Can use known additives.The object lesson of plastifier comprises the plastifier that is used for general resin, for example Dibutyl phthalate and dioctyl phthalate.The content of plastifier preferably is not more than 20 weight %, more preferably no more than 10 weight %, in the general assembly (TW) of the solid constituent of coating fluid.The object lesson of levelling agent comprises silicone oil, for example dimethyl silicon oil and methyl phenyl silicone oil; And the polymkeric substance and the oligomer that in side chain, contain perfluorinated alkyl.The content of levelling agent preferably is not more than 3 weight %.

Crosslinked top layer can be by dip coated, spray, be coated with limit (bead coating), ring-type cladding process or the like method applies.Because spraying method can be controlled the amount of residual solvent in the crosslinked top layer when forming crosslinked top layer, therefore preferred the use.

In the present invention, coating fluid coated with cambium layer after, this layer is applied external energy forms crosslinked top layer to harden this layer.External energy comprises heating, light and radiation.Use air, gas (as nitrogen), steam, various heating medium, infrared ray or electromagnetic wave, apply heat energy to crosslinked top layer from coated side or from base material.The preferred 100-170 of heating-up temperature ℃.When heating-up temperature was lower than 100 ℃, the slow and reaction of reaction velocity was carried out not exclusively.When temperature of reaction was higher than 170 ℃, reaction was carried out inhomogeneous and on crosslinked top layer big distortion can be taken place.In order to carry out sclerous reaction equably, after the heating, be reflected to be not less than under 100 ℃ and finish effectively under less than 100 ℃ relative low temperature.The object lesson of luminous energy comprises: ultraviolet irradiator, for example high-pressure mercury-vapor lamp, have the metal halide lamp of ultraviolet light emission wavelength; And the visible light source that is suitable for the wavelength of radical polymerization compound and Photoepolymerizationinitiater initiater absorption.The preferred 50-1 of the amount of radiant light, 000 milliwatt/cm ²When radiant light intensity less than 50mW/cm ²The time, sclerous reaction is consuming time.When greater than 1,000 milliwatt/cm ²The time, reaction is carried out surface, inhomogeneous and crosslinked top layer and is had big roughness.Radiation energy comprises the radiation energy that uses electron beam.In these energy,, therefore use them more effective because the reaction velocity of light and heat energy is easy to control and device is simple.

Because crosslinked top layer of the present invention has different thickness, thickness is decided by the layer structure of the photoreceptor that uses crosslinked top layer, therefore will explain the thickness on crosslinked top layer according to the explanation of following layer structure.

Next set forth with reference to the accompanying drawings and be used for Electrophtography photosensor of the present invention.

Figure 1A and 1B are the drawings in side sectional elevation of embodiment of each layer of Electrophtography photosensor of the present invention, and it is served as reasons and has charge generation function and charge migration function and cover the individual layer photoreceptor that the photosensitive layer (33) of conductive substrate (31) forms.In Figure 1A, photosensitive layer is crosslinked fully and sclerosis forms crosslinked top layer.In Figure 1B, crosslinked top layer (32) are formed on photosensitive layer (33) surface.

Fig. 2 A and 2B are the drawings in side sectional elevation of other embodiment of each layer of Electrophtography photosensor of the present invention, the multilayer photoreceptor that its electric charge migrating layer (37) of serving as reasons charge generation layer (35) with charge generation function and having the charge migration function forms, and charge generation layer and electric charge migrating layer cover on the conductive substrate (31).In Fig. 2 A, electric charge migrating layer (37) is crosslinked fully and sclerosis forms crosslinked top layer.In Fig. 2 B, crosslinked top layer (32) are to form on the surface of electric charge migrating layer (37).

The material that is fit to as conductive substrate (31) comprises that volume resistance is not more than 10 ¹⁰The material of Ω cm.The object lesson of this type of material comprises: plastic cylinder, plastic foil or papery sheet material, deposition or splash-proofing sputtering metal (for example aluminium, nickel, chromium, nickel-chrome, copper, gold, silver, platinum or the like) or metal oxide (for example tin oxide, indium oxide or the like) on the surface of these materials.In addition, the sheet material and the metallic cylinder of metal (for example aluminium, aluminium alloy, nickel and stainless steel) also can be used as base material, metal (for example above-mentioned metal) through as impact to squeeze and to draw or directly squeeze the method for drawing and carry out tubulation, the surface of handling pipe then by disposal routes such as cutting, super finishing, polishings, thus make metallic cylinder.In addition, the endless belt of metal (for example nickel and stainless steel) also can be used as base material (31), and it is open in Japanese publication 52-36016.

In addition, can also be the base material that wherein on above-mentioned carrier, has applied the coating fluid that contains adhesive resin and electroconductive powder as base material (31).

The object lesson of electroconductive powder comprises the powder and the metal oxide (for example tin oxide of electric conductivity, ITO or the like) of carbon black, acetylene black, metal (for example aluminium, nickel, iron, nickel-chrome, copper, zinc, silver or the like).The object lesson of adhesive resin comprises known thermoplastic resin, thermoset resin and optical cross-linked resin, for example polystyrene, styrene-acrylonitrile copolymer, Styrene-Butadiene, styrene-maleic anhydride copolymer, polyester, Polyvinylchloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, polyarylate, phenoxy resin, polycarbonate, the cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral resin, vinyl-formal resin, polyvinyl toluene, the poly-N-vinyl carbazole, acrylic resin, organic siliconresin, epoxy resin, melamine resin, urethane resin, phenolics, alkyd resin or the like.Conductive layer can form by the liquid that applies coating fluid, dry this coating, and in coating fluid, electroconductive powder and adhesive resin are dispersed in the solvent, solvent such as tetrahydrofuran, methylene chloride, methyl ethyl ketone, toluene or the like.

In addition, what also can be preferably used as base material (31) is such base material, wherein, with conductive material, on the surface of the cylindrical shape base material that uses the heat-shrinkable pitch tube of making by the combination of resin (as Polyvinylchloride, polypropylene, polyester, polyvinylidene chloride, tygon, chlorinated rubber and TEFLON (registered trademark)), form electroconductive resin film.

Next will set forth photosensitive layer.Photosensitive layer can be individual layer or multilayer.The multilayer photosensitive layer is to be formed by charge generation layer with charge generation function and the electric charge migrating layer with charge migration function.The individual layer photosensitive layer has charge generation function and charge migration function simultaneously.

Hereinafter, will set forth multilayer photosensitive layer and individual layer photosensitive layer respectively.

Charge generation layer (CGL) (35) is mainly formed by charge generating material, and randomly contains adhesive resin.The charge generating material that is fit to comprises inorganic material and organic material.

The object lesson of inorganic charge generating material comprises crystallization selenium, amorphous selenium, selenium-tellurium alloy, selenium-tellurium-halogen alloy and selenium-arsenic alloy.

The object lesson that organic charge produces material comprises known material, for example phthalocyanine color (as metal phthalocyanine and metal-free phthalocyanine), Azulene  (azulenium) pigment, squaric acid methine pigment, AZO pigments with carbazole skeleton, AZO pigments with triphenylamine skeleton, AZO pigments with diphenylamine skeleton, AZO pigments with dibenzothiophen skeleton, AZO pigments with Fluorenone skeleton, AZO pigments with  diazole skeleton, AZO pigments with two stilbene skeletons, AZO pigments with diphenylethyllene  diazole skeleton, AZO pigments with diphenylethyllene carbazole skeleton, perylene pigment, anthraquinone pigment, many ring quinone pigments, quinone imines pigment, diphenyl-methane pigment, triphenyl methane pigment, benzoquinones pigment, naphthoquinones pigment, phthalocyanine pigments, azomethine pigment, indigoid pigment, bisbenzimidazole pigment or the like.

In these pigment, use phthalocyanine color effectively, particularly when with the Cu-K alpha-irradiation, in X-ray diffraction spectrum, under 9.6 ± 0.2 °, 24.0 ± 0.2 ° and 27.2 ± 0.2 °, there is the crystalline form titanyl phthalocyanine of Prague (2 θ) main peak.

These charge generating materials can be used alone or in combination.

The object lesson that randomly is used for the adhesive resin of CGL (35) comprises: polyamide, urethane resin, epoxy resin, polyketone resin, polycarbonate resin, organic siliconresin, acrylic resin, polyvinyl butyral resin, vinyl-formal resin, polyvinyl ketone resin, polystyrene resin, poly-N-vinyl carbazole resin, polyacrylamide resin, or the like.These resins can be used alone or in combination.In addition, except that above-mentioned adhesive resin, can also be charge transfer polymerization thing material as the adhesive resin among the CGL.Its object lesson comprises: the polymeric material with arylamine skeleton, biphenylamine skeleton, hydrazone skeleton, carbazole skeleton, stilbene skeleton, dihydropyazolo skeleton, as polycarbonate resin, vibrin, urethane resin, polyether resin, polyorganosiloxane resin and acrylic resin, or the like; With polymeric material with polysilane skeleton.

The object lesson of the former polymeric material comprises disclosed charge transfer polymerization thing material: 01-001728 in the following Japanese publication, 01-009964,01-013061,01-019049,01-241559,04-011627,04-175337,04-183719,04-225014,04-230767,04-320420,05-232727,05-310904,06-234838,06-234839,06-234840,06-234839,06-234840,06-234841,06-236051,06-295077,07-056374,08-176293,08-208820,08-211640,08-253568,08-269183,09-062019,09-043883,09-71642,09-87376,09-104746,09-110974,09-110976,09-157378,09-221544,09-227669,09-235367,09-241369,09-268226,09-272735,09-302084,09-302085,09-328539, or the like.

The object lesson of latter's polymeric material is included in disclosed poly-silylene polymkeric substance among Japanese publication 63-285552,05-19497,05-70595,10-73944 or the like.

CGL (35) can also comprise the low-molecular-weight charge transporting material.

The low-molecular-weight charge transporting material comprises hole transporting material and electron transfer material.

The object lesson of electron transfer material comprises: electronics is accepted material, as tetrachloroquinone (chloranil), tetrabromoquinone, tetracyanoethylene, four cyano quinone bismethane (tetracyanoquinodimethane), 2,4,7-trinitro--9-Fluorenone, 2,4,5,7-tetranitro-9-Fluorenone, 2,4,5,7-tetranitro-xanthone, 2,4,8-trinitro-thioxanthones, 2,6,8-trinitro--4H-indeno [1,2-b] thiophene-4-ketone, 1,3,7-trinitrobenzen bithiophene-5,5-dioxide, phenoquinone derivant, or the like.These electron transfer materials can be used alone or in combination.

The object lesson of hole (positive hole) transport materials comprises power supply sub-material, for example  Zole derivatives, the  oxadiazole derivative, imdazole derivatives, the monoarylamine derivant, Diaromatic amine derivatives, the triarylamine derivant, stilbene derivative, α-phenyl stilbene derivative, benzidine derivative, the diarylmethanes derivant, triarylmethane derivatives, 9-styryl anthracene derivant, the dihydropyazolo derivant, the divinyl benzene derivative, hydazone derivative, indene derivative, butadiene derivatives, pyrene derivatives, two stilbene derivative, enamine derivates, with other known material.These hole transporting materials can be used alone or in combination.

The method that is fit to that is used to form charge generation layer (35) roughly is divided into vacuum film forming method and solvent dispersion casting.

The former comprises by the object lesson of vacuum film forming method: vacuum vapor deposition method, glow discharge decomposition method, ion plating, sputtering method, reactive sputtering, CVD (chemical vapour desposition) method, or the like.Above-mentioned inorganic and organic material layer can form by these methods.

The casting method that forms charge generation layer generally comprises the following step:

(1) by following preparation coating fluid: with solvent, tetrahydrofuran for example, two  alkane, dioxolanes, toluene, methylene chloride, monochloro-benzene, ethylene dichloride, cyclohexanone, cyclopentanone, anisole, dimethylbenzene, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate etc., producing in the material one or more with above-mentioned inorganic or organic charge randomly mixes with adhesive resin and levelling agent, levelling agent such as dimethyl silicon oil and methyl phenyl silicone oil, use bowl mill then, masher, sand mill, ball mills (beads mill) etc. disperse these materials, prepare the CGL coating fluid;

(2) by as dip coated, spray, be coated with limit and ring-type painting method, the CGL coating fluid is coated on the base material, can dilute coating fluid in the time of if necessary; And

(3) the dry liquid that applies is to form CGL.

The about 5 μ m of the preferably about 0.01-of the thickness of CGL, the more preferably from about about 2 μ m of 0.05-.

Electric charge migrating layer (CTL) (37) is the layer with the transportable property of electric charge, and crosslinked top layer of the present invention (32) can be used as CTL effectively.As mentioned above, when crosslinked top layer (32) are whole C TL (37), of the present invention do not have the charge migration structure contain three or multi-functional free yl polymerizating monomer and the coating fluid (hereinafter referred to as free yl polymerizating composition) of radical polymerization compound with simple function of charge migration structure be coated in after CGL (35) goes up, randomly dry on CGL, forming coat, and it is applied external energy form crosslinked top layer with the hard-coating layer.

The preferred 10-30 μ of the thickness on crosslinked top layer m, more preferably 10-25 μ m.When thickness during, can not keep enough charging potentials (charged potential) less than 10 μ m.When thickness during greater than 30 μ m, the volumetric contraction on crosslinked top layer is easy to produce separating of crosslinked top layer and lower floor during sclerosis.

Shown in Fig. 2 B, when crosslinked top layer forms on CTL (37) surface, CTL (37) is by applying CGL (35) with coating fluid to form coat, then dry this coat forms, in coating fluid, charge transporting material and adhesive resin with the transportable property of electric charge are dispersed in the suitable solvent.Crosslinked top layer is to make with this coating layer of sclerosis by applying CGL with coating fluid to form coating layer on CGL, following with external energy is crosslinked, and this coating fluid comprises the free yl polymerizating composition of the invention described above.

The object lesson of charge transporting material comprises electron transfer material, hole transporting material and the charge transfer polymerization thing material that is used for CGL (35).Particularly, when CGL went up the coating top layer, charge transfer polymerization thing material was used to reduce the dissolving of lower floor effectively.

CTL preferably contains the charge transporting material of 20-300 weight portion, and more preferably 40-150 weight portion is in 100 weight portion adhesive resins.Yet charge transfer polymerization thing material can use separately, perhaps is used in combination with adhesive resin.

The object lesson of adhesive resin comprises: thermoplastic resin or thermoset resin, for example polystyrene resin, styrene-acrylonitrile copolymer, Styrene-Butadiene, styrene-maleic anhydride copolymer, vibrin, Corvic, vinyl chloride vinyl acetate copolymer, vinylite, the polyvinylidene chloride resin, polyarylate resin, phenoxy resin, polycarbonate resin, the cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral resin, vinyl-formal resin, the tygon toluene resin, poly-N-vinyl carbazole resin, acrylic resin, organic siliconresin, epoxy resin, melamine resin, urethane resin, phenolics, and alkyd resin.

Shown in Fig. 2 B, the object lesson that is used for applying the solvent of CTL (37) comprises the solvent that is used for applying CGL, and preferred especially the use charge transporting material and adhesive resin dissolving excellent solvent.These solvents can be used alone or in combination.CTL can prepare by the painting method identical with applying CGL (35).

Shown in Fig. 2 B, CTL (37) can randomly comprise plastifier and levelling agent.

The object lesson of plastifier comprises the plastifier that is used for general resin, for example Dibutyl phthalate and dioctyl phthalate.The preferred 0-30 weight portion of the content of plastifier is in 100 weight portion adhesive resins.

The object lesson of levelling agent comprises silicone oil, for example dimethyl silicon oil and methyl phenyl silicone oil; The polymkeric substance or the oligomer that in side chain, contain perfluorinated alkyl.The preferred 0-1 weight portion of the content of levelling agent is in 100 weight portion adhesive resins.

Shown in Fig. 2 B, the preferred 5-40 μ of the thickness m of CTL (37), more preferably 10-30 μ m.

When the crosslinked top layer (32) shown in Fig. 2 B covers on the CTL (37), method as the crosslinked top layer of above-mentioned preparation, the coating fluid that comprises free yl polymerizating composition of the present invention is coated on the CTL, randomly dry then to form the coat on the CTL, then it is applied external energy with the hard-coating layer, thereby on CTL, form crosslinked top layer.The preferred 1-20 μ of the thickness on crosslinked top layer m, more preferably 2-10 μ m.When thickness during less than 1 μ m, the inhomogeneous meeting of crosslinked skin depth causes its uneven permanance.When thickness during greater than 20 μ m, CTL (37) and crosslinked top layer (32) to such an extent as to the very big electric charge of gross thickness disperse, cause the image reproducibility deterioration of the photoreceptor that makes.In addition, crosslinked top layer of the present invention more preferably prepares according to coating, radiation (crosslinked) and dry order with respect to for the order preparation of coating, drying and radiation (crosslinked).This part ground is that solvent reduces and viscosity increased, thereby has hindered cross-linking reaction owing to occur in radiation (crosslinked) before the time when drying, and partly be since when drying polymerization initiator may distil.

Shown in Figure 1A, the individual layer photosensitive layer has charge generation function and charge migration function, and the crosslinked top layer that has the charge migration structure and contain the charge generating material with charge generation function of the present invention can be used as the individual layer photosensitive layer effectively.As what in the casting method of preparation CGL (35), mention, charge generating material is dispersed in the coating fluid that contains free yl polymerizating composition, then coating fluid is coated on the base material of electric conductivity, randomly dry then, thereby on base material, form coat, with external energy, sclerous reaction is carried out to form crosslinked top layer in coat then.Can be dispersed in charge generating material in advance and prepare dispersion in the solvent, then this dispersion be added in the coating fluid that is used to form crosslinked top layer.The preferred 10-30 μ of the thickness on crosslinked top layer m, more preferably 10-25 μ m.When thickness during, can not keep enough charging potentials less than 10 μ m.When thickness during greater than 30 μ m, the volumetric contraction on crosslinked top layer during sclerosis is easy to cause crosslinked top layer to separate with undercoat.

Shown in Figure 1B, when crosslinked top layer covers on the individual layer photosensitive layer (33), as the preparation crosslinked top layer method described in, the coating fluid that contains free yl polymerizating composition of the present invention and adhesive resin is coated on the photosensitive layer, randomly dry then, thereby on photosensitive layer, form coating layer, then it is applied the external energy coating layer that hardens, thereby on photosensitive layer, form crosslinked top layer.The preferred 1-20 μ of the thickness on crosslinked top layer m, more preferably 2-10 μ m.When thickness during less than 1 μ m, the inhomogeneous meeting of crosslinked skin depth causes its uneven permanance.

The preferred 1-30 weight of the amount % of the electric charges contained generation material of individual layer photosensitive layer, the preferred 10-70 weight portion of the amount of the amount of contained adhesive resin preferred 20-80 weight % and electric charges contained transport materials is in the general assembly (TW) of individual layer photosensitive layer.

When crosslinked top layer covers on the photosensitive layer, can there be the middle layer in photoreceptor of the present invention between crosslinked top layer and photosensitive layer.The middle layer can prevent down that the component of photosensitive layer sneaks into crosslinked top layer, thereby avoids the uneven of the inhibition of sclerous reaction and crosslinked top layer.In addition, the adhesiveness between crosslinked top layer and the photosensitive layer can be improved in the middle layer.

The middle layer with resin as principal ingredient.The object lesson of resin comprises polyamide, pure molten nylon, water miscible polyvinyl butyral, polyvinyl butyral, polyvinyl alcohol (PVA), or the like.The middle layer can be by a kind of preparation the in the above-mentioned known painting method.The preferred 0.05-2 μ of the thickness in middle layer m.

Can there be undercoat in photoreceptor of the present invention between base material (31) and photosensitive layer.Undercoat with resin as principal ingredient.Because generally by the liquid that contains organic solvent is applied, thereby form photosensitive layer on undercoat, the resin in the undercoat preferably has good tolerance for common organic solvents.The object lesson of this resinoid comprises water soluble resin, for example polyvinyl alcohol resin, casein and polyacrylic acid sodium salt; Alcohol-sol-resin, for example nylon copolymer and methoxy nylon resin; With the thermoset resin that can form three-dimensional network, for example urethane resin, melamine resin, alkyd-melamine resin, epoxy resin or the like.Undercoat can comprise the fine powder of metal oxide, and for example titanium dioxide, silica, alumina, zirconia, tin oxide and indium oxide are with the rest potential that prevents ripple to occur in the image of record and reduce photoreceptor.

Undercoat can also apply coating fluid and form by the coating process that uses suitable solvent and be fit to, suitable solvent and painting method can adopt with above-mentioned formation photosensitive layer in used similar solvent and method.Undercoat can use silane coupling agent, titanium coupling agent or chromium coupling agent to form.In addition, be preferably used as also comprising of undercoat: alumina layer that is formed by anodizing and the organic compound that is formed by vacuum vapor deposition method (for example poly-to xylylene (poly-terephthaldehyde's support)) layer or mineral compound are (as SiO, SnO ₂, TiO ₂, ITO or CeO ₂) layer.Except that these materials, can use known material.The thickness of undercoat is 0-5 μ m preferably.

In the present invention, each layer (being crosslinked top layer, charge generation layer, electric charge migrating layer, undercoat and middle layer) can use antioxidant, thereby can reach the stability of improving anti-environmental baseline, promptly avoid the reduction of photosensitivity and the increase of rest potential.

The preferred 0.01-10 weight of the amount of the contained antioxidant of each layer % is in the general assembly (TW) of each layer.

The object lesson that is used for antioxidant of the present invention comprises following compounds.

(1) phenolic compound

2,6-two-tert-butyl group-paracresol, butylated hydroxy anisole (BHA), 2,6-two-tert-butyl group-4-ethyl-phenol, n-octadecane base-3-(4 '-hydroxyl-3 ', 5 '-two-tert-butyl phenol), 2,2 '-methylene-two-(4-methyl-6-tert butyl phenol), 2,2 '-methylene-two-(4-ethyl-6-tert-butyl phenol), 4,4 '-thiobis-(3 methy 6 tert butyl phenol), 4,4 '-butylidene two-(3 methy 6 tert butyl phenol), 1,1,3-three-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethyl-2,4,6-three (3,5-two-tertiary butyl-4-hydroxy benzyl) benzene, four-[methylene-3-(3 ', 5 '-two-tert-butyl group-4 '-hydroxyphenyl) propionic ester] methane, two [3,3 '-two (4 '-hydroxyl-3 '-tert-butyl-phenyl) butyric acid] glycol ester, tocopherol (tocophenol) compound, or the like.

(2) p-phenylenediamine (PPD) compound

N-phenyl-N '-isopropyl-p-phenylenediamine (PPD), N, N '-two-sec-butyl-p-phenylenediamine (PPD), N-phenyl-N-sec-butyl-p-phenylenediamine (PPD), N, N '-two-isopropyl-p-phenylenediamine (PPD), N, N '-dimethyl-N, N '-two-tert-butyl group-p-phenylenediamine (PPD), or the like.

(3) hydroquinone compound

2,5-two-uncle-octyl group quinhydrones, 2, the two dodecyl quinhydrones of 6-, 2-dodecyl quinhydrones, 2-dodecyl-5-chlorohydroquinone, uncle 2--octyl group-5-methylnaphthohydroquinone, 2-(2-vaccenic acid base (octadecenyl))-5-methylnaphthohydroquinone, or the like.

(4) sulfur-containing organic compound

Two lauryls-3,3 '-thiodipropionate, distearyl-3,3 '-thiodipropionate, two myristyl-3,3 '-thiodipropionate, or the like.

(5) organophosphorus compound

Triphenylphosphine, three (nonyl phenyl) phosphine, three (dinonyl phenyl) phosphine, trimethylphenyl phosphine, three (2,4-dibutyl phenoxy group) phosphine, or the like.

The known antioxidant that can be used as rubber, plastics, fat etc. of these compounds, and its commercially available prod can easily obtain.

In layer composition as shown in Figure 2, between crosslinked top layer and photosensitive layer, can form bonding coat.

Because prevent the separation and the wearing and tearing on top layer and the permanance of improving the top layer, it is down 1-20mPas and the radical polymerization compound that does not possess the charge migration structure at 25 ℃ that bonding coat preferably includes viscosity.

When not being formed for improving adhering mode betwixt, the top layer is shunk and is had a very big internal stress when three-dimensional network in the top layer forms.Therefore, when inner abrasion took place on the top layer, cracking took place and separates from photosensitive layer in the top layer, thereby causes the top layer rapid wearing.Bonding coat has improved the adhesiveness between top layer and photosensitive layer, because the sclerosis of the height on top layer, adhesiveness reduces.Form bonding coat by following steps: comprising that the adhesive resin that is used for above-mentioned photosensitive layer, three or the polyfunctional free yl polymerizating monomer that do not have the charge migration structure, 25 ℃ of following viscosity are that 1-20mPas and the coating fluid that do not have the radical polymerization compound of charge migration structure and randomly have a simple function radical polymerization compound of charge migration structure are coated to photosensitive layer; Apply the top layer coating fluid; With luminous energy these coating fluids that harden.

The object lesson that is used to prepare the solvent of coating fluid comprises: alcohols, for example methyl alcohol, ethanol, propyl alcohol and butanols; Ketone, for example acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Ester class, for example ethyl acetate and butyl acetate; Ethers, for example tetrahydrofuran, two  alkane and propyl ethers; Halogen, for example methylene chloride, ethylene dichloride, trichloroethanes and chlorobenzene; Aromatic compounds, for example benzene, toluene and dimethylbenzene; And cellosolve, for example methyl cellosolve, ethyl cellosolve and cellosolve acetate.These solvents can be used alone or in combination.

The principle that makes top layer and photosensitive layer combination of bonding coat of the present invention is unclear fully, but it is generally acknowledged as follows.

Bonding coat of the present invention is to be made by the coating fluid that comprises low viscosity and do not have a radical polymerization compound of charge migration structure.That is, having low viscous radical polymerization compound is a kind of solvent, and when adhering to CTL surperficial, radical polymerization compound moves in CTL and dissolves CTL simultaneously.Simultaneously, the top layer comprises three or multifunctional free yl polymerizating monomer with charge migration structure, to have wearing quality.Three or multifunctional free yl polymerizating monomer have high viscosity and permeate CTL deficiently.Yet, when with move to bonding coat among the CTL when crosslinked, obtained the bond effect of CTL, and thought that the top layer is firmly bonding with CTL.

When the viscosity of radical polymerization compound during less than 1mpas, can't be formed uniformly bonding coat to such an extent as to the flowability of compound is very high, thereby cause adhesiveness inconsistent under 25 ℃.When viscosity during greater than 20mPas, radical polymerization compound can't move in CTL, thereby causes bond strength not enough.

Radical polymerization compound is preferably dual functional.When compound was simple function, keyed jointing point (bonding site) was to such an extent as to be that adhesive capacity is not enough so less.When compound is three or when polyfunctional,, thereby cause adhesiveness not enough to such an extent as to too high this radical polymerization compound of viscosity can't permeate CTL fully.

Viscosity comprises at the 25 ℃ times object lessons for the radical polymerization compound of the no charge migration structure of 1-20mPas: diacrylate 1,6-hexanediol ester, 2-(2-ethoxy ethoxy) ethyl propylene acid esters, tetrahydrofurfuryl acrylate, the acrylic acid Lauryl Ester, acrylic acid 2-phenoxy ethyl, isodecyl acrylate, Isooctyl acrylate monomer, acrylic acid tridecyl (tridecyl) ester, acrylic acid 1, the 3-butanediol ester, acrylic acid 1, the 4-butanediol ester, diacrylate tetraethylene glycol ester, the diacrylate triethyleneglycol ester, ethoxylated neopentylglycol diacrylate (propoxylated neopentylglycoldiacrylate), the ethoxylation neopentylglycol diacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, the methacrylic acid Lauryl Ester, methacrylic acid 2-phenoxy ethyl, methacrylic acid tridecyl ester, the dimethacrylate triethyleneglycol ester, Ethylene glycol dimethacrylate, dimethacrylate tetraethylene glycol ester, methacrylic acid 1, the 4-butanediol ester, dimethacrylate diglycol ester, dimethacrylate 1,6-hexanediol ester, the dimethacrylate DOPCP, dimethacrylate 1, the 3-butanediol ester, or the like.These compounds can be used alone or in combination.

Bonding coat comprises that the amount of the radical polymerization compound of the simple function with charge migration structure is preferably 20-80 weight %, and more preferably 30-70 weight % is to have the compound of the transportable property of electric charge.When this compounds content during less than 20 weight %, bonding coat can not keep the transportable property of electric charge, thereby owing to reuse the deterioration that causes sensitivity and electrical property, the photoreceptor rest potential that for example makes increases.When the content of compound during greater than 80 weight %, the radical polymerization compound that does not have the charge migration structure reduces, thereby causes the deterioration of bond strength.

When forming (crosslinked) bonding coat, can randomly be used for bonding coat to the polymerization initiator that is used for the top layer, can effectively carry out cross-linking reaction equally.Polymerization initiator can be used alone or in combination.The content of initiating agent is preferably the 0.5-40 weight portion, and more preferably 1-20 weight portion is in 100 weight portion radical polymerization compounds.

Bonding coat is preferably placed between top layer and photosensitive layer and does not have interphase.Shown in SEM (scanning electron microscope) cross-section photograph of the photoreceptor of putting down in writing among the embodiment, be included in the adhesive resin anisotropically dissolving mutually in each layer, and can not clearly differentiate the interphase in the layer.

Fig. 5 is the synoptic diagram of xsect of the 4th embodiment of explanation Electrophtography photosensor of the present invention, and it is the individual layer photoreceptor, comprises base material 231 and the photosensitive layer 233 with charge generation and the transportable property of electric charge on base material 231.238 expression bonding coats, 239 expression top layers.

Fig. 6 is the synoptic diagram of xsect of the 5th embodiment of explanation Electrophtography photosensor of the present invention, and it is the multilayer photoreceptor, is included in the CGL235 and the transportable CTL237 of electric charge of the produced electric charge on the base material 231.238 expression bonding coats, 239 expression top layers.

Bonding coat preferably comprises adhesive resin at least and does not have three or polyfunctional free yl polymerizating monomer of charge migration structure.In addition, can also use simple function or dual functional radical polymerization compound with charge migration structure.

The object lesson of adhesive resin comprises: thermoplastic resin or thermoset resin, for example polystyrene resin, styrene-acrylonitrile copolymer, Styrene-Butadiene, styrene-maleic anhydride copolymer, vibrin, Corvic, vinyl chloride vinyl acetate copolymer, vinylite, the polyvinylidene chloride resin, polyarylate resin, phenoxy resin, polycarbonate resin, the cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral resin, vinyl-formal resin, the tygon toluene resin, poly-N-vinyl carbazole resin, acrylic resin, organic siliconresin, epoxy resin, melamine resin, urethane resin, phenolics, and alkyd resin.These resins can be used alone or in combination.In these resins, according to photosensitive layer in the compatibility of adhesive resin, preferably use the adhesive resin identical with adhesive resin in the photosensitive layer.Especially, preferably use polycarbonate resin.

In bonding coat, the mixing ratio of adhesive resin and radical polymerization compound (adhesive resin/radical polymerization compound) is preferably 90/10-10/90, more preferably 70/30-30/70.When the mixing ratio of adhesive resin was too high, the hardness that the adhesive resin migration enters top layer and top layer descended, thereby caused the top layer wearing and tearing faster.Cross when low when the mixing ratio of binder resin, the top layer is easy to separate with bonding coat.

Bonding coat forms by dip coated method, spraying process, rolling method, ring-type cladding process, nozzle coating process, silk screen print method or the like method.According to the stability and the quality that form, preferably use spraying process and ring-type coating process.

The preferred 0.05-5 μ of the thickness of bonding coat m, more preferably 0.1-3 μ m.When thickness during less than 0.05 μ m, the top layer may be separated with photosensitive layer.When thickness during greater than 5 μ m, the surface potential of photoreceptor increases after radiation, thereby causes the deterioration of image density.

Next will describe formation method of the present invention and imaging device in detail, referring to accompanying drawing.

Formation method of the present invention and imaging device comprise: have the photoreceptor on the crosslinked top layer of migration low-surface-energy, level and smooth, wherein to photoreceptor charging with use the imaging radiation, thereby form electrostatic latent image on photoreceptor; Thereby latent electrostatic image developing forms toner image; This toner image is transferred to image-carrier (transfer sheet (transfer sheet)) goes up also photographic fixing in the above; The surface of cleaning photoreceptor.

Method is not limited in this class methods, as directly being transferred to electrostatic latent image on the transfer sheet and making latent electrostatic image developing thereon.

Fig. 3 represents the partial cross section synoptic diagram of imaging device embodiment of the present invention.Charger (3) is used for to photoreceptor (1) uniform charging.The object lesson of charger comprises known charger, for example corona unit, scorotron device, solid-state charger, needle electrode device, cylinder charging device and conduction brush device.

Can use contact or non-contact charger among the present invention.The contact charging device comprises blade (charging blade) of charging roller, charging brush, charging or the like, and it directly contacts photoreceptor.Non-contact charger comprises, for example is positioned at the charging roller near the photoreceptor position, and the interval of the two is not more than 200 μ m.When the interval was oversize, photoreceptor can't stably charge.When at interval too in short-term, charge member, for example charging roller can be left in the toner contamination on the photoreceptor.Therefore, the preferred 10-200 μ of length m at interval, more preferably 10-100 μ m.

Secondly, image-forming radiation body (5) is used for going up the formation electrostatic latent image at photoreceptor (1).The light source that is fit to comprises general light emitter, for example fluorescent light, tungsten lamp, Halogen lamp LED, mercury vapor lamp, sodium vapor lamp, light emitting diode (LEDs), laser diode (LDs), use the light source of electroluminescence (EL), or the like.In addition, for obtaining light with desired wavelength scope, can use wave filter, for example sharp filter, bandpass filter, near infrared cut-off filter (near-infrared cutting filter), two tropism's wave filters, interference filter and colour temperature switched filter.

Next, use developing cell (6) latent electrostatic image developing on photoreceptor (1).Developing method comprises single component development method and the bi-component developing method that uses dry toner; With the wet developing method of using wet toner.When positively charged or electronegative photoreceptor is exposed to imaging, on photoreceptor, form the electrostatic latent image of band plus or minus electric charge.When during with positively charged image development, obtaining erect image with electronegative toner.On the contrary, when during positively charged image development, obtaining negative-appearing image with positively charged toner.

Next, use transfer printing charger (10) that video picture is transferred on the transfer sheet (9) at the toner image on the photoreceptor.Can carry out transfer printing better with pre-transfer charger (7).The transfer printing device that is fit to comprises the mechanical transfer printing device and the crosstalk device of transfer printing charger, the static printing device that uses biasing roller, gluing transfer printing device, working pressure.Above-mentioned charger can be used as the static printing device.

Next, use separating charger (11) and separate pick (pick) (12) transfer sheet (9) and photoreceptor (1) are separated.Other separate mode comprises that static absorbs induction separation vessel, side belt separator, folder top travelling belt (tip grip conveyor), flex apart device or the like.Above-mentioned charger also can be used as separating charger (11).

Next, remove the toner that remains in after the transfer printing on the photoreceptor with hairbrush (14) and cleaning blade (cleaning blade) (15).Clean more effective with pre-cleaning charger (13).Other clearer comprises netted clearer, magnetic brush clearer or the like, and these clearers can be used alone or in combination.

Next, randomly use discharger to remove sub-image on the photoreceptor.Discharger comprises discharge lamp (2) and discharger, and can use above-mentioned light source and charger respectively.

Other initial reading process (original reading process), paper supply process, fixing, paper delivery process or the like can be adopted in a known manner.

Above-mentioned image-generating unit can be fixed in duplicating machine, facsimile recorder or the printing machine.Yet image-generating unit can be used as handle box and removably is placed in one.Fig. 4 represents that the present invention is used as the cross sectional representation of embodiment of the handle box of imaging device.

Handle box is a kind of image-generating unit (or device), and it comprises photoreceptor (101), and charger (102), image developing device (104), transfer printing device (106), clearer (107) and discharger (not shown) is at least a.

When direction rotation that photoreceptor (101) is indicated with arrow, with charger (102) photoreceptor (101) charging, use irradiator (103) then thus the irradiation photoreceptor forms the electrostatic latent image relevant with imaging.With the image developing device (104) that has toner latent electrostatic image developing, thereby form toner image, use transfer printing device (106) that toner image is transferred on the transfer sheet to be printed off (105) then, thereby realize duplicating.Next, after the toner image transfer printing, with clearer (107) photosensitive surface is cleared up, again with the discharge of discharger (not shown), and these processes can repeat.

Can know clearly that by top explanation Electrophtography photosensor of the present invention can be widely used for the xerography application, for example laser beam printer, CRT printing machine, LED printing machine, liquid crystal printer and laser engraving.

More than described general status of the present invention, further explained the present invention below by specific embodiment, these specific embodiments only are used for the present invention is described and are not limited only to this.Below in the description of embodiment, unless otherwise mentioned, the numeral weight part ratio.

Embodiment

＜have a synthetic embodiment of radical polymerization compound of the simple function of charge migration structure 〉

Compound with charge migration structure of the present invention passes through, and for example disclosed method is synthesized in the Jap.P. 3164426.Below method be among its embodiment one.

(1) synthetic triarylamine compound with hydroxyl replacement of following formula B

The triarylamine compound of the methoxyl replacement with formula A of 113.85g (0.3mol), sodium iodide and the 240ml sulfolane of 138g (0.92mol) are mixed, thereby make potpourri.Potpourri is heated to 60 ℃ in nitrogen stream.

With 1 hour the trimethyl chlorosilane of 99g (0.91mol) is splashed in the potpourri, and potpourri was stirred 4 hours down at 60 ℃.In potpourri, add the toluene of about 1.5L, then potpourri is cooled to room temperature, then water and aqueous sodium carbonate washed mixture repeatedly.Then, solvent is removed from potpourri and used with silica gel and purify as the column chromatography of developer solution as absorbing medium with toluene and ethyl acetate (20: 1).In the lurid yellow oil (buff yellow oil) of such preparation, add cyclohexane, so that crystal separation is come out.Thereby make the white crystal of 88.1g (productive rate is 80.4%), it has following formula B and fusing point is 64.0-66.0 ℃.

Ultimate analysis value (%)

	C	H	N
	C	H	N	Measured value	85.06	6.41	3.73
Calculated value	85.44	6.34	3.83	Measured value	85.06	6.41	3.73

(2) the amino acrylate compounds (compound 54 in the table 1) that replaces of triaryl

The triarylamine compound that the hydroxyl with formula B of the 82.9g (0.227mol) of preparation in (1) is replaced is dissolved in the 400ml tetrahydrofuran, thereby makes potpourri.Then in nitrogen stream, sodium hydrate aqueous solution (being made by 12.4gNaOH and 100ml water) is splashed in the potpourri.Potpourri is cooled to 5 ℃, and in 40 minutes, 25.2g (0.272mol) propylene dichloride acid esters (chloride acrylate) is splashed into wherein.Under 5 ℃, potpourri was stirred 3 hours then.Potpourri put in the water and with toluene extract.Water and aqueous sodium carbonate repeatedly clean the liquid of extraction.Then, solvent is removed from the liquid of extraction and by purifying as the column chromatography of developer solution as absorbing medium and toluene with silica gel.In the water white oil of such preparation, add normal hexane, so that crystal separation is come out.Thereby make the white crystal of the compound 54 of 80.73g (productive rate is 84.8%), its fusing point is 117.5-119.0 ℃.

Ultimate analysis value (%)

	C	H	N
	C	H	N	Measured value	83.13	6.01	3.16
Calculated value	83.02	6.00	3.33	Measured value	83.13	6.01	3.16

(3) the synthetic embodiment of acrylate compounds

(i) preparation diethyl 2-hydroxy benzenes methyl phosphonate

The 2-salicylic alcohol of 38.4g (from TOKYO KASEI KOGYO company) and 80ml o-xylene are put in the reactor, and this reactor has stirrer, thermometer and tap funnel.In nitrogen stream, splash into wherein at leisure at 80 ℃ of following 62.8g triethyl phosphites, and be reflected under the identical temperature and carried out again 1 hour.Then, by decompression distillation the ethanol, o-xylene and the unreacted triethyl phosphite that produce are removed from reaction, thereby made the 2-diethyl hydroxy benzenes methyl phosphonate that productive rate is 90% 66g, its boiling point is 120.0 ℃/1.5 mm Hg.

(ii) prepare 2-hydroxyl-4 '-(two-right-tolyl amino) stilbene

Uncle 14.8g-butoxy potassium (kalium-tert-butoxide) and 50ml tetrahydrofuran are put into reactor, and this reactor has stirrer, thermometer and tap funnel.In nitrogen, at room temperature, be reflected under the identical temperature and carried out again 2 hours being dissolved in the solution that obtains in the tetrahydrofuran and splashing into lentamente in the reactor by 4-(two-right-tolyl amino) benzaldehyde with 9.90g diethyl 2-hydroxy benzenes methyl phosphonate and 5.44g.Then, water is added in the reactor, use the water cooling reaction product simultaneously; Then add hydrochloric acid solution with normal concentration 2, thus this reaction product of acidifying; Then remove tetrahydrofuran, thereby extract the crude product that contains toluene with evaporator.Water, sodium bicarbonate solution and saturated brine clean toluene mutually successively, make the toluene phase dehydration thereby then add magnesium sulphate.After filtration, thereby remove toluene preparation oiliness crude product, then the oiliness crude product is further carried out post-purification with silica gel, thereby in hexane crystallization obtain the 2-hydroxyl-4 of 5.09g '-(two-right-tolyl amino) stilbene, its productive rate is 72%, boiling point is 136.0-138.0 ℃.

(iii) prepare 4 '-(two-right-tolyl amino) stilbene-2-base acrylate (ylacrylate)

Is the 2-hydroxyl-4 ' of 14.9g-(two-right-tolyl amino) stilbene, 100ml tetrahydrofuran and concentration that 12% 21.5g sodium bicarbonate solution is put reactor into, and reactor has stirrer, thermometer and tap funnel.In nitrogen stream, 5.17g propylene dichloride acid esters is splashed into wherein in following 30 minutes at 5 ℃, and be reflected under the identical temperature and carried out again 3 hours.Reaction liquid is put into water, carry out post-purification with toluene extraction, condensation and with silica gel, thereby make crude product.With crude product with ethanol crystallization again, thereby make the yellow acicular crystal 4 of 13.5g '-(two-right-tolyl amino) stilbene-2-base acrylate (exemplary compounds 2), its productive rate is 79.8%, boiling point is 104.1-105.2 ℃.Its ultimate analysis is as follows.

Ultimate analysis value (%)

	C	H	N
	C	H	N	Measured value	83.46	6.06	3.18
Calculated value	83.57	6.11	3.14	Measured value	83.46	6.06	3.18

Embodiment 1

Be coated in undercoat coating fluid, charge generation coating fluid and charge migration coating fluid according to following prescription on the aluminium cylinder successively and drying, the diameter of this aluminium cylinder is 30mm, thereby forms the undercoat that thickness is 3.5 μ m thereon, CGL, the thickness that thickness is 0.2 μ m is the CTL of 23 μ m.

The undercoat coating fluid

Alkyd resin 6

(BEKKOZOL 1307-60-EL is from Dainippon Ink ﹠amp; Chemicals, Inc.)

Melamine resin 4

(SUPER BEKKAMIN G-821-60 is from Dainippon Ink ﹠amp; Chemicals, Inc.)

Titania powder 40

Methyl ethyl ketone 50

The CGL coating fluid

Polyvinyl butyral 0.5

(XYHL is from Union Carbide company)

Cyclohexanone 200

Methyl ethyl ketone 80

Disazo pigment 2.5 with following formula (I)

The CTL coating fluid

Bisphenol Z polycarbonate 10

(Panlite TS-2050 is from TEIJIN CHEMICALS LTD.)

Tetrahydrofuran 100

The tetrahydrofuran solution 0.2 of the silicone oil of concentration 1%

(KF50-100CS is from Shin-Etsu Chemical Industry Co., Ltd.)

Charge transporting material 7 with following formula (II)

Adopt spraying method, on CTL, further apply crosslinked top layer coating fluid according to following prescription.

Crosslinked top layer coating fluid

Three or the polyfunctional free yl polymerizating monomer 10 that do not have the charge migration structure

Molecular weight is 296 trimethylolpropane triacrylate

(KAYARAD TMPTA is from NIPPON KAYAKU CO., LTD.)

Radical polymerization compound 10 with simple function of charge migration structure

Molecular weight is 445 and the acrylate triarylamine compound XII of a functional group is arranged

Photoepolymerizationinitiater initiater 1

1-hydroxyl-cyclohexyl-phenyl-ketone, molecular weight are 204 and do not contain functional group

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Butyl acetate 120

Boiling point is that 126 ℃, saturation vapour pressure are 13 mm Hg/25 ℃

Trimethylolpropane triacrylate and acrylate triarylamine compound XII have free radical polymerization functional group.The number of its acrylic acid groups (acrylic group) is as follows.

(1) number of the acrylic acid groups of trimethylolpropane triacrylate is

10×6.02×10 ²³×3/296＝6.10×10 ²²

(2) number of the acrylic acid groups of acrylate triarylamine compound XII is

10×6.02×10 ²³/445＝1.35×10 ²²

(3) sum of acrylic acid groups obtains the number of the free radical polymerization functional group in the 1g solid constituent divided by the general assembly (TW) of solid constituent

(6.10×10 ²²+1.35×10 ²²)/(10+10+1)＝3.55×10 ²¹

Shone coating layer 30 seconds with ultraviolet lamp system, H bulb (Hbulb), bulb power that this system has from FUSION are that 200W/cm, radiation intensity are 450mW/cm ², descended further dry 30 minutes at 130 ℃ then, be the crosslinked top layer of 5.0 μ m thereby form thickness.Thereby, make Electrophtography photosensor.

Embodiment 2

Except that 120 parts of butyl acetates in the coating fluid of crosslinked top layer being replaced to 30 parts of butyl acetates and 90 parts of tetrahydrofurans, the step that repeats embodiment 1 preparation Electrophtography photosensor prepares Electrophtography photosensor.

Embodiment 3

Except that butyl acetate being replaced to boiling point is that 156 ℃, saturation vapour pressure are the cyclohexanone of 3.95 mm Hg/25 ℃, and the step that repeats preparation Electrophtography photosensor among the embodiment 2 prepares Electrophtography photosensor.

Embodiment 4

Except that butyl acetate being replaced to boiling point is that 82 ℃, saturation vapour pressure are the 2-propyl alcohol of 32.4 mm Hg/25 ℃, and the step that repeats preparation Electrophtography photosensor among the embodiment 2 prepares Electrophtography photosensor.

Embodiment 5

Except that butyl acetate being replaced to solubility parameters is 8.8 the dimethylbenzene, and the step that repeats preparation Electrophtography photosensor among the embodiment 2 prepares Electrophtography photosensor.

Embodiment 6

Except that butyl acetate being replaced to solubility parameters is 9.9 the two  alkane, and the step that repeats preparation Electrophtography photosensor among the embodiment 2 prepares Electrophtography photosensor.

Embodiment 7

Except that butyl acetate being replaced to solubility parameters is 9.5 the chlorobenzene, and the step that repeats preparation Electrophtography photosensor among the embodiment 2 prepares Electrophtography photosensor.

Embodiment 8

Except that 120 parts of butyl acetates in the coating fluid of crosslinked top layer being replaced to 63 parts cyclohexanone, the step that repeats embodiment 1 preparation Electrophtography photosensor prepares Electrophtography photosensor.

Embodiment 9

Except that 120 parts of butyl acetates in the coating fluid of crosslinked top layer are replaced to 399 parts of butyl acetates, the step that repeats embodiment 1 preparation Electrophtography photosensor prepares Electrophtography photosensor.

Embodiment 10

Except that the radical polymerization compound that has the simple function of charge migration structure in the coating fluid of crosslinked top layer to be replaced to molecular weight be 431 and have the acrylate triarylamine compound VII of a functional group, the step that repeats embodiment 1 preparation Electrophtography photosensor prepares Electrophtography photosensor.

Embodiment 11

Except that the radical polymerization compound that has the simple function of charge migration structure in the coating fluid of crosslinked top layer to be replaced to molecular weight be 828 and have the acrylate triarylamine compound XV of a functional group, the step that repeats embodiment 1 preparation Electrophtography photosensor prepares Electrophtography photosensor.

Embodiment 12

Except that the radical polymerization compound that has the simple function of charge migration structure in the coating fluid of crosslinked top layer to be replaced to molecular weight be 419 and have the triarylamine exemplary compounds 54 of a functional group, the step that repeats embodiment 1 preparation Electrophtography photosensor prepares Electrophtography photosensor.

Embodiment 13

Except that the radical polymerization compound that has the simple function of charge migration structure in the coating fluid of crosslinked top layer to be replaced to molecular weight be 371 and have the triarylamine exemplary compounds 16 of a functional group, the step that repeats embodiment 1 preparation Electrophtography photosensor prepares Electrophtography photosensor.

Embodiment 14

Except that the radical polymerization compound that has the simple function of charge migration structure in the coating fluid of crosslinked top layer to be replaced to molecular weight be 419 and have the triarylamine exemplary compounds 24 of a functional group, the step that repeats embodiment 1 preparation Electrophtography photosensor prepares Electrophtography photosensor.

Embodiment 15

Remove 10 parts three or the multifunctional free yl polymerizating monomer KAYARAD TMPTA (trimethylolpropane triacrylate) that do not have the charge migration structure in the coating fluid of crosslinked top layer replaced to 5 parts of KAYARAD TMPTA and 5 parts of KAYARAD DPHA (dipentaerythritol acrylates, from NIPPON KAYAKU CO., LTD.) in addition, the step that repeats embodiment 2 preparation Electrophtography photosensors prepares Electrophtography photosensor, and wherein the mean molecular weight of KAYARAD DPHA is 536, has 5.5 functional groups and have following formula:

Wherein a be 5 and b be 1, perhaps a be 6 and b be 0.

Embodiment 16

Remove 10 parts three or the multifunctional free yl polymerizating monomer KAYARAD TMPTA (trimethylolpropane triacrylate) that do not have the charge migration structure in the coating fluid of crosslinked top layer replaced to 5 parts of KAYARAD TMPTA and 5 parts of KAYARAD DPCA-120 (dipentaerythritol acrylates, from NIPPON KAYAKU CO., LTD.) in addition, the step that repeats embodiment 12 preparation Electrophtography photosensors prepares Electrophtography photosensor, wherein the mean molecular weight of KAYARAD DPCA-120 is 1,948 and has 6 functional groups.

Comparative Examples 1

Remove three or polyfunctional free yl polymerizating monomer in the coating fluid of crosslinked top layer are replaced to KAYARAD FM-280 (PO-modified acroleic acid glycerine ester, from NIPPON KAYAKU CO., LTD.) in addition, the step that repeats preparation Electrophtography photosensor among the embodiment 1 prepares Electrophtography photosensor, wherein the mean molecular weight of KAYARAD FM-280 is 463 and has 3 functional groups, the number of the acrylic acid groups in the 1g solid constituent wherein, be the number of free radical polymerization functional group, less than 2.5 * 10 ²¹

Comparative Examples 2

Remove three or polyfunctional free yl polymerizating monomer in the coating fluid of crosslinked top layer are replaced to dual functional diacrylate 1, beyond the 6-hexanediol ester, the step that repeats embodiment 1 preparation Electrophtography photosensor prepares Electrophtography photosensor, wherein do not use three or polyfunctional free yl polymerizating monomer, wherein diacrylate 1, the molecular weight of 6-hexanediol ester is 226, from Wako Pure Chemical Industries, Ltd.

Comparative Examples 3

Except not containing simple function radical polymerization compound and 10 part three in the coating fluid of crosslinked top layer or polyfunctional free yl polymerizating monomer being replaced to 20 parts of dual functional polyethyleneglycol diacrylates with charge migration structure, the step that repeats embodiment 1 preparation Electrophtography photosensor prepares Electrophtography photosensor, wherein do not use the radical polymerization compound of the simple function with charge migration structure, the molecular weight of polyethyleneglycol diacrylate is 308, from Shin-nakamura ChemicalCorporation.

Comparative Examples 4

Except not containing simple function radical polymerization compound and 10 part three in the coating fluid of crosslinked top layer or polyfunctional free yl polymerizating monomer being replaced to 20 parts of dual functional diacrylic acid pentyl diol esters with charge migration structure, the step that repeats embodiment 1 preparation Electrophtography photosensor prepares Electrophtography photosensor, wherein do not use the radical polymerization compound of the simple function with charge migration structure, the molecular weight of diacrylic acid pentyl diol ester is 212, from Shin-nakamura ChemicalCorporation.

Comparative Examples 5

Except not containing three or polyfunctional free yl polymerizating monomer, and 10 parts of radical polymerization compounds with simple function of charge migration structure are replaced to beyond 20 parts, and the step that repeats embodiment 1 preparation Electrophtography photosensor prepares Electrophtography photosensor.

Comparative Examples 6

Except not containing the simple function radical polymerization compound with charge migration structure, and 10 part three or polyfunctional free yl polymerizating monomer replaced to beyond 20 parts, the step that repeats embodiment 1 preparation Electrophtography photosensor prepares Electrophtography photosensor.

Comparative Examples 7

Except that the simple function radical polymerization compound with charge migration structure being replaced to following material, the step that repeats embodiment 1 preparation Electrophtography photosensor prepares Electrophtography photosensor.

Wherein do not use the radical polymerization compound of simple function with charge migration structure.

Comparative Examples 8

Except that the simple function radical polymerization compound with charge migration structure is replaced to following non--the radical polymerization condensation material, the step that repeats embodiment 1 preparation Electrophtography photosensor prepares Electrophtography photosensor.

Comparative Examples 9

Except not forming crosslinked top layer, and the thickness of CTL changed into beyond the 27 μ m, the step that repeats preparation Electrophtography photosensor among the embodiment 1 prepares Electrophtography photosensor.

Comparative Examples 10

Except that the method formation thickness according to embodiment 4 among the Japanese publication 2004-302451 is the crosslinked top layer of 5 μ m, the method that repetition embodiment 1 prepares Electrophtography photosensor prepares Electrophtography photosensor, wherein monomer meets the demands, but the peel strength of discontented unabridged version invention.

Comparative Examples 11

Except that the method formation thickness according to embodiment 9 among the Japanese publication 2004-302452 is the crosslinked top layer of 5 μ m, the method that repetition embodiment 1 prepares Electrophtography photosensor prepares Electrophtography photosensor, wherein monomer meets the demands, but the peel strength of discontented unabridged version invention.

Comparative Examples 12

Except that the method formation thickness according to embodiment 1 among the Japanese publication 2001-183858 is the crosslinked top layer of 5 μ m, the method that repetition embodiment 1 prepares Electrophtography photosensor prepares Electrophtography photosensor, the number of free radical polymerization functional group and peel strength of the present invention in the 1g solid constituent that it does not meet the demands.

The evaluation test method of the photoreceptor for preparing in embodiment and Comparative Examples is as follows.

＜peeling strength test 〉

Use SAICASDN-20 (from DAIPLA WINTES company) second with 0.1 μ m/ second of horizontal resection speed and perpendicular cuts speed 0.01 μ m/, its cutting blade width is 0.5mm.Cutting depth is greater than the thickness on crosslinked top layer.Peel strength is measured divided by the cutting blade width by the horizontal load of cutting depth.

＜hardenability test 〉

The hardenability on crosslinked top layer is to estimate by its solubleness in organic solvent.A tetrahydrofuran is dripped on the photoreceptor, visually observe change then at air dry rear surface profile.When under-ageing, the surface portion dissolving, and have loop concave and convex surface or cloud form decorative pattern (cloud).

＜endurancing 〉

Is the crosslinked top layer of photoreceptor that the packaging film (from Sumitomo3M company) of 0.3 μ m, the 3.5 μ m that locate at an arbitrary position to wear and tear are dark and 10cm is axially wide with surfaceness.Photoreceptor is installed in the handle box, and handle box is installed among improved imager (imagio) MF2200 (from Ricoh company), MF2200 use wavelength as the laser diode (LD) of 655nm as imaging source, cleaning blade with 1.5 times of contact pressures.The dark space of photoreceptor (not rubbing) potential setting is 700 (V), produce 30,000 A4 images, thereby 10,000 images of every generation is measured the thickness and the assess image quality of wearing part.Measure the current potential of initial dark space and the current potential of illuminated portion, and their current potentials after having produced 30,000 images.Measure the thickness of photoreceptor by eddy current film thickness measuring instrument (from Fischer Instruments K.K).

＜crazing-resistance test 〉

(finger grease) is attached to photosensitive surface finger-like railway grease, and it was placed 3 days under 50 ℃, normal pressure, observes its surface then.

Table 4 has shown the peel strength and the hardenability test findings of the photoreceptor of embodiment 1-16 and Comparative Examples 1-12 preparation.

Table 4

Photoreceptor	The number of free radical polymerization functional group	Peel strength (N/mm)	Hardenability
Photoreceptor	The number of free radical polymerization functional group	Peel strength (N/mm)	Hardenability	Embodiment 1	3.55×10 ²¹	0.13	Soluble
Embodiment 2	The same	0.24	Soluble	Embodiment 1	3.55×10 ²¹	0.13	Soluble
Embodiment 2	The same	0.24	Soluble	Embodiment 3	The same	0.32	Soluble
Embodiment 4	The same	0.15	Soluble	Embodiment 3	The same	0.32	Soluble
Embodiment 4	The same	0.15	Soluble	Embodiment 5	The same	0.26	Soluble
Embodiment 6	The same	0.27	Soluble	Embodiment 5	The same	0.26	Soluble
Embodiment 6	The same	0.27	Soluble	Embodiment 7	The same	0.30	Soluble
Embodiment 8	The same	0.11	Soluble	Embodiment 7	The same	0.30	Soluble
Embodiment 8	The same	0.11	Soluble	Embodiment 9	The same	0.25	Soluble
Embodiment 10	3.57×10 ²¹	0.21	Soluble	Embodiment 9	The same	0.25	Soluble
Embodiment 10	3.57×10 ²¹	0.21	Soluble	Embodiment 11	3.25×10 ²¹	0.16	Soluble
Embodiment 12	3.59×10 ²¹	0.15	Soluble	Embodiment 11	3.25×10 ²¹	0.16	Soluble
Embodiment 12	3.59×10 ²¹	0.15	Soluble	Embodiment 13	3.68×10 ²¹	0.14	Soluble
Embodiment 14	3.59×10 ²¹	0.23	Soluble	Embodiment 13	3.68×10 ²¹	0.14	Soluble
Embodiment 14	3.59×10 ²¹	0.23	Soluble	Embodiment 15	3.52×10 ²¹	0.22	Soluble
Embodiment 16	2.58×10 ²¹	0.42	Soluble	Embodiment 15	3.52×10 ²¹	0.22	Soluble
Embodiment 16	2.58×10 ²¹	0.42	Soluble	Comparative Examples 1	2.50×10 ²¹	0.20	Soluble
Comparative Examples 2	3.18×10 ²¹	0.40	Solubilized	Comparative Examples 1	2.50×10 ²¹	0.20	Soluble
Comparative Examples 2	3.18×10 ²¹	0.40	Solubilized	Comparative Examples 3	3.72×10 ²¹	0.33	Soluble
Comparative Examples 4	5.41×10 ²¹	0.21	Soluble	Comparative Examples 3	3.72×10 ²¹	0.33	Soluble
Comparative Examples 4	5.41×10 ²¹	0.21	Soluble	Comparative Examples 5	1.37×10 ²¹	Not plastic
Comparative Examples 6	5.81×10 ²¹	0.03	Soluble	Comparative Examples 5	1.37×10 ²¹	Not plastic
Comparative Examples 6	5.81×10 ²¹	0.03	Soluble	Comparative Examples 7	4.29×10 ²¹	0.05	Soluble
Comparative Examples 8	2.91×10 ²¹	1.20	Solubilized	Comparative Examples 7	4.29×10 ²¹	0.05	Soluble
Comparative Examples 8	2.91×10 ²¹	1.20	Solubilized	Comparative Examples 9	0	0.35	Solubilized
Comparative Examples 10	3.84×10 ²¹	0.06	Soluble	Comparative Examples 9	0	0.35	Solubilized
Comparative Examples 10	3.84×10 ²¹	0.06	Soluble	Comparative Examples 11	3.37×10 ²¹	0.08	Soluble
Comparative Examples 12	7.55×10 ²¹	0.03	Soluble	Comparative Examples 11	3.37×10 ²¹	0.08	Soluble

The photoreceptor of the present invention for preparing in embodiment 1-16, it contains 2.55 * 10 in crosslinked top layer ²¹Or polyradical polymer functional group/1g solid constituent more, and peel strength is no less than 0.1N/mm simultaneously.That is, can think that crosslinked top layer has closely knit three-dimensional net structure and has good adhesiveness with following photosensitive layer (lowerphotosensitive layer).All photoreceptors that prepare among the embodiment all have good hardenability.In embodiment 2-4, when the solvent with less saturation vapour pressure or higher boiling point was used for crosslinked top layer, it is big that the peel strength on crosslinked top layer becomes.In embodiment 5-7, when solvent has the solubility parameters of 8.5-11.0, and during preferred 9.0-9.7, it is big that peel strength becomes.In addition, in embodiment 1,8 and 9, when the solid component concentration of crosslinked top layer coating fluid more after a little while, it is big that peel strength becomes.In embodiment 15 and 16, even when when having the polyfunctional monomer sclerosis of 5 or a plurality of functional groups, crosslinked top layer has enough peel strengths.

Simultaneously, the photoreceptor that comprises bifunctional monomer in the crosslinked top layer in the Comparative Examples 2, the photoreceptor that only contains charge migration compound in the crosslinked top layer in the Comparative Examples 5 with free radical polymerization group, the photoreceptor that does not have crosslinked top layer in photoreceptor that comprises the low-molecular-weight charge transporting material in crosslinked top layer in the Comparative Examples 8 and the Comparative Examples 9 all dissolves in organic solvent.Comparative Examples 2,5 and 8 crosslinked top layer be sclerosis fully.Photoreceptor in the Comparative Examples 1 has than 2.50 * 10 in crosslinked top layer ²¹Though the photoreceptor among the free radical polymerization functional group that/1g solid constituent is few and Comparative Examples 6,7 and the 10-12 has enough free radical polymerization functional groups and has little peel strength, and think that their top layer and following photosensitive layer do not have enough adhesivenesses.Photoreceptor in the Comparative Examples 3 and 4 has enough free radical polymerization functional groups, good peel strength and hardenability.Yet owing to contain too many bifunctional monomer, their illuminated portion has high surface potential and image density deterioration at first, and is as shown in table 5.

Table 5 has shown the endurancing result of the photoreceptor that embodiment 1-16 and Comparative Examples 1,3,4,6,7,9,10-12 prepare.

Table 5

	Wear extent (μ m)			The initial surface current potential (V)		Surface potential after 30,000
	Wear extent (μ m)			The initial surface current potential (V)		Surface potential after 30,000		10,000	20,000	30,000	The dark space	Illuminated portion	The dark space	Illuminated portion
	Embodiment 1	0.11	0.22	0.33	700	110	680	10,000	20,000	30,000	The dark space	Illuminated portion	The dark space	Illuminated portion	120
Embodiment 2	Embodiment 1	0.11	0.22	0.33	700	110	680	0.12	0.24	0.37	700	110	680	120	120
Embodiment 2	Embodiment 3	0.21	0.43	0.65	700	115	670	0.12	0.24	0.37	700	110	680	120	110
Embodiment 4	Embodiment 3	0.21	0.43	0.65	700	115	670	0.12	0.25	0.36	700	110	685	120	110
Embodiment 4	Embodiment 5	0.12	0.24	0.36	700	110	680	0.12	0.25	0.36	700	110	685	120	120
Embodiment 6	Embodiment 5	0.12	0.24	0.36	700	110	680	0.13	0.25	0.36	700	110	680	120	120
Embodiment 6	Embodiment 7	0.12	0.23	0.37	700	110	680	0.13	0.25	0.36	700	110	680	120	120
Embodiment 8	Embodiment 7	0.12	0.23	0.37	700	110	680	0.12	0.24	0.36	700	115	680	120	120
Embodiment 8	Embodiment 9	0.12	0.27	0.38	700	110	675	0.12	0.24	0.36	700	115	680	120	115
Embodiment 10	Embodiment 9	0.12	0.27	0.38	700	110	675	0.22	0.42	0.62	700	110	670	110	115
Embodiment 10	Embodiment 11	0.16	0.32	0.48	700	105	675	0.22	0.42	0.62	700	110	670	110	110
Embodiment 12	Embodiment 11	0.16	0.32	0.48	700	105	675	0.15	0.39	0.45	700	110	675	110	110
Embodiment 12	Embodiment 13	0.14	0.27	0.42	700	110	675	0.15	0.39	0.45	700	110	675	110	115
Embodiment 14	Embodiment 13	0.14	0.27	0.42	700	110	675	0.25	0.50	0.75	700	110	665	105	115
Embodiment 14	Embodiment 15	0.09	0.18	0.26	700	110	680	0.25	0.50	0.75	700	110	665	105	115
Embodiment 16	Embodiment 15	0.09	0.18	0.26	700	110	680	0.11	0.22	0.33	700	110	680	115	115
Embodiment 16	Comparative Examples 1	0.61	1.22	1.83	700	110	660	0.11	0.22	0.33	700	110	680	115	95
Comparative Examples 3	Comparative Examples 1	0.61	1.22	1.83	700	110	660	Image density just reduces from the beginning, and test stops			700	355	-	-	95

Comparative Examples 4	Image density just reduces from the beginning, and test stops			700	360	-	-
Comparative Examples 4				700	360	-	-	Comparative Examples 6	Image density just reduces from the beginning, and test stops			700	350	-	-
Comparative Examples 7	1.29	3.69	3.87	700	115	-	-	Comparative Examples 6				700	350	-	-
Comparative Examples 7	1.29	3.69	3.87	700	115	-	-	Comparative Examples 9	1.88	3.76	5.65	700	80	655	60
Comparative Examples 10	1.32	3.65	-	700	115	-	-	Comparative Examples 9	1.88	3.76	5.65	700	80	655	60
Comparative Examples 10	1.32	3.65	-	700	115	-	-	Comparative Examples 11	1.25	3.60	-	700	115	-	-
Comparative Examples 12	1.98	-	-	700	225	-	-	Comparative Examples 11	1.25	3.60	-	700	115	-	-

The photoreceptor of embodiment 1-16 preparation is frayed less and their wear extent is stable.In addition, the surface potential of its illuminated portion is less in the change of producing 30,000 images front and back generations.In the present invention, the interphase between crosslinked top layer and the following photosensitive layer also keeps high permanance.The photoreceptor with few free radical polymerization functional group in the Comparative Examples 1 does not have enough wearing qualities.In the Comparative Examples 6,7 with little peel strength, 10-12, because crosslinked skin depth is 5 μ m, the illuminated portion and the Comparative Examples 12 that do not have the Comparative Examples 6 of charge migration structure on crosslinked top layer have noble potential at first.In addition, Comparative Examples 12 has big wear extent, thinks that its crosslinked top layer does not have enough adhesivenesses.Having the Comparative Examples 7,10 of little peel strength and 11 crosslinked skin depth reduces soon.In crosslinked top layer, do not have the Comparative Examples 3 of charge migration structure and 4 illuminated portion and have very high current potential at first.Comparative Examples 9 proofs, high wearing quality of Electrophtography photosensor and stable electrical property are given in crosslinked top layer of the present invention.

Table 6 has shown the crazing-resistance test result of the photoreceptor that embodiment 1-16 is prepared into.

Table 6

	Beginning	After 3 days
	Beginning	After 3 days	Embodiment 1	Smooth surface	No cracking
Embodiment 2	Smooth surface	No cracking	Embodiment 1	Smooth surface	No cracking
Embodiment 2	Smooth surface	No cracking	Embodiment 3	Smooth surface	No cracking
Embodiment 4	Smooth surface	No cracking	Embodiment 3	Smooth surface	No cracking
Embodiment 4	Smooth surface	No cracking	Embodiment 5	Smooth surface	No cracking
Embodiment 6	Smooth surface	No cracking	Embodiment 5	Smooth surface	No cracking
Embodiment 6	Smooth surface	No cracking	Embodiment 7	Smooth surface	No cracking
Embodiment 8	Smooth surface	No cracking	Embodiment 7	Smooth surface	No cracking
Embodiment 8	Smooth surface	No cracking	Embodiment 9	Smooth surface	No cracking
Embodiment 10	Smooth surface	No cracking	Embodiment 9	Smooth surface	No cracking
Embodiment 10	Smooth surface	No cracking	Embodiment 11	Smooth surface	No cracking
Embodiment 12	Smooth surface	No cracking	Embodiment 11	Smooth surface	No cracking
Embodiment 12	Smooth surface	No cracking	Embodiment 13	Smooth surface	No cracking
Embodiment 14	Smooth surface	No cracking	Embodiment 13	Smooth surface	No cracking
Embodiment 14	Smooth surface	No cracking	Embodiment 15	Smooth surface	No cracking
Embodiment 16	Smooth surface	No cracking	Embodiment 15	Smooth surface	No cracking

Cracking does not take place in photoreceptor of the present invention, and this proves that its crosslinked top layer contains the compound with charge migration structure equably.

(synthetic embodiment 1)

1 of 292g, 3-diimino isoindoline and 2, the sulfolane of 000ml mixes, and in nitrogen stream 204g four titanium butoxide (titaniumtetrabutoxide) is splashed in the potpourri then.Potpourri little by little heated up to mixture temperature reach 180 ℃, and stirred 5 hours, simultaneously temperature of reaction is remained on 170-180 ℃.After the potpourri cooling, precipitation precipitate (powder) is filtered, become blueness with the chloroform cleaning up to powder then.Next step powder with washed with methanol several times, and then is that 80 ℃ hot water cleans several times with temperature, thereby makes thick titanyl phthalocyanine pigment.Thick titanyl phthalocyanine pigment is sneaked in the dense sulfonic acid, and the amount of dense sulfonic acid is 20 times of thick titanyl phthalocyanine amount of pigment, stir then, thereby pigment dissolved in dense sulfonic acid; While stirring potpourri is splashed in the frozen water then, the amount of frozen water is 100 times of potpourri amount; (precipitated) crystal that precipitation is separated out filters then.Next, the water that the crystal water is cleaned repeatedly after cleaning becomes neutrality, thereby makes the wet cake of titanyl phthalocyanine pigment.Wet cake is cleaned with ion exchange water fully, do not find the xx ion in the ion exchange water after cleaning.

The 20g wet cake is put into 1 of 200g, in the 2-ethylene dichloride, then potpourri was stirred 4 hours.1, the methyl alcohol of 000g filters and drying composite, thereby makes the titanyl phthalocyanine pigment powder after putting into potpourri and potpourri being stirred 1 hour.

Under following condition, measure the X-ray diffraction spectrum of titanyl phthalocyanine powder, discovery is with the Cu-K alpha-irradiation time, the titanyl phthalocyanine powder has Prague (2 θ) main peak 9.6 ± 0.2 °, 24.0 ± 0.2 ° and 27.2 ± 0.2 °, as shown in Figure 7 at least in X-ray diffraction spectrum.

X-ray tube: Cu

Voltage: 40 kilovolts

Electric current: 20mA

Sweep speed: 1 °/minute

Sweep limit: 3-40 °

Time constant: 2 seconds

Embodiment 17

Be coated in undercoat coating fluid, charge generation coating fluid and charge migration coating fluid according to following prescription on the aluminium cylinder successively and drying, the diameter of this aluminium cylinder is 30mm, is that the undercoat of 3.5 μ m, CGL, the thickness that thickness is 0.3 μ m are the CTL of 23 μ m thereby form thickness.

Adopt spraying method, on CTL, further apply bonding coat coating fluid and top layer coating fluid according to following prescription.

With metal halide lamp with 160W/cm, 120mm radiation length and 500mW/cm ²Bonding coat coating fluid that irradiation applies under the radiation intensity and top layer coating fluid 120 seconds, thus make its sclerosis, descending dry 20 minutes at 130 ℃ then, thereby make Electrophtography photosensor of the present invention, its bondline thickness is that 0.5 μ m, skin depth are 4 μ m.Fig. 8 has shown the cross section electron scanning micrograph of photoreceptor.

The undercoat coating fluid

Alkyd resin 6

(BEKKOZOL 1307-60-EL is from Dainippon Ink ﹠amp; Chemicals, Inc.)

Melamine resin 4

(SUPER BEKKAMIN G-821-60 is from Dainippon Ink ﹠amp; Chemicals, Inc.)

Titania powder 40

Methyl ethyl ketone 50

The CGL coating fluid

Polyvinyl butyral 0.5

(XYHL is from Union Carbide company)

Cyclohexanone 200

Methyl ethyl ketone 80

Disazo pigment 2.5 with following formula (I)

The CTL coating fluid

Bisphenol Z polycarbonate 10

(Panlite TS-2050 is from TEIJIN CHEMICALS LTD.)

Tetrahydrofuran 100

The tetrahydrofuran solution 1 of the silicone oil of concentration 1%

(KF50-100CS is from Shin-Etsu Chemical Industry Co., Ltd.)

Charge transporting material 7 with following formula (II)

The bonding coat coating fluid

Polyarylate (Polyarylate) 1

(U-POLYMER U-100 is from Unitika company)

Three or the polyfunctional free yl polymerizating monomer 9 that do not have the charge migration structure

Molecular weight is 296, molecular weight/functional group is 99 trimethylolpropane triacrylate

(KAYARAD TMPTA is from NIPPON KAYAKU CO., LTD.)

Radical polymerization compound 5 with simple function of charge migration structure

(exemplary compounds 54)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

The top layer coating fluid

(KAYARAD TMPTA is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 54)

Photoepolymerizationinitiater initiater 1

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 100

Embodiment 18

Except that this bonding coat being replaced to the bonding coat with following prescription, the step that repeats preparation Electrophtography photosensor among the embodiment 17 prepares Electrophtography photosensor.

Polyarylate 3

(U-POLYMER U-100 is from Unitika company)

Three or the polyfunctional free yl polymerizating monomer 7 that do not have the charge migration structure

(KAYARAD TMPTA is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 54)

Photoepolymerizationinitiater initiater 0.5

Molecular weight is 204 and does not contain the 1-hydroxyl-cyclohexyl-phenyl-ketone of functional group

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

Embodiment 19

Polyarylate 5

(U-POLYMER U-100 is from Unitika company)

Three or the polyfunctional free yl polymerizating monomer 5 that do not have the charge migration structure

(KAYARAD TMPTA is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 54)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

Embodiment 20

Polyarylate 7

(U-POLYMER U-100 is from Unitika company)

Three or the polyfunctional free yl polymerizating monomer 3 that do not have the charge migration structure

(KAYARAD TMPTA is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 54)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

Embodiment 21

Polyarylate 9

(U-POLYMER U-100 is from Unitika company)

Three or the polyfunctional free yl polymerizating monomer 1 that do not have the charge migration structure

Molecular weight is the trimethylolpropane triacrylate of 296,99 functional groups

(KAYARAD TMPTA is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 54)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

Embodiment 22

Be coated in undercoat coating fluid, charge generation coating fluid and charge migration coating fluid according to following prescription on the aluminium cylinder successively and drying, the diameter of this aluminium cylinder is 30mm, thereby forms the undercoat that thickness is 1.5 μ m thereon, CGL, the thickness that thickness is 0.3 μ m is the CTL of 23 μ m.

With metal halide lamp with 160W/cm, 120mm radiation length and 500mW/cm ²Bonding coat coating fluid that irradiation applies under the radiation intensity and top layer coating fluid 120 seconds, thus make its sclerosis, descending dry 20 minutes at 130 ℃ then, thereby make Electrophtography photosensor of the present invention, its bondline thickness is that 0.03 μ m, skin depth are 4 μ m.

The undercoat coating fluid

Titanium dioxide 40

The molten nylon 32 of alcohol

Methyl alcohol 400

Isopropyl alcohol 160

The CGL coating fluid

Synthetic titanyl phthalocyanine powder 4 in synthetic embodiment 1

Polyvinyl butyral 2

Methyl ethyl ketone 150

The CTL coating fluid

Bisphenol Z polycarbonate 10

(Panlite TS-2050 is from TEIJIN CHEMICALS LTD.)

Tetrahydrofuran 100

Concentration is the tetrahydrofuran solution 1 of 1% silicone oil

(KF50-100CS is from Shin-Etsu Chemical Industry Co., Ltd.)

Charge transporting material with following formula (II): 7

The bonding coat coating fluid

Bisphenol Z polycarbonate 5

(Panlite TS-2050 is from TEIJIN CHEMICALS LTD.)

Three or the polyfunctional free yl polymerizating monomer 5 that do not have the electron transfer structure

Molecular weight is that 536,5.5 functional groups and molecular weight/functional group are 97 trimethylolpropane triacrylate

(KAYARAD DPHA is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 105)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

The top layer coating fluid

(KAYARAD DPHA is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 105)

Photoepolymerizationinitiater initiater 1

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 100

Embodiment 23

Except that bondline thickness being changed into 0.06 μ m, the step that repeats preparation Electrophtography photosensor among the embodiment 22 prepares Electrophtography photosensor.

Embodiment 24

Except that bondline thickness being changed into 0.09 μ m, the step that repeats preparation Electrophtography photosensor among the embodiment 22 prepares Electrophtography photosensor.

Embodiment 25

Except that bondline thickness being changed into 0.12 μ m, the step that repeats preparation Electrophtography photosensor among the embodiment 22 prepares Electrophtography photosensor.

Embodiment 26

Except that bondline thickness being changed into 0.2 μ m, the step that repeats preparation Electrophtography photosensor among the embodiment 22 prepares Electrophtography photosensor.

Embodiment 27

Except that bondline thickness being changed into 0.5 μ m, the step that repeats preparation Electrophtography photosensor among the embodiment 22 prepares Electrophtography photosensor.

Embodiment 28

Except that bondline thickness being changed into 0.8 μ m, the step that repeats preparation Electrophtography photosensor among the embodiment 22 prepares Electrophtography photosensor.

Embodiment 29

Except that bondline thickness being changed into 1.2 μ m, the step that repeats preparation Electrophtography photosensor among the embodiment 22 prepares Electrophtography photosensor.

Embodiment 30

Except that bondline thickness being changed into 4 μ m, the step that repeats preparation Electrophtography photosensor among the embodiment 22 prepares Electrophtography photosensor.

Embodiment 31

Except that bondline thickness being changed into 7 μ m, the step that repeats preparation Electrophtography photosensor among the embodiment 22 prepares Electrophtography photosensor.

Embodiment 32

Except that bonding coat being replaced to the bonding coat with following prescription, the step that repeats preparation Electrophtography photosensor among the embodiment 19 prepares Electrophtography photosensor.

Bisphenol Z polycarbonate 5

(Panlite TS-2050 is from TEIJIN CHEMICALS LTD.)

(KAYARAD TMPTA is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 54)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

Comparative Examples 13

Except that not applying the bonding coat coating fluid, the step that repeats preparation Electrophtography photosensor among the embodiment 17 prepares Electrophtography photosensor.

Fig. 9 has shown the cross section electron scanning micrograph of photoreceptor.In Fig. 9,, can clearly distinguish CTL and top layer owing to there is not bonding coat.In Fig. 8, bonding coat is present between CTL and the top layer, and does not have interphase.

The photoreceptor that embodiment 17-32 and Comparative Examples 13 are prepared is installed among imager (imagio) Neo270, its use wavelength as the laser diode of 655nm as the imaging irradiator, and producing 100,000 S3 bar chart images on the My Paper in the A4 size under the initial potential of-700V from NBS Ricoh company.Estimate polishing machine, inner potential and picture quality.Table 7-9 has shown these results.

Table 7

	Wear extent (μ m)
	Wear extent (μ m)		50,000	100,000
	Embodiment 17	0.71	50,000	100,000	2.26
Embodiment 18	Embodiment 17	0.71	0.73	1.51	2.26
Embodiment 18	Embodiment 19	0.68	0.73	1.51	1.42
Embodiment 20	Embodiment 19	0.68	0.71	1.48	1.42
Embodiment 20	Embodiment 21	0.69	0.71	1.48	2.41
Embodiment 22	Embodiment 21	0.69	0.70	1.84	2.41
Embodiment 22	Embodiment 23	0.72	0.70	1.84	1.74
Embodiment 24	Embodiment 23	0.72	0.69	1.66	1.74
Embodiment 24	Embodiment 25	0.71	0.69	1.66	1.44
Embodiment 26	Embodiment 25	0.71	0.71	1.42	1.44
Embodiment 26	Embodiment 27	0.66	0.71	1.42	1.43
Embodiment 28	Embodiment 27	0.66	0.67	1.39	1.43
Embodiment 28	Embodiment 29	0.70	0.67	1.39	1.39
Embodiment 30	Embodiment 29	0.70	0.72	1.40	1.39
Embodiment 30	Embodiment 31	0.69	0.72	1.40	1.36
Embodiment 32	Embodiment 31	0.69	0.67	1.40	1.36
Embodiment 32	Comparative Examples 13	2.11	0.67	1.40	6.92

Table 8

	Surface potential
	Surface potential						Initial (V)		50,000(-V)		100,000(-V)
	The dark space	Illuminated portion	The dark space	Illuminated portion	The dark space	Illuminated portion	Initial (V)		50,000(-V)		100,000(-V)
	The dark space	Illuminated portion	The dark space	Illuminated portion	The dark space	Illuminated portion	Embodiment 17	700	120	640	130	610	140
Embodiment 18	700	140	680	150	630	160	Embodiment 17	700	120	640	130	610	140
Embodiment 18	700	140	680	150	630	160	Embodiment 19	700	150	680	160	650	180
Embodiment 20	700	180	660	190	640	190	Embodiment 19	700	150	680	160	650	180
Embodiment 20	700	180	660	190	640	190	Embodiment 21	700	180	630	200	600	220
Embodiment 22	700	110	650	120	630	100	Embodiment 21	700	180	630	200	600	220
Embodiment 22	700	110	650	120	630	100	Embodiment 23	700	100	640	90	660	110
Embodiment 24	700	100	640	110	650	130	Embodiment 23	700	100	640	90	660	110
Embodiment 24	700	100	640	110	650	130	Embodiment 25	700	110	660	100	640	120
Embodiment 26	700	110	680	110	660	120	Embodiment 25	700	110	660	100	640	120
Embodiment 26	700	110	680	110	660	120	Embodiment 27	700	120	670	120	630	140
Embodiment 28	700	110	690	120	650	140	Embodiment 27	700	120	670	120	630	140
Embodiment 28	700	110	690	120	650	140	Embodiment 29	700	120	690	140	670	130
Embodiment 30	700	160	690	180	670	230	Embodiment 29	700	120	690	140	670	130
Embodiment 30	700	160	690	180	670	230	Embodiment 31	700	200	700	230	680	260
Embodiment 32	700	120	680	130	660	160	Embodiment 31	700	200	700	230	680	260
Embodiment 32	700	120	680	130	660	160	Comparative Examples 13	700	150	620	170	500	190

Table 9

	Picture quality
	Picture quality			Initially	50,000	100,000
	Embodiment 17	◎	◎	Initially	50,000	100,000	△
Embodiment 18	Embodiment 17	◎	◎	◎	◎	◎	△
Embodiment 18	Embodiment 19	◎	◎	◎	◎	◎	◎
Embodiment 20	Embodiment 19	◎	◎	◎	◎	◎	◎
Embodiment 20	Embodiment 21	◎	◎	◎	◎	◎	△
Embodiment 22	Embodiment 21	◎	◎	◎	◎	○	△
Embodiment 22	Embodiment 23	◎	◎	◎	◎	○	○
Embodiment 24	Embodiment 23	◎	◎	◎	◎	○	○
Embodiment 24	Embodiment 25	◎	◎	◎	◎	○	◎
Embodiment 26	Embodiment 25	◎	◎	◎	◎	◎	◎
Embodiment 26	Embodiment 27	◎	◎	◎	◎	◎	◎
Embodiment 28	Embodiment 27	◎	◎	◎	◎	◎	◎
Embodiment 28	Embodiment 29	◎	◎	◎	◎	◎	◎
Embodiment 30	Embodiment 29	◎	◎	◎	◎	◎	◎
Embodiment 30	Embodiment 31	◎	◎	◎	◎	◎	◎
Embodiment 32	Embodiment 31	◎	◎	◎	◎	◎	◎
Embodiment 32	Comparative Examples 13	◎	×	◎	◎	◎	×

◎: fine

Zero: good

△: locality produces stripe pattern

*: produce stripe pattern equably

Even the photoreceptor for preparing in embodiment 17-32 has good wearing quality and produce the image (quality image) of high-quality after producing 100,000 images.Yet the photoreceptor of preparation is worn away soon in Comparative Examples 13, and produces the image that has stripe pattern equably after producing 50,000 images.

Embodiment 33

Be coated in undercoat coating fluid, charge generation coating fluid and charge migration coating fluid according to following prescription on the aluminium cylinder successively and drying, the diameter of this aluminium cylinder is 30mm, thereby forms the undercoat that thickness is 3.5 μ m thereon, CGL, the thickness that thickness is 0.3 μ m is the CTL of 23 μ m.

With metal halide lamp with 160W/cm, 120mm radiation length and 500mW/cm ²Bonding coat coating fluid that irradiation applies under the radiation intensity and top layer coating fluid 120 seconds, thus make its sclerosis, descending dry 20 minutes at 130 ℃ then, thereby make Electrophtography photosensor of the present invention, its bondline thickness is that 0.5 μ m, skin depth are 4 μ m.

The undercoat coating fluid

Alkyd resin 6

(BEKKOZOL 1307-60-EL is from Dainippon Ink ﹠amp; Chemicals, Inc.)

Melamine resin 4

(SUPER BEKKAMIN G-821-60 is from Dainippon Ink ﹠amp; Chemicals, Inc.)

Titania powder 40

Methyl ethyl ketone 50

The CGL coating fluid

Polyvinyl butyral 0.5

(XYHL is from Union Carbide company)

Cyclohexanone 200

Methyl ethyl ketone 80

Disazo pigment 2.5 with following formula (I)

The CTL coating fluid

Bisphenol Z polycarbonate 10

(Panlite TS-2050 is from TEIJIN CHEMICALS LTD.)

Tetrahydrofuran 100

Concentration is the tetrahydrofuran solution 1 of 1% silicone oil

(KF50-100CS is from Shin-Etsu Chemical Industry Co., Ltd.)

Charge transporting material with following formula (II): 7

The bonding coat coating fluid

Two or the polyfunctional free yl polymerizating monomer 5 that does not have the charge migration structure

25 ℃ of following viscosity is the diacrylate with 2 functional groups 1 of 8mPAs, the 4-butanediol ester

(SR213 is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 54)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

The top layer coating fluid

(KAYARAD TMPTA is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 54)

Photoepolymerizationinitiater initiater 1

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 100

Embodiment 34

Except that bonding coat being replaced to the bonding coat with following prescription, the step that repeats preparation Electrophtography photosensor among the embodiment 33 prepares Electrophtography photosensor.

25 ℃ of following viscosity is the diacrylate diglycol ester with 2 functional groups of 12mPAs

(SR230 is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 54)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

Embodiment 35

25 ℃ of following viscosity is the diacrylate tetraethylene glycol ester with 2 functional groups of 20mPAs

(SR268 is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 54)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

Embodiment 36

25 ℃ of following viscosity is the diacrylate triethyleneglycol ester with 2 functional groups of 15mPAs

(SR272 is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 54)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

Embodiment 37

25 ℃ of following viscosity is the propoxylation dipropyl with 2 functional groups of 15mPAs

Olefin(e) acid DOPCP (Propoxylated neopentylglycoldiacrylate)

(SR268 is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 54)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

Embodiment 38

25 ℃ of following viscosity is the n-butyl acrylate with 2 functional groups of 0.81mPAs

(from TOKYO KASEI KOGYO company)

(exemplary compounds 54)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

Embodiment 39

25 ℃ of following viscosity is the n-butyl acrylate with 2 functional groups of 24mPAs

(SR560 is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 54)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

Comparative Examples 14

Except that not applying the bonding coat coating fluid, the step that repeats preparation Electrophtography photosensor among the embodiment 33 prepares Electrophtography photosensor.

The photoreceptor that embodiment 33-39 and Comparative Examples 14 are prepared is installed among imager (imagio) Neo270, its use wavelength as the laser diode of 655nm as the imaging irradiator, and producing 100,000 S3 bar chart images on the My Paper in the A4 size under the initial potential of-700V from NBS Ricoh company.Estimate polishing machine, inner potential and picture quality.The results are shown among the table 10-12.

Table 10

	Wear extent (μ m)
	Wear extent (μ m)		50,000	100,000
	Embodiment 33	0.59	50,000	100,000	1.61
Embodiment 34	Embodiment 33	0.59	0.67	1.51	1.61
Embodiment 34	Embodiment 35	0.68	0.67	1.51	1.42
Embodiment 36	Embodiment 35	0.68	0.79	1.48	1.42
Embodiment 36	Embodiment 37	0.69	0.79	1.48	1.74
Embodiment 38	Embodiment 37	0.69	0.70	2.28	1.74
Embodiment 38	Embodiment 39	0.72	0.70	2.28	2.16
Comparative Examples 14	Embodiment 39	0.72	2.11	9.15	2.16

Table 11

	Surface potential
	Surface potential						Initial (V)		50,000(-V)		100,000(-V)
	The dark space	Illuminated portion	The dark space	Illuminated portion	The dark space	Illuminated portion	Initial (V)		50,000(-V)		100,000(-V)
	The dark space	Illuminated portion	The dark space	Illuminated portion	The dark space	Illuminated portion	Embodiment
33	700	120	640	130	610	140	Embodiment
33	700	120	640	130	610	140	Embodiment 34	700	140	680	150	630	160
Embodiment 35	700	150	680	160	650	180	Embodiment 34	700	140	680	150	630	160
Embodiment 35	700	150	680	160	650	180	Embodiment 36	700	180	660	190	640	190
Embodiment 37	700	180	630	200	600	220	Embodiment 36	700	180	660	190	640	190
Embodiment 37	700	180	630	200	600	220	Embodiment 38	700	110	650	120	630	100
Embodiment 39	700	100	640	90	660	110	Embodiment 38	700	110	650	120	630	100
Embodiment 39	700	100	640	90	660	110	Comparative Examples 14	700	120	620	130	500	140

Table 12

	Picture quality
	Picture quality			Initially	50,000	100,000
	Embodiment 33	○	○	Initially	50,000	100,000	×
Embodiment 34	Embodiment 33	○	○	○	○	○	×
Embodiment 34	Embodiment 35	○	○	○	○	○	○
Embodiment 36	Embodiment 35	○	○	○	○	○	○
Embodiment 36	Embodiment 37	○	○	○	○	○	○
Embodiment 38	Embodiment 37	○	○	○	○	×	○
Embodiment 38	Embodiment 39	○	○	○	○	×	×
Comparative Examples 13	Embodiment 39	○	○	○	×	×	×

◎: fine

Zero: good

△: locality produces stripe pattern

*: produce stripe pattern equably

Embodiment 40

Be coated in undercoat coating fluid, charge generation coating fluid and charge migration coating fluid according to following prescription on the aluminium cylinder successively and drying, the diameter of this aluminium cylinder is 30mm, thereby forms the undercoat that thickness is 1.0 μ m thereon, CGL, the thickness that thickness is 0.3 μ m is the CTL of 23 μ m.

The undercoat coating fluid

Titanium dioxide 40

The molten nylon 32 of alcohol

Methyl alcohol 400

Isopropyl alcohol 160

The CGL coating fluid

Synthetic titanyl phthalocyanine powder 4 in synthetic embodiment 1

Polyvinyl butyral 2

(S-LEC BM-S is from Sekisui CHEMICALS Co., LTD.)

Methyl ethyl ketone 150

The CTL coating fluid

Bisphenol Z polycarbonate 10

(Panlite TS-2050 is from TEIJIN CHEMICALS LTD.)

Tetrahydrofuran 100

Concentration is the tetrahydrofuran solution 1 of 1% silicone oil

(KF50-100CS is from Shin-Etsu Chemical Industry Co., Ltd.)

Charge transporting material 7 with following formula (II)

The bonding coat coating fluid

25 ℃ of following viscosity is the dimethyl propylene with 2 functional groups of 7mPAs

Olefin(e) acid 1, the 4-butanediol ester

(SR214 is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 105)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

The top layer coating fluid

Molecular weight be 536,5.5 functional groups and molecular weight/functional group be 97 three

The hydroxymethyl-propane triacrylate

(KAYARAD DPHA is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 105)

Photoepolymerizationinitiater initiater 1

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 100

Embodiment 41

Except that bonding coat being replaced to the bonding coat with following prescription, the step that repeats preparation Electrophtography photosensor among the embodiment 40 prepares Electrophtography photosensor.

25 ℃ of following viscosity is the dimethyl allene with 2 functional groups of 8mPAs

Acid diglycol ester

(SR231E is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 105)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

Embodiment 42

25 ℃ of following viscosity is the dimethyl allene with 2 functional groups of 14mPAs

Acid tetraethylene glycol ester

(SR209 is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 105)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

Embodiment 43

25 ℃ of following viscosity is the dimethyl allene with 2 functional groups of 11mPAs

The acid triethyleneglycol ester

(SR205 is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 105)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

Embodiment 44

The acid DOPCP

(SR248 is from NIPPON KAYAKU CO., LTD.)

(exemplary compounds 105)

Photoepolymerizationinitiater initiater 0.5

(IRGACURE 184, from CIBA SPECIALTY CHEMICALS)

Tetrahydrofuran 400

Embodiment 45

Except that bondline thickness being changed into 0.05 μ m, the step that repeats preparation Electrophtography photosensor among the embodiment 40 prepares Electrophtography photosensor.

Embodiment 46

Except that bondline thickness being changed into 6 μ m, the step that repeats preparation Electrophtography photosensor among the embodiment 40 prepares Electrophtography photosensor.

Comparative Examples 15

Except that not applying the bonding coat coating fluid, the step that repeats preparation Electrophtography photosensor among the embodiment 40 prepares Electrophtography photosensor.

The photoreceptor that embodiment 40-46 and Comparative Examples 15 are prepared is installed among imager (imagio) Neo270, its use wavelength as the laser diode of 655nm as the imaging irradiator, and produce 100,000 S3 bar chart images on the My Paper in the A4 size under-700V initial potential from NBS Ricoh company.Estimate polishing machine, inner potential and picture quality.The results are shown among the table 13-15.

Table 13

	Wear extent (μ m)
	Wear extent (μ m)		50,000	100,000
	Embodiment 40	0.69	50,000	100,000	1.38
Embodiment 41	Embodiment 40	0.69	0.64	1.44	1.38
Embodiment 41	Embodiment 42	0.71	0.64	1.44	1.42
Embodiment 43	Embodiment 42	0.71	0.66	1.43	1.42
Embodiment 43	Embodiment 44	0.67	0.66	1.43	1.39
Embodiment 45	Embodiment 44	0.67	0.82	4.84	1.39
Embodiment 45	Embodiment 46	0.59	0.82	4.84	1.54
Comparative Examples 15	Embodiment 46	0.59	2.21	8.89	1.54

Table 14

	Surface potential
	Surface potential						Initial (V)		50,000(-V)		100,000(-V)
	The dark space	Illuminated portion	The dark space	Illuminated portion	The dark space	Illuminated portion	Initial (V)		50,000(-V)		100,000(-V)
	The dark space	Illuminated portion	The dark space	Illuminated portion	The dark space	Illuminated portion	Embodiment 40	700	100	640	110	650	130
Embodiment 41	700	110	660	100	640	120	Embodiment 40	700	100	640	110	650	130
Embodiment 41	700	110	660	100	640	120	Embodiment 42	700	110	680	110	660	120
Embodiment 43	700	120	670	120	630	140	Embodiment 42	700	110	680	110	660	120
Embodiment 43	700	120	670	120	630	140	Embodiment 44	700	110	690	120	650	140
Embodiment 45	700	110	680	110	670	130	Embodiment 44	700	110	690	120	650	140
Embodiment 45	700	110	680	110	670	130	Embodiment 46	700	150	680	160	670	180
Comparative Examples 15	700	110	620	120	520	140	Embodiment 46	700	150	680	160	670	180

Table 15

	Picture quality
	Picture quality			Initially	50,000	100,000
	Embodiment 40	○	○	Initially	50,000	100,000	○
Embodiment 41	Embodiment 40	○	○	○	○	○	○
Embodiment 41	Embodiment 42	○	○	○	○	○	○
Embodiment 43	Embodiment 42	○	○	○	○	○	○
Embodiment 43	Embodiment 44	○	○	○	○	○	○
Embodiment 45	Embodiment 44	○	○	○	△	×	○
Embodiment 45	Embodiment 46	○	○	○	△	×	△
Comparative Examples 15	Embodiment 46	○	○	○	×	×	△

◎: fine

Zero: good

△: locality produces stripe pattern

*: produce stripe pattern equably

The photoreceptor for preparing in embodiment 33-46 has good wearing quality and produce the image (quality image) of high-quality after producing 100,000 images.Yet the photoreceptor of preparation is worn away soon in Comparative Examples 14 and 15, and produces the image that has stripe pattern equably after producing 50,000 images.

The application requires the right of priority of Japanese patent application 2005-205998,2005-198071 and 2005-198531, and contain the theme relevant with these Japanese patent applications, these Japanese patent applications are submitted on July 14th, 2005, on July 6th, 2005 and on July 7th, 2005 respectively, and its full content is introduced as a reference at this.

Now the present invention has been carried out abundant description, those of ordinary skills can be obvious, do not exceed the spirit and scope of the present invention set forth herein, can make a lot of changes and improvements to the present invention.

Claims

1. Electrophtography photosensor comprises:

Conductive substrate and

Photosensitive layer, this photosensitive layer comprises at least: do not have three or multifunctional free yl polymerizating monomer of charge migration structure and the simple function radical polymerization compound with charge migration structure;

Wherein the amount of the contained free radical polymerization of this photosensitive layer functional group is for to have 2.55 * 10 in 1g photosensitive layer solid constituent ²¹-7.50 * 10 ²¹, and the peel strength of photosensitive layer is no less than 0.1N/mm when measuring with the SAICAS method.

2. Electrophtography photosensor according to claim 1, wherein this charge migration structure is to be selected from triarylamine structure, hydrazone structure, dihydropyazolo structure and carbazole structure.

3. Electrophtography photosensor according to claim 1 and 2, wherein this charge migration structure is the triarylamine structure.

4. according to each described Electrophtography photosensor among the claim 1-3, wherein this three or multifunctional free yl polymerizating monomer that does not have the charge migration structure has three or more functional group that is selected from acryloxy and methacryloxy.

5. according to each described Electrophtography photosensor among the claim 1-4, further comprise:

The top layer; With

Bonding coat between photosensitive layer and top layer,

Wherein this top layer comprises three or multifunctional free yl polymerizating monomer with charge migration structure and the simple function radical polymerization compound with charge migration structure at least.

6. wherein there is this bonding coat in Electrophtography photosensor according to claim 5 and does not have interphase.

7. according to claim 5 or 6 described Electrophtography photosensors, wherein this bonding coat comprises three or multifunctional free yl polymerizating monomer and adhesive resin with charge migration structure at least.

8. Electrophtography photosensor according to claim 7, wherein this viscosity that does not have three or multifunctional free yl polymerizating monomer of charge migration structure is 1-20mPas down at 25 ℃.

9. according to claim 7 or 8 described Electrophtography photosensors, wherein this three or multifunctional free yl polymerizating monomer that does not have the charge migration structure can be dual functional.

10. according to each described Electrophtography photosensor among the claim 5-9, wherein this bonding coat further comprises the simple function radical polymerization compound with charge migration structure.

11. according to each described Electrophtography photosensor among the claim 5-10, wherein this photosensitive layer also comprises this adhesive resin.

12. according to each described Electrophtography photosensor among the claim 5-11, wherein this adhesive resin comprises polycarbonate resin at least.

13. according to each described Electrophtography photosensor among the claim 5-12, wherein this bonding coat comprises that content is three or the multifunctional free yl polymerizating monomer that do not have the charge migration structure of 10-90 weight % and simple function radical polymerization compound and the adhesive resin with charge migration structure, in the bonding coat general assembly (TW).

14. according to each described Electrophtography photosensor among the claim 5-13, wherein the thickness of this bonding coat is 0.05-5 μ m.

15. according to each described Electrophtography photosensor among the claim 5-14, wherein the thickness of this bonding coat is 0.1-5 μ m.

16. according to each described Electrophtography photosensor among the claim 1-15, wherein this photosensitive layer comprises that further titanyl phthalocyanine is as charge generating material.

17. according to each described Electrophtography photosensor among the claim 1-16, wherein this titanyl phthalocyanine comprises the crystalline form with the Cu-K α X-ray diffraction spectrum that comprises a plurality of diffraction peaks, and wherein observe main peak, and these angles can change in ± 0.2 ° scope in Prague (2 θ) angle of 9.6 °, 24.0 ° and 27.2 °.

18. according to each described Electrophtography photosensor among the claim 1-17, wherein this photosensitive layer is the individual layer photosensitive layer.

19. according to each described Electrophtography photosensor among the claim 1-18, wherein this photosensitive layer is the multilayer photosensitive layer, further comprises:

Charge generation layer; With

Cover the electric charge migrating layer on this charge generation layer.

20. a method for preparing each described Electrophtography photosensor among the claim 1-19 comprises:

This three or multifunctional free yl polymerizating monomer, this simple function radical polymerization compound with charge migration structure that does not have the charge migration structure is dissolved in the solvent to the major general, thereby make coating fluid, this solvent has the saturation vapour pressure that is not higher than 100 mm Hg/25 ℃;

This coating fluid is coated on this Electrophtography photosensor surface; And

This coating fluid of polymerization, thus on this Electrophtography photosensor, form outermost layer.

21. method according to claim 20, wherein the boiling point of this solvent is 60-150 ℃.

22. according to the method for claim 20 or 21, wherein the solubility parameters of this solvent is 8.5-11.0.

23. according to each described method among the claim 20-22, wherein this solvent is selected from butyl acetate and cyclohexanone.

24., further comprise according to each described method among the claim 20-23:

On this outermost layer, apply the bonding coat coating fluid;

On this bonding coat, apply the top layer coating fluid; And

This coating fluid of polymerization, thus this bonding coat and top layer formed.

25. a formation method comprises:

Each described Electrophtography photosensor among the claim 1-19 is charged;

Shine this Electrophtography photosensor, thereby on this Electrophtography photosensor, form electrostatic latent image;

With this electrostatic latent image of toner development, thereby on this Electrophtography photosensor, form toner image; And

This toner image is transferred on the reception material.

26. an electrophotographic imaging forming apparatus comprises:

Each described Electrophtography photosensor among the claim 1-19;

Set up with charger this Electrophtography photosensor charging;

Set up with irradiator, on this photoreceptor, to form electrostatic latent image with this Electrophtography photosensor of rayed;

Set up with image developing device, on this Electrophtography photosensor, to form toner image with this electrostatic latent image of toner development; And

Set up the transfer printing device that receives on the material so that this toner image is transferred to.

27. the handle box that can dismantle from imaging device comprises:

Each described this Electrophtography photosensor among the claim 1-19; And

At least a in charger, image developing device, transfer printing device, clearer and the discharger.