CN102621831B

CN102621831B - Charge transport material, lysate, photoelectric conversion device, Electrophtography photosensor, image forming apparatus and handle box

Info

Publication number: CN102621831B
Application number: CN201110353434.6A
Authority: CN
Inventors: 额田克己; 园部健矢; 山田涉; 土井孝次; 宫本刚; 岩馆侑子
Original assignee: Fuji Xerox Co Ltd
Current assignee: Fujifilm Business Innovation Corp
Priority date: 2011-01-28
Filing date: 2011-11-09
Publication date: 2016-12-14
Anticipated expiration: 2031-11-09

Abstract

The present invention relates to charge transport material, lysate, photoelectric conversion device, Electrophtography photosensor, image forming apparatus and handle box.The present invention provides a kind of charge transport material containing mercapto represented by below general formula (1): F [(G)_a1‑(X)_a2‑Y‑SH]_b(1) wherein, F represents the organic group from charge-transporting compound, G represents the divalent organic group with 1～5 carbon atom, X represents selected from CO O group, O CO group and the group of O group, Y represents the divalent organic group with 1～5 carbon atom, a1 and a2 represents that 0 or 1, b represent the integer of 1～6 independently of one another.

Description

Charge transport material, lysate, photoelectric conversion device, Electrophtography photosensor, image Formation equipment and handle box

Technical field

The present invention relates to the charge transport material containing mercapto, the charge transport material lysate containing mercapto, light Electrical switching device, Electrophtography photosensor, image forming apparatus and handle box.

Background technology

Recently, active development such as Electrophtography photosensor, organic EL device, organic transistor, organic solar electricity Ponds etc. use the electronic installation of organic compound.

Particularly, it is known that cross-linked structure is effective in terms of thermostability and intensity.Disclose a kind of organic EL device, its In employ heat cured film or photocuring film (for example, with reference to WO 97/33193 A2).It is also disclosed to which use and has comprised electricity The Electrophtography photosensor of the acrylate copolymer of lotus transporting group is (for example, with reference to Unexamined Patent 5-202135 publication, JP Flat 6-256428 publication and Unexamined Patent 9-12630 publication).Charge-transporting base is comprised additionally, also disclose wherein to use Group and the acrylate copolymer of reactive group form Electrophtography photosensor that then film carry out cross-linking (for example, with reference to spy Open 2005-002291 publication).It addition, disclose then make it solidify by coating containing light-cured type acrylic monomers and The film (for example, with reference to Unexamined Patent 5-40360 publication) formed.Additionally disclose the monomer by making to have carbon-carbon double bond, The mixture of the charge transport material and adhesive resin with carbon-carbon double bond accepts luminous energy or heat energy so that described monomer The film that the carbon-carbon double bond of carbon-carbon double bond and described charge transport material carries out reacting and formed.Furthermore disclosed the organic mistake of use Oxide is by charge transport material acrylic modified for simple function, the methacrylic acid monomer of non-delivered charge and poly-carbonic acid Ester resin solidification (for example, with reference to Unexamined Patent 5-216249 publication).

Disclosing a kind of film, described film comprises and has two or more chain polymerization functional group by being aggregated in same a part Cavity conveying compound and the compound (for example, with reference to JP 2000-206715 publication) that obtains.Additionally, be also disclosed A kind of Electrophtography photosensor, employs by mixing the sky with mercapto in silicone matrix in described photoreceptor Cave transporting compound and the film (for example, with reference to JP 2000-310870 publication) that solidifies.It addition, disclose a kind of electronics Electrophotographic photoconductor, employs in described photoreceptor and mixes the cavity conveying with mercapto in oxetanes substrate Compound and the film (for example, with reference to Unexamined Patent 2006-184803 publication) that solidifies.

And then also disclosing a kind of Electrophtography photosensor, described photoreceptor comprises the chemical combination with charge-transporting structure Thing, the free radical polymerization monomer without charge-transporting structure and chain-transferring agent, and have because of caused by optical energy irradiation unit Cross linking membrane (for example, with reference to JP 2007-322483 publication).

Furthermore disclosed a kind of image forming apparatus, in this image forming apparatus, exposure wavelength is set as 500nm Hereinafter, facula area is set as 2000 μm²Below (for example, with reference to JP 2004-21136 publication).Have it addition, disclose The photoreceptor of surface layer exposes when wavelength is 380nm～500nm, utilizes electronic beam curing to have chain and gather in described surface layer The agent delivery (for example, with reference to JP 2005-55818 publication) of He Xing functional group.Furthermore disclosed and there are 1 μm～10 μm The photoreceptor of sealer exposes when wavelength is 380nm～450nm, and spot diameter is that below 40 μm are (for example, with reference to JP 2005-70648 publication).Make photoreceptor at the weight average that wavelength is 380nm～450nm and toner it addition, also disclose (for example, with reference to JP 2005-70649 publication) is developed when particle diameter is below 6 μm.Also disclose wavelength be 380nm～ Use AZOpigments as electric charge producing agent (for example, with reference to JP 2006-126327 publication) during 500nm.

Summary of the invention

According to the first aspect of the invention, it is provided that a kind of conveying of the electric charge containing mercapto represented by below general formula (1) Material:

F-[(G)_a1-(X)_a2-Y-SH]_b (1)

Wherein, F represents the organic group from charge-transporting compound, and G represents the bivalence with 1～5 carbon atom Organic group, X represents that Y represents have 1～5 carbon atom selected from-CO-O-group ,-O-CO-group and the group of-O-group Divalent organic group, a1 and a2 represents 0 or 1 independently of one another, and b represents the integer of 1～6.

According in the charge transport material containing mercapto of second aspect, in described formula (1), F can be to have The organic group of hole transporting ability.

According in the charge transport material containing mercapto of the third aspect, by described formula (1) represent containing sulfur The charge transport material of alcohol radical can be represented by below general formula (1) ':

F-[(G)_a-X-Y-SH]_b (1)′

Wherein, F represents the organic group from charge-transporting compound, and G represents the bivalence with 1～5 carbon atom Organic group, X represents-CO-O-group or-O-CO-group, and Y represents the divalent organic group with 1～5 carbon atom, a table Show 0 or 1, and b represents the integer of 1～6.

According in the charge transport material containing mercapto of fourth aspect, by described formula (1) represent containing sulfur The charge transport material of alcohol radical can be represented by below general formula (2):

Wherein, D represents by-(G)_a1-(X)_a2The conjugated group that-Y-SH represents, Ar¹～Ar⁴Represent independently of one another and have Substituent group or not there is the aryl of substituent group, Ar⁵Represent and there is substituent group or not there is the aryl of substituent group or there is replacement Base or do not have the arlydene of substituent group, G represents the divalent organic group with 1～5 carbon atom, and X represents selected from-CO-O- Group ,-O-CO-group and the group of-O-group, Y represents the divalent organic group with 1～5 carbon atom, a1 and a2 is each Represent 0 or 1, Ar independently¹～Ar⁵In one to four have can with by-(G)_a1-(X)_a2The combination base that-Y-SH represents The key that group combines, c1～c5 represents the integer of 0～2 independently of one another, and k represents 0 or 1.

In the charge transport material containing mercapto according to the 5th aspect, wherein by containing that described formula (1) ' represents The charge transport material having mercapto can be represented by below general formula (2) ':

Wherein, D represents by-(G)_aThe conjugated group that-X-Y-SH represents, Ar¹～Ar⁴Represent that there is replacement independently of one another Base or not there is the aryl of substituent group, Ar⁵Represent have substituent group or do not have substituent group aryl or have substituent group or Not having the arlydene of substituent group, G represents the divalent organic group with 1～5 carbon atom, and X represents-CO-O-group or-O- CO-group, Y represents the divalent organic group with 1～5 carbon atom, and a represents 0 or 1.Ar¹～Ar⁵In one to four tool Have can with by-(G)_aThe key that the conjugated group that-X-Y-SH represents combines, c1～c5 represents the integer of 0～2 independently of one another, And k represents 0 or 1.

According to the sixth aspect of the invention, it is provided that a kind of charge transport material lysate containing mercapto, in this dissolving The charge transport material containing mercapto represented by below general formula (1) in liquid dissolves in a solvent:

F-[(G)_a1-(X)_a2-Y-SH]_b (1)

According in the charge transport material lysate containing mercapto of the 7th aspect, wherein represented by formula (1) Charge transport material containing mercapto can be represented by below general formula (1) ':

F-[(G)_a-X-Y-SH]_b (1)′

According to the eighth aspect of the invention, it is provided that a kind of photoelectric conversion device, described device includes by using the most molten Solution has the lysate of the charge transport material containing mercapto represented by below general formula (1) and the film that formed:

F-[(G)_a1-(X)_a2-Y-SH]_b (1)

In the photoelectric conversion device according to the 9th aspect, described formula (1) electric charge containing mercapto represented is defeated Sending material can be the material represented by below general formula (1) ':

F-[(G)_a-X-Y-SH]_b (1)′

In the photoelectric conversion device according to the tenth aspect, described film can be described containing mercapto containing being wherein polymerized The polymer of charge transport material.

According to the eleventh aspect of the invention, it is provided that a kind of Electrophtography photosensor, described photoreceptor is included in electric conductivity Use on matrix and be wherein dissolved with the lysate of the charge transport material containing mercapto represented by below general formula (1) and formed Layer:

F-[(G)_a1-(X)_a2-Y-SH]_b (1)

In the Electrophtography photosensor according to the 12nd aspect, described formula (1) electricity containing mercapto represented Lotus conveying material can be represented by below general formula (1) ':

F-[(G)_a-X-Y-SH]_b (1)′

According to the thirteenth aspect of the invention, it is provided that a kind of have conductive base and the sense on described conductive base The Electrophtography photosensor of photosphere, described photosensitive layer contain by be polymerized at least one by below general formula (I) represent containing sulfur The charge transport material of alcohol radical and at least one polymer that there is the compound of unsaturated bond and formed:

F-[(G)_a1-(X)_a2-Y-SH]_b (I)

Wherein, F represents the organic group from charge-transporting compound, and G represents the bivalence with 1～5 carbon atom Organic group, X represents that Y represents the divalent organic base with 1～5 carbon atom selected from-CO-O-,-O-CO-and the group of-O- , it can have-SH group alternatively base, a1 and a2 represents 0 or 1 independently of one another, and b represents the integer of 1～6.

According in the Electrophtography photosensor of fourteenth aspect, in logical formula (I), F can be to have hole transporting ability Organic group.

In the Electrophtography photosensor according to the 15th aspect, logical formula (I) the electric charge containing mercapto represented is defeated Sending material can be the charge transport material containing mercapto represented by below general formula (II):

Wherein, D represents by-(G)_a1-(X)_a2The conjugated group that-Y-SH represents, Ar¹～Ar⁴Represent independently of one another and have Substituent group or not there is the aryl of substituent group, Ar⁵Represent and there is substituent group or not there is the aryl of substituent group or there is replacement Base or do not have the arlydene of substituent group, G represents the divalent organic group with 1～5 carbon atom, and X represents selected from-CO- The group of O-,-O-CO-and-O-, Y represents the divalent organic group with 1～5 carbon atom, and it can have-SH group and make For substituent group, a1 and a2 represents 0 or 1, Ar independently of one another¹～Ar⁵In one to four have can with by-(G)_a1- (X)_a2The key that the conjugated group that-Y-SH represents combines, c1～c5 represents the integer of 0～2 independently of one another, and k represents 0 or 1.

In the Electrophtography photosensor according to the 16th aspect, described in have the compound of unsaturated bond can be to have The monomer of charge-transporting skeleton, oligomer or polymer.

In the Electrophtography photosensor according to the 17th aspect, described in have the compound of unsaturated bond can be with One molecule has two or more unsaturated bond and not there is the monomer of charge-transporting skeleton, oligomer or polymer.

In the Electrophtography photosensor according to the 18th aspect, described photosensitive layer can contain lubricant particle.

According to the nineteenth aspect of the invention, it is provided that a kind of image forming apparatus, described image forming apparatus includes: electronics Electrophotographic photoconductor, described Electrophtography photosensor has the photosensitive layer being positioned on conductive base, and described photosensitive layer contains and passes through It is polymerized at least one charge transport material containing mercapto represented by below general formula (I), with described at least one, there is insatiable hunger The polymer formed with the compound of key；Charging device, the surface of described Electrophtography photosensor is filled by described charging device Electricity；Exposure device, described exposure device makes the surface of charged described Electrophtography photosensor expose with on said surface Form electrostatic latent image；Developing unit, described developing unit makes described latent electrostatic image developing to form toner image；With transfer dress Putting, described toner image is transferred to offset medium by described transfer device:

F-[(G)_a1-(X)_a2-Y-SH]_b (1)

According to a twentieth aspect of the invention, it is provided that a kind of handle box including Electrophtography photosensor, wherein, described electricity Sub-electrophotographic photoconductor includes the photosensitive layer being positioned on conductive base, and described photosensitive layer contains by being polymerized at least one by following The charge transport material containing mercapto that logical formula (I) represents is formed with having the compound of unsaturated bond described at least one Polymer, and wherein, described handle box can be dismantled from image forming apparatus:

F-[(G)_a1-(X)_a2-Y-SH]_b (1)

Wherein, F represents the organic group from charge-transporting compound, and G represents the bivalence with 1～5 carbon atom Organic group, X represents that Y represents have 1～5 carbon atom selected from-CO-O-group ,-O-CO-group and the group of-O-group Divalent organic group, a1 and a2 represents that 0 or 1, b represent the integer of 1～6 independently of one another.

According to the first aspect of the invention, with do not use the charge transport material containing mercapto represented by formula (1) Situation compare, be obtained in that excellent by the film using the charge transport material containing mercapto that represented by formula (1) to be formed Different electrical property.

According to the second aspect of the invention, compared with the situation that F is not the organic group with hole transporting ability, pass through (wherein F is the organic group with hole transporting ability to the charge transport material containing mercapto that use is represented by formula (1) Group) film that formed is obtained in that the cavity conveying of excellence.

According to the third aspect of the invention we, with do not use the charge transport material containing mercapto represented by formula (1) ' Situation compare, be obtained in that excellent by the film using the charge transport material containing mercapto that represented by formula (1) ' to be formed Different electrical property.

According to the fourth aspect of the invention, with do not use the charge transport material containing mercapto represented by formula (2) Situation compare, be obtained in that excellent by the film using the charge transport material containing mercapto that represented by formula (2) to be formed Different cavity conveying.

According to the fifth aspect of the invention, with do not use the charge transport material containing mercapto represented by formula (2) ' Situation compare, be obtained in that excellent by the film using the charge transport material containing mercapto that represented by formula (2) ' to be formed Different cavity conveying.

According to the sixth aspect of the invention, with the undissolved charge transport material containing mercapto represented by formula (1) Situation compare, be obtained in that excellent by the film using the charge transport material containing mercapto that represented by formula (1) to be formed Different electrical property.

According to the seventh aspect of the invention, with the undissolved charge transport material containing mercapto represented by formula (1) ' Situation compare, be obtained in that excellent by the film using the charge transport material containing mercapto that represented by formula (1) ' to be formed Different electrical property.

According to the eighth aspect of the invention, with do not have by use wherein be dissolved with by formula (1) represent containing sulfur The solution of the charge transport material of alcohol radical and the situation of film that formed is compared, it is possible to obtain the light Denso of the electrical property with excellence Changing device.

According to the ninth aspect of the invention, with do not have by use wherein be dissolved with by formula (1) ' represent containing sulfur The solution of the charge transport material of alcohol radical and the situation of film that formed is compared, it is possible to obtain the light Denso of the electrical property with excellence Changing device.

According to the tenth aspect of the invention, with do not comprise by being polymerized the electric charge containing mercapto represented by formula (1) The situation of the polymer carrying material and formed is compared, it is possible to the light Denso obtaining the mechanical strength and thermostability with excellence changes Device.

According to the eleventh aspect of the invention, wherein it is dissolved with by containing that formula (1) represents by use with not having The solution of the charge transport material of mercapto and the situation of layer that formed is compared, it is possible to obtain the electronics of the electrical property with excellence Electrophotographic photoconductor.

According to the twelfth aspect of the invention, wherein it is dissolved with by containing that formula (1) represents by use with not having The solution of the charge transport material of mercapto and the situation of layer that formed is compared, it is possible to obtain the electronics of the electrical property with excellence Electrophotographic photoconductor.

According to the twelfth aspect of the invention, wherein it is dissolved with by containing that formula (1) ' represents by use with not having The solution of the charge transport material of mercapto and the situation of layer that formed is compared, it is possible to obtain the electronics of the electrical property with excellence Electrophotographic photoconductor.

According to the thirteenth aspect of the invention, with the conveying of the electric charge containing mercapto used except being represented by formula (1) The situation of the charge transport material outside material is compared, it is possible to obtain excellent electrical property.

According to the fourteenth aspect of the invention, it not the organic group with hole transporting ability with the F in formula (1) Situation is compared, it is possible to obtain excellent cavity conveying.

According to the fifteenth aspect of the invention, with the conveying of the electric charge containing mercapto used except being represented by logical formula (II) The situation of the charge transport material outside material is compared, it is possible to obtain excellent cavity conveying.

According to the sixteenth aspect of the invention, with the compound with unsaturated bond, not there is charge-transporting skeleton The situation of monomer, oligomer or polymer is compared, it is possible to obtain the Electrophtography photosensor of the electrical property with excellence.

According to the seventeenth aspect of the invention, do not have in same a part with the compound with unsaturated bond two with Upper unsaturated bond and/or this compound are not the situation phases without the monomer of charge-transporting skeleton, oligomer or polymer Ratio, it is possible to obtain the Electrophtography photosensor of the mechanical strength with excellence.

According to the eighteenth aspect of the invention, compared with the situation not comprising lubricant particle, it is possible to obtain and there is excellence The Electrophtography photosensor of electrical property of long-time stability.

According to the nineteenth aspect of the invention, use except containing of being represented by formula (1) with Electrophtography photosensor The situation of the charge transport material outside the charge transport material of mercapto is compared, it is possible to obtains and has excellent image quality Image.

According to a twentieth aspect of the invention, use except containing of being represented by formula (1) with Electrophtography photosensor The situation of the charge transport material outside the charge transport material of mercapto is compared, it is possible to obtains and has excellent image quality Image.

Accompanying drawing explanation

The illustrative embodiments of the present invention is described in detail, wherein based on the following drawings:

Fig. 1 is the part of an example of the layer composition showing the Electrophtography photosensor according to this illustrative embodiments Schematic cross-section.

Fig. 2 is the portion of another example of the layer composition showing the Electrophtography photosensor according to this illustrative embodiments Partial cross-section schematic diagram.

Fig. 3 is the portion of another example of the layer composition showing the Electrophtography photosensor according to this illustrative embodiments Partial cross-section schematic diagram.

Fig. 4 is the partial cross section signal showing the image forming apparatus with handle box according to this illustrative embodiments Figure.

Fig. 5 is the schematic cross-section showing the tandem type image forming apparatus according to this illustrative embodiments.

Fig. 6 A, 6B and 6C are individually the explanatory diagram showing ghost image evaluation criterion.

Fig. 7 is the portion of an example of the layer composition showing the organic electroluminescent device according to this illustrative embodiments Partial cross-section schematic diagram.

Fig. 8 is to show another example that the layer of the organic electroluminescent device according to this illustrative embodiments is constituted Partial sectional schematic view.

Fig. 9 is to show another example that the layer of the organic electroluminescent device according to this illustrative embodiments is constituted Partial sectional schematic view.

Figure 10 is the diagram showing photohead.

Figure 11 is the diagram showing the state utilizing photohead to be exposed photoreceptor.

Figure 12 is to show the IR spectrogram of the charge transport material containing mercapto of synthesis in embodiment.

Figure 13 is to show the IR spectrogram of the charge transport material containing mercapto of synthesis in embodiment.

Figure 14 is to show the IR spectrogram of the charge transport material containing mercapto of synthesis in embodiment.

Detailed description of the invention

The illustrative embodiments of the present invention is described more fully below.

The charge transport material containing mercapto of this novel illustrative embodiments is represented by below general formula (1):

F-[(G)_a1-(X)_a2-Y-SH]_b (1)

(in formula (1), F represents the organic group from charge-transporting compound, and G represents have 1～5 carbon atom Divalent organic group, X represents that Y represents have 1～5 selected from-CO-O-group ,-O-CO-group and the group of-O-group The divalent organic group of carbon atom, a1 and a2 represents 0 or 1 independently of one another, and b represents the integer of 1～6).

The preference of G includes following organic group: have substituent group or do not have substituent group containing 1～5 carbon atom Alkylidene (including straight-chain alkyl-sub-, branched alkylidene and cyclic alkylidene) or there is substituent group or not there is containing of substituent group The alkylidene of 1～5 carbon atom and the combination of-O-.Wherein, following organic group: straight chain, not there is substituent group Alkylidene containing 1～5 carbon atom or straight chain, the alkylidene containing 1～5 carbon atom without substituent group and-O-group Close.

The more specifically preference of G includes-CH₂-、-C₂H₄-、-C₃H₆-、-C₄H₈-、-C₅H₁₀-、-O-C₂H₄-O-、-CH₂- O-C₂H₄-O-etc..

The preference of Y includes having substituent group or does not have the alkylidene containing 1～5 carbon atom of substituent group and (include straight Chain alkylidene, branched alkylidene and cyclic alkylidene), there is substituent group or not there is the alkene containing 1～5 carbon atom of substituent group Base etc..Additionally, the example of substituent group includes-SH group, halogen atom, alkyl, alkoxyl etc., and wherein particularly preferably-SH Group.

Wherein, the more preferably alkylidene of straight or branched, described alkylidene replaces-CH₃Or-SH group, or do not have Substituted base, and there is 1～5 carbon atom.

The more specifically preference of Y includes-CH₂-、-C₂H₄-、-CH(CH₃)-CH₂-、-CH(CH₃)-、-CH₂-CH(SH)- CH₂-、-CH₂-CH(CH₂-SH)-etc..

F represents the structure with charge-transporting matter, specifically, uses phthalocyanine-like compound, porphyrins, idol Pyridine compounds, triarylamine compounds, diphenyl amine compound, aromatic yl paraffin compounds, there is aryl substituent Ethylene compounds, stilbene compound, anthracene compounds, hydrazone compounds, quinones, Fluorenone compounds etc..

Wherein, preferably there is the compound of arylamine skeleton, because this compounds has charge-transporting matter, particularly In the charge transport material containing mercapto represented by formula (1), particularly preferably those electricity represented by below general formula (2) Lotus conveying material.

In formula (2), D represents by-(G)_a1-(X)_a2The conjugated group that-Y-SH represents, Ar¹～Ar⁴Represent independently of one another There is substituent group or not there is the aryl of substituent group, Ar⁵Represent and there is substituent group or not there is the aryl of substituent group or have Substituent group or not there is the arlydene of substituent group, G represents the divalent organic group with 1～5 carbon atom, X represent selected from- CO-O-group ,-O-CO-group and the group of-O-group, Y represents the divalent organic group with 1～5 carbon atom, a1 and A2 represents 0 or 1 independently of one another.Ar¹～Ar⁵In one to four have can with by-(G)_a1-(X)_a2-Y-SH represents The key that conjugated group combines, c1～c5 represents the integer of 0～2 independently of one another, and k represents 0 or 1.

In formula (2), Ar¹、Ar²、Ar³And Ar⁴Represent independently of one another and there is substituent group or not there is the virtue of substituent group Base, and, Ar¹、Ar²、Ar³And Ar⁴Can be to be same to each other or different to each other.

Herein, there is the example of substituent group in the aryl of substituent group, except-D is (that is, by-(G)_a1-(X)_a2-Y-SH represents Conjugated group) outside, including there is the alkyl of 1～4 carbon atom, there is the alkoxyl of 1～4 carbon atom, having 6～10 The aryl etc. of individual carbon atom.Additionally, these alkyl, alkoxyl and aryl can have substituent group or not have substituent group.

The charge transport material containing mercapto of this illustrative embodiments is preferably represented by below general formula (1) ':

F-[(G)_a-X-Y-SH]_b (1)′

(in formula (1) ', F represents the organic group from charge-transporting compound, and G represents have 1～5 carbon atom Divalent organic group, X represents-CO-O-group or-O-CO-group, and Y represents the divalent organic base with 1～5 carbon atom Group, a represents 0 or 1, and b represents the integer of 1～6).

It is assumed that the charge transport material containing mercapto owing to being represented by formula (1) ' has-SH as polar group, And the number such as the polar group of the obstruction carrier transport such as-OH ,-NH-is less, the film suppression therefore formed by this material is used for The formation of the trap of capture electric charge, and thus suppress the accumulation of residual voltage potential.

It addition, typically, for by cross-linking the film that multifunctional charge transport material obtains, along with immobilized enter OK, the residual stress in film increases, and for the charge transport material containing mercapto represented by formula (1) ', in order to pass through Having the thioester group of high degree of motion degree of freedom and make electric charge conveying composition crosslinking, the residual stress in film is suppressed, therefore Unsuitable generating structure trap, thus speculates the electrical property having obtained excellence.

As a result, while obtaining excellent electrical property, the thickness of the film of formation can be increased further.

Additionally, in order to increase in the case of the film strength of formation, by charge transport material additionally with multifunctional third Acrylic monomer mixes to form film, and the compatibility in common charge transport material of both compositions is relatively low, therefore, limits The increase of the addition of polyfunctional acrylic monomer.But, it is assumed that due to the electricity containing mercapto represented by formula (1) ' Lotus conveying material has the ester structure similar with polyfunctional acrylic monomer, and the compatibility of two kinds of compositions is good, therefore, and nothing Need to be separated and can polyfunctional acrylic monomer cross-link, and thus obtain the film with electrical property and intensity.

Additionally, by using the charge transport material containing mercapto represented by formula (1) ' to form film, crystallization is subject to To suppression, thus, it is easy to obtain the thin film that uneven thickness is suppressed, the most thus produce the electrical property of excellence.

Additionally, by providing cross-linked structure, obtained the film with higher thermostability and solvent resistance, it is thus possible to obtain Obtain the performance of long-time stable.

The charge transport material containing mercapto of this novel illustrative embodiments is preferably by below general formula (1) ' table Show:

F-[(G)_a-X-Y-SH]_b (1)′

The preference of G includes: has substituent group or does not have the alkylidene containing 1～5 carbon atom of substituent group and (include straight Chain alkylidene, branched alkylidene and cyclic alkylidene), there is substituent group or not there is the Asia containing 1～5 carbon atom of substituent group Thiazolinyl, have substituent group or do not have the alkylidene containing 1～5 carbon atom of substituent group and the combination of-O-organic group or Person has substituent group or does not have the organic group of the alkenylene containing 1～5 carbon atom of substituent group and the combination of-O-.Wherein, Following group: straight chain, the alkylidene containing 1～5 carbon atom without substituent group or straight chain, do not have and take The alkylidene containing 1～5 carbon atom of Dai Ji and the organic group of the combination of-O-.

Additionally, the example of substituent group includes halogen atom, alkyl, alkoxyl etc..

The more specifically preference of G includes-CH₂-、-C₂H₄-、-C₃H₆-、-C₄H₈-、-C₅H₁₀-、-O-C₂H₄-O-、-CH₂- O-C₂H₄-O-,-CH=CH-CH₂-、-O-C₂H₂-O-、-CH₂-O-C₂H₂-O-etc., and wherein, particularly preferably-CH₂-、- C₂H₄-、-C₃H₆-、-C₄H₈-、-C₅H₁₀-、-O-C₂H₄-O-and-CH₂-O-C₂H₄-O-。

The preference of Y includes having substituent group or does not have the alkylidene containing 1～5 carbon atom of substituent group and (include straight Chain alkylidene, branched alkylidene and cyclic alkylidene), there is substituent group or not there is the Asia containing 1～5 carbon atom of substituent group Thiazolinyl etc..Additionally, the example of substituent group includes-SH group, halogen atom, alkyl, alkoxyl etc., the most particularly preferably-SH base Group.

Wherein, the more preferably alkylidene of straight or branched, described alkylidene replaces-SH group, or does not have replacement Base, and there is 1～5 carbon atom.

Wherein, preferably there is the compound of arylamine skeleton, because this compounds has charge-transporting matter, particularly In the charge transport material containing mercapto represented by formula (1) ', particularly preferably those are represented by below general formula (2) ' Charge transport material.

In formula (2) ', D represents by-(G)_aThe conjugated group that-X-Y-SH represents, Ar¹～Ar⁴Represent tool independently of one another Substituted base or not there is the aryl of substituent group, Ar⁵Represent to there is substituent group or not there is the aryl of substituent group or have and take For base or the arlydene without substituent group, G represents the divalent organic group with 1～5 carbon atom, and X represents-CO-O-base Group or-O-CO-group, Y represents the divalent organic group with 1～5 carbon atom, and a represents 0 or 1.Ar¹～Ar⁵In one To four have can with by-(G)_aThe key that the conjugated group that-X-Y-SH represents combines, c1～c5 represents 0～2 independently of one another Integer, k represents 0 or 1.

In formula (2) ', Ar¹、Ar²、Ar³And Ar⁴Represent independently of one another and there is substituent group or not there is the virtue of substituent group Base, and, Ar¹、Ar²、Ar³And Ar⁴Can be to be same to each other or different to each other.

Herein, there is the example of substituent group in the aryl of substituent group, except-D is (that is, by-(G)_aThe knot that-X-Y-SH represents Close group) outside, including there is the alkyl of 1～4 carbon atom, there is the alkoxyl of 1～4 carbon atom, there are 6～10 carbon The aryl etc. of atom.Additionally, these alkyl, alkoxyl and aryl can have substituent group or not have substituent group.

Ar¹、Ar²、Ar³And Ar⁴It is preferably any one in following formula (1)～(7).It addition, following formula (1)～(7) represent "- (D)_C", it generally represents can be by each Ar¹、Ar²、Ar³And Ar⁴Substituted "-(D)_C1"～"-(D)_C4”。

In formula (1)～(7), R¹Represent select free hydrogen atom, there is the alkyl of 1～4 carbon atom, replacement has and has 1～4 The alkyl of individual carbon atom or have 1～4 carbon atom alkoxyl phenyl, not there is the phenyl of substituent group and have 7～10 One in the group of the aralkyl composition of individual carbon atom, R²、R³And R⁴Represent the free hydrogen atom of choosing independently of one another, have 1～4 The alkyl of individual carbon atom, have the alkoxyl of 1～4 carbon atom, replace have the phenyl of the alkoxyl with 1～4 carbon atom, Not having the one in the group of the phenyl of substituent group, the aralkyl with 7～10 carbon atoms and halogen atom composition, Ar represents Having substituent group or do not have the arlydene of substituent group, D represents by-(G)_a1-(X)_a2The conjugated group that-Y-SH represents, c represents 0,1 or 2, s represent that 0 or 1, t represent the integer of 0～3, and Z ' represents divalent organic linking group.

Herein, the Ar in formula (7) is preferably represented by following structural formula (8) or (9).

In formula (8) and (9), R⁵And R⁶Independently of one another represent select free hydrogen atom, have 1～4 carbon atom alkyl, Have the alkoxyl of 1～4 carbon atom, replacement has the phenyl of the alkoxyl with 1～4 carbon atom, does not have substituent group One in the group of phenyl, the aralkyl with 7～10 carbon atoms and halogen atom composition, and each t ' represents 0～3 Integer.

It addition, in formula (7), Z ' is preferably represented by any one in following formula (10)～(17).It addition, each s represents 0 or 1.

In formula (10)～(17), R⁷And R⁸Represent the alkane selecting free hydrogen atom, there is 1～4 carbon atom independently of one another Base, the alkoxyl with 1～4 carbon atom or replacement have the phenyl of the alkoxyl with 1～4 carbon atom, do not have replacement One in the group of the phenyl of base, the aralkyl with 7～10 carbon atoms and halogen atom composition, W represents divalent group, q The integer of 1～10, each t is represented independently of one another with r " represent the integer of 0～3.

Any one divalent group that W in formula (16) and (17) is preferably represented by following formula (18)～(26).But, formula (25), in, u represents the integer of 0～3.

Additionally, in formula (2), the Ar when k is 0⁵It is to there is substituent group or not there is the aryl of substituent group, this aryl Example is included in Ar¹～Ar⁴Description in the aryl that enumerates.It addition, when k is 1, Ar⁵It is to there is substituent group or not there is replacement The arlydene of base, the example of this arlydene includes from Ar¹～Ar⁴Description in the aryl that enumerates remove a hydrogen atom and obtain The arlydene obtained.

-D in formula (2) is (that is, by-(G)_a1-(X)_a2The conjugated group that-Y-SH represents) in, the example of G and Y includes leading to The each group enumerated in the description of formula (1).

In formula (2), c1～c5 represents 0,1 or 2 independently of one another, and the sum of D is more than 1.Obtained from increasing Solidification film strength from the viewpoint of thus suppressing to reuse the deterioration of rear image quality, the sum of D is preferably more than 2, More preferably more than 4.

Herein, formula (1) instantiation of the charge transport material containing mercapto represented is as follows, but not It is limited to this.It addition, in showing the following table of example of the compound represented by formula (1), F-(G)_a1-and-(X)_a2Between- Coupling part be expressed as " * " ,-(X)_a2-and Y-SH between coupling part be expressed as " # ".But, in the case of a2=0, " * " and " # " are directly connected to.

In upper table, Compound represents compound

Next synthetic method is described.

The charge transport material containing mercapto represented by formula (1) and formula (1) ' is closed by common esterification Become.

Such as, described material is synthesized by following method: make the novel arylamine compound containing ester group and the alcohol containing mercaptan Carry out the method for esterification, the novel arylamine compound containing ester group is become free carboxy acid is then esterified as containing sulfur through hydrolysis The alcohol of alcohol or the method containing the chloride of hydrocarbon of mercaptan, bromide, iodide etc. or other method.It addition, described material Material can also be synthesized by following method: the novel arylamine compound lithium aluminium hydride reduction containing ester group, sodium borohydride etc. is reduced to Corresponding alcohol, then reacts with the carboxylic acid compound containing mercaptan.

Additionally, use alcohol that the such as acid catalyst such as sulphuric acid, p-methyl benzenesulfonic acid represented by below general formula (3), lead to below The esterification of carboxylic acid that carboxylic acid that formula (4) represents, below general formula (5) represent or the alcohol that below general formula (6) represents synthesizes containing sulfur The charge transport material of alcohol radical.Further, it is possible to use the carboxylic acid chloride of correspondence replaces described carboxylic acid.

F-[(G)_a1-OH]_b (3)

HOOC-Y-SH (4)

F-[(G)_a1-COOH]_b (5)

HO-Y-SH (6)

(wherein, F represents the organic group from charge-transporting compound, and G represents the bivalence with 1～5 carbon atom Organic group, Y represents the divalent organic group with 1～5 carbon atom, and it can have-SH group alternatively base, a1 table Show 0 or 1, and b represents the integer of 1～6).

Additionally, wherein X be the alcohol that represents of the alcohol that represented by below general formula (7) of the compound of ehter bond, below general formula (8) or The alcohol that alcohol that halogenide, below general formula (9) represent or halogenide and below general formula (10) represent synthesizes.

F-[(G)_a1-OH]_b (7)

J-Y-SH (8)

F-[(G)_a1-J]_b (9)

HO-Y-SH (10)

(wherein, F represents the organic group from charge-transporting compound, and G represents the bivalence with 1～5 carbon atom Organic group, Y represents the divalent organic group with 1～5 carbon atom, and it can have-SH group alternatively base, a1 table Showing that 0 or 1, b represent the integer of 1～6, J represents hydroxyl or chlorine, bromine or iodine).

As at such as Experimental Chemistry Lecture Course, the 4th edition, volume 28, page 217 etc. Described in, use the alcohol containing mercaptan of excess and the organo-metallic compound of such as titanium, stannum, zinc etc. to carry out ester by heating Change.

Relative to the ester group of novel arylamine compound, the alcohol containing mercaptan be preferably with more than 1 equivalent, be preferably 1.2 work as Amount is above, be more preferably the amount addition of more than 1.5 equivalents.

The such as mineral acid such as sulphuric acid, phosphoric acid can be added；Titanium alkoxides；The acetate of calcium, cobalt etc. or carbonate；Or zinc or The oxide of lead is as catalyst.Novel arylamine compound based on 1 weight portion, the consumption of catalyst is preferably 1/10000 weight Amount part～1 weight portion, preferably 1/1000 weight portion～1/2 weight portion.

Reaction is preferably carried out under the reaction temperature of 100 DEG C～300 DEG C, the more preferably temperature more than the boiling point making alcohol depart from Degree is carried out.

As the ester group of novel arylamine compound, for the purpose low boiling such as the most such as methanol, ethanol etc. promoting esterification The ester of some alcohol.

Reaction is preferably carried out in the such as noble gas such as nitrogen, argon, it addition, reaction can use methyl. isopropyl The high boiling solvents such as base benzene, 1-chloronaphthalene are carried out.

As such as Experimental Chemistry Lecture Course, the 4th edition., volume 20, page 51 etc. Described in, use such as NaOH, K₂CO₃Deng base catalyst, or such as the acidic catalyst such as phosphoric acid, sulphuric acid makes arylamine chemical combination The ester group of thing is hydrolyzed, thus obtains described novel arylamine compound carboxylic acid.Herein, as solvent, it is possible to use various solvents, It is, however, preferred to use alcohols solvents such as such as methanol, ethanol, ethylene glycol, or its mixture with water.Additionally, in dissolubility relatively In the case of low, dichloromethane, chloroform, toluene, dimethyl sulfoxide, ether, oxolane etc. can be added.

The amount of solvent is not particularly limited, but the novel arylamine compound containing ester group based on 1 weight portion is preferably 1 weight Amount part～100 weight portions, preferably 2 weight portions～50 weight portions.

Reaction temperature is set as below the room temperature (20 DEG C) boiling point with up to solvent, it is contemplated that reaction rate, preferably 50 More than DEG C.

The amount of catalyst is not particularly limited, but the novel arylamine compound containing ester group based on 1 weight portion is preferably 0.001 weight portion～1 weight portion, more preferably 0.01 weight portion～0.5 weight portion.

In the case of use base catalyst is hydrolyzed after hydrolysis, the salt obtained is neutralized by acid such as all example hydrochloric acids, Therefore dissociate out.And then, this product fully washing with water and can use after drying, and if desired can also be with such as The suitable solvents such as methanol, ethanol, toluene, ethyl acetate, acetone carry out recrystallization and are then dried.

Based on novel arylamine compound carboxylic acid, the alcohol containing mercaptan be preferably with more than 1 equivalent, more than preferably 1.2 equivalents, And then the amount that more preferably 1.5 is more than equivalent adds.

Use such as the organic acid such as the mineral acid such as sulphuric acid, phosphoric acid or such as p-methyl benzenesulfonic acid as the catalyst to be dehydrated And esterification, thus synthesize.Novel arylamine compound based on 1 weight portion, it is generally desirable to catalyst with 1/10000 weight portion～ 1 weight portion, the amount of preferably 1/1000 weight portion～1/2 weight portion uses.

It is preferably used and can the solvent of azeotrope with water react, thus remove the water generated in the course of the polymerization process.Toluene, Chlorobenzene, 1-chloronaphthalene etc. are effective, and novel arylamine compound based on 1 weight portion, it is generally desirable to 1 weight portion～100 weights The amount of amount part, preferably 2 weight portions～50 weight portions uses.

Reaction temperature arbitrarily sets, but to remove the water generated in polymerization process, reaction is preferably at the boiling point of solvent Carry out.After having reacted, reactant liquor is poured into water, extracts with such as toluene, hexane, ethyl acetate etc., and make if desired It is purified with the such as adsorbent such as activated carbon, silica gel, Woelm Alumina, alukalin.

It addition, acidic group based on novel arylamine compound carboxylic acid, make 1 equivalent～5 equivalents, be preferably 1.1 equivalents～3 equivalents There is the hydrocarbon containing mercaptan and pyridine, piperidines, triethylamine, dimethyl aminopyridine, the front three of the halogen atoms such as such as Cl, Br, I The alkali such as amine, DBU, sodium hydride, sodium hydroxide, potassium hydroxide react to synthesize in organic solvent, described organic solvent example As for aprotic polar solvent, such as N-Methyl pyrrolidone, dimethyl sulfoxide, DMF etc.；Ketones solvent, such as third Ketone, methyl ethyl ketone etc.；And ether solvent, such as diethyl ether, oxolane etc..

Described alkali is preferably to use based on the amount that carboxylic acid is 1 equivalent～3 equivalents, preferably 1 equivalent～2 equivalents.Institute Aprotic organic solvent be preferably to be 1 weight portion～50 weight portions based on carboxylic acid derivates, be preferably 1.5 weight portions ～30 weight portion amount use.

Reaction temperature can arbitrarily set in 0 DEG C with the scope below up to solvent boiling point, but preferably 0 DEG C～150 DEG C. After having reacted, reactant liquor is poured into water, extracts with such as toluene, hexane, ethyl acetate etc., and use if desired such as The adsorbents such as activated carbon, silica gel, Woelm Alumina, alukalin are purified.

It addition, as at Experimental Chemistry Lecture, 4^thEd., Vol.20, P.10 described in grade, can To use lithium hydride, sodium borohydride etc. that the ester group of novel arylamine compound is reduced into corresponding alcohol, and enter with the carboxylic acid containing mercaptan Row esterification is to synthesize.

By by by formula (1) or (1) ' charge transport material containing mercapto that represents dissolves and forms root in a solvent The charge transport material lysate containing mercapto according to this illustrative embodiments.

As solvent, the such as aromatic solvent such as toluene, dimethylbenzene；Such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), hexamethylene The ketones solvents such as ketone；The such as esters solvent such as ethyl acetate, butyl acetate；Such as oxolane, twoThe ether solvents such as alkane；All Such as cellosolve type solvents such as glycol monoethyl ethers；The such as alcohols solvent such as isopropanol, butanol can be used alone or as mixed Compound uses.

It addition, for will be by formula (1) or (1) ' charge transport material containing mercapto that represents dissolves in a solvent Method can be common method, such as at 10 DEG C～150 DEG C, preferably 15 DEG C～120 DEG C time mix with stirring solvent Method, or use the method for ultrasonic irradiation etc..

The charge transport material lysate containing mercapto of this illustrative embodiments is such as used for opto-electronic conversion dress Put the film forming in (organic EL device, Electrophtography photosensor etc.), or the formation of solaode, organic transistor etc..

It follows that photoelectric conversion device will be described.

The charge transport material containing mercapto of this illustrative embodiments can be used for being formed as vapor deposition film Film, and the lysate being wherein dissolved with the charge transport material containing mercapto may be used for forming film.Additionally, this film can wrap Containing the polymer being wherein polymerized the charge transport material containing mercapto.

It addition, wherein contain the charge transport material of mercapto as molecular dispersion at such as polycarbonate resin, poly-virtue Film in the resins such as ester resin (polyarylate resin), polyester resin is outstanding, and most preferably Use by with there is the monomer of double bond, oligomer or polymer mixed after the cured film that is solidified to form.

The Electrophtography photosensor (it is sometimes referred to simply as " photoreceptor ") of this illustrative embodiments has conductive base With the photosensitive layer being positioned on described conductive base, described photosensitive layer contains by being polymerized at least one by below general formula (I) table The charge transport material containing mercapto shown has the compound of unsaturated bond (hereinafter sometimes referred to simply as " spy with at least one Determine polymer ") and the polymer that formed.

F-[(G)_a1-(X)_a2-Y-SH]_b (I)

(in logical formula (I), F represents the organic group from charge-transporting compound, and G represents have 1～5 carbon atom Divalent organic group, X represents that selected from-CO-O-,-O-CO-and the group of-O-, Y represents the bivalence with 1～5 carbon atom Organic group, it can have-SH group alternatively base, a1 and a2 represents 0 or 1 independently of one another, and b represents 1～6 Integer).

It is assumed that the charge transport material containing mercapto owing to being represented by logical formula (I) has-SH as polar group Group, and the electronegativity of sulphur atom is relatively low, therefore different from-OH ,-NH-etc., the effect hindering carrier transport is relatively small.Cause And, using the film formed by this material, the formation of the trap for capturing electric charge is suppressed, and the accumulation of residual voltage potential is pressed down System, thus potential stability is excellent.

It addition, typically, for by cross-linking the film that multifunctional charge transport material obtains, along with immobilized enter OK, the residual stress in film increases, and for the charge transport material containing mercapto represented by logical formula (I), for passing through Having a thioester substrate of high degree of motion degree of freedom and the purpose of cross-linked charge conveying composition, the residual stress in film is suppressed, because of This is difficult to generating structure trap, thus speculates the electrical property having obtained excellence.

Additionally, in order to increase in the case of the film strength of formation, can be by charge transport material additionally with multifunctional Acrylic monomers mixes to form film, and the compatibility in common charge transport material of both compositions is relatively low, therefore, limits The increase of the addition of polyfunctional acrylic monomer.But, it is assumed that due to represented by logical formula (I) containing mercapto Charge transport material has the ester structure similar with polyfunctional acrylic monomer, and the compatibility of two kinds of compositions is good, therefore, Polyfunctional acrylic monomer can cross-link without being separated, and thus obtained having electrical property and intensity simultaneously Film.

Therefore, the charge transport material containing mercapto represented by logical formula (I) by use, define and there is electricity simultaneously Character and the photosensitive layer of intensity.Especially it is possible to realize the situation of the thicker film that thickness is more than 10 μm.It addition, comprise logical Cross and be polymerized at least one by leading to the charge transport material containing mercapto that formula (I) represents and at least one has unsaturated bond Compound (specific compound) and the layer of polymer that formed are the outmost surface of the photoreceptor constituting this illustrative embodiments Surface layer, and the formation of above relatively thick film inhibits the decline of the image quality after Reusability.There is high intensity table In the case of surface layer, the life-span of photoreceptor is confirmed as the time point of surface layer abrasion.Therefore, the formation of relatively thick film is effectively Photoreceptor provides the longer life-span.

Additionally, in order to form image, photoreceptor is charged by electric discharge and is used, and now, due to electric stress and The stress caused by discharge gas such as such as ozone, causes the deterioration of the surfacing of photoreceptor as a result, easily absorption such as claims Ammonium nitrate isoiony material for discharging product.Therefore, especially, water is absorbed at high humidity, the sheet resistance of photoreceptor Rate reduces.Therefore, in the image formed, occur sub-image fuzzy as a result, be susceptible to the deterioration of image.In order to suppress this Phenomenon, following method is effective: providing the parts to be cleaned contacted with photoreceptor, the friction with parts to be cleaned is suitable Worn away surface layer, thus eliminate discharging product and inhibit sub-image bleeding.Further, since band during imaging electrically and Cleaning mode greatly affects abrasion loss, thus the shape etc. of the toner used is highly dependent on image formation system.Therefore, The intensity of the surface layer adjusting photoreceptor is particularly significant.

In this respect, in the Electrophtography photosensor of this illustrative embodiments, can be to containing of being represented by formula (1) Ratio and the electric charge containing mercapto represented by logical formula (I) of the crosslinking component of the charge transport material etc. of mercapto carry material The structure of the reactive monomer of material etc. selects, thus forms the most suitable surface layer of intensity for system.

Additionally, by using the charge transport material containing mercapto itself represented by logical formula (I) as multifunctional electricity Lotus transporting monomer, can give photosensitive layer intensity without reducing the concentration of electric charge conveying composition.

In the charge transport material containing mercapto represented by logical formula (I), preferably there is the material of arylamine skeleton, Reason is that this material has higher charge-transporting matter, and those materials particularly preferably represented by below general formula (II) Material.

(in logical formula (II), D represents by-(G)_a1-(X)_a2The conjugated group that-Y-SH represents, Ar¹～Ar⁴Table independently of one another Show and there is substituent group or not there is the aryl of substituent group, Ar⁵Represent and there is substituent group or not there is aryl or the tool of substituent group Substituted base or not there is the arlydene of substituent group, G represents the divalent organic group with 1～5 carbon atom, X represent selected from- The group of CO-O-,-O-CO-and-O-, Y represents the divalent organic group with 1～5 carbon atom, and it can have-SH group Alternatively base, a1 and a2 represents 0 or 1, Ar independently of one another¹～Ar⁵In one to four have can with by-(G)_a1- (X)_a2The key that conjugated group that-Y-SH represents combines, c1～c5 represents the integer of 0～2 independently of one another, and k represent 0 or 1)。

-have the compound of unsaturated bond-

It follows that describe the compound with unsaturated bond.Do not have electric charge conveying composition described compound include with Lower compound.

The example of monofunctional monomer includes Isobutyl 2-propenoate, tert-butyl acrylate, Isooctyl acrylate monomer, lauryl Ester, stearyl acrylate base ester, isobornyl acrylate, cyclohexyl acrylate, acrylic acid 2-methoxy acrylate, methoxyethyl Triglycol ester, acrylic acid 2-ethoxy ethyl ester, acrylic acid tetrahydro furfuryl ester, benzyl acrylate, acrylic acid ethyl carbitol Ester, acrylate, 2-hydroxy acrylate, acrylic acid 2-hydroxy propyl ester, acrylic acid 4-hydroxybutyl, acrylic acid first Epoxide macrogol ester, methacrylic acid methoxyl group macrogol ester, acrylic acid phenoxy group macrogol ester, methacrylic acid benzene Epoxide macrogol ester, hydroxy ethyl o-phenyl phenol ester, acrylic acid o-phenyl phenol (+)-2,3-Epoxy-1-propanol ether-ether, styrene Deng.

The example of bifunctional monomer includes two (methyl) acrylic acid binaryglycol ester, two (methyl) polyalkylene glycol acrylate Ester, two (methyl) acrylic acid polypropylene glycol ester, two (methyl) acrylic acid DOPCP, two (methyl) acrylic acid 1,6-hexanediol Ester, divinylbenzene, diallyl phthalate etc..

The example of trifunctional monomer includes trimethylolpropane tris (methyl) acrylate, three (methyl) acrylic acid Ji Wusi Alcohol ester, aliphatic three (methyl) acrylate, triethylene cyclohexane etc..

The example of four functional monomers includes four (methyl) acrylate, pentaerythritol, double trimethylolpropane four (methyl) third Olefin(e) acid ester, aliphatic four (methyl) acrylate etc..

The example of monomers more than five senses includes five (methyl) acrylic acid dipentaerythritol ester, six (methyl) acrylic acid two Pentaerythritol ester etc., and there is (methyl) acrylate of polyester backbone, carbamate skeleton or phosphine nitrile skeleton.

It addition, the example of reactive polymer includes Japanese Unexamined Patent Publication 5-216249 publication, Japanese Unexamined Patent Publication 5- No. 323630 publications, Japanese Unexamined Patent Publication 11-52603 publication, Japanese Unexamined Patent Publication 2000-264961 publication and Japanese Unexamined Patent Publication Those disclosed polymer such as 2005-2291 publication.

Having unsaturated bond at compound but do not have in the case of electric charge conveying composition, it can be used alone or as two Plant above mixture to use.There is unsaturated bond but do not have electric charge conveying composition compound for forming electrofax The outmost surface layer of photoreceptor, total inclusion admittedly based on the compositions for surface layer, its consumption is preferably below 60 weight %, Below more preferably 55 weight %, and then below more preferably 50 weight %.

Next compound (monomer, the oligomer and poly-also with charge-transporting skeleton with unsaturated bond is described Compound).

(I) there is in same a part chain polymerization functional group and the compound of charge-transporting skeleton

With the chain polymerization official's energy in the compound in a part with chain polymerization functional group and charge-transporting skeleton Group is not particularly limited, as long as the functional group of radical polymerization can be carried out, such as, it is at least to have carbon-carbon double bond Functional group.Its instantiation includes containing selected from vinyl, vinyl ether group, vinyl sulfide base, styryl, acryloyl The group of at least one in base, methylacryloyl and derivant thereof, etc..Wherein, it is contemplated that during high response, described chain Polymerizable functional group is preferably containing in vinyl, styryl, acryloyl group, methylacryloyl and derivant thereof The group of at least one.

It addition, with the electric charge in (I) compound in a part with chain polymerization functional group and charge-transporting skeleton Transporting skeleton is not particularly limited, as long as it has known structure in Electrophtography photosensor, such as, described skeleton For the skeleton from the cavity conveying compound containing nitrogen, described cavity conveying compound such as triaryl amine chemical combination Thing, diphenyl amine compound, hydrazone compounds etc..The example includes and the structure of nitrogen-atoms conjugation.Wherein, preferred triarylamine Skeleton.

Herein, as having (I) compound of chain polymerization functional group and charge-transporting skeleton in same a part, because of Of fine quality different excellent with chain polymerization for charge-transporting, it may be mentioned that the compound represented by below general formula (A) is as preference.

In formula (A), Ar¹～Ar⁴Represent independently of one another and there is substituent group or not there is the aryl of substituent group, Ar⁵Represent Having substituent group or do not have the aryl of substituent group or have substituent group or do not have the arlydene of substituent group, D represents have The group of the functional group containing carbon-carbon double bond, c1～c5 represents that 0,1 or 2, k represent 0 or 1 independently of one another, and the sum of D is More than 1 (preferably more than 2).

Herein, formula (A) compound represented can be such compound: wherein D represents have selected from acryloyl Base, methylacryloyl, ethenylphenyl, pi-allyl, vinyl, vinyl ether group, allyl vinyl ether base and derivative The group (particularly, there is the group of described group at end) of at least one in thing.

It addition, the compound represented by formula (A) can be such compound: wherein D represents-(CH₂)_d-(O-CH₂- CH₂)_e-O-CO-C (R ')=CH₂(wherein, R ' represents hydrogen atom or methyl, and d represents the integer of 1～5, and e represents 0 or 1).

In formula (A), Ar¹～Ar⁴Represent independently of one another and there is substituent group or not there is the aryl of substituent group.Ar¹~ Ar⁴Can be identical or different each other.

Herein, there is the example of substituent group in the aryl of substituent group, in addition to the group represented by D, including having 1 ～the alkyl of 4 carbon atoms, have 1～4 carbon atom alkoxyl, there are 6～10 carbon atoms there is substituent group or not There is the aryl etc. of substituent group.

Ar¹～Ar⁴Instantiation can be any one in following formula (1)～(7).It addition, following formula (1)～(7) represent "- (D)_C", it represents synoptically can be by Ar¹～Ar⁴In each substituted "-(D)_C1"～"-(D)_C4”。

In formula (1)～(7), R¹Represent select free hydrogen atom, there is the alkyl of 1～4 carbon atom, replacement has and has 1～4 The alkyl of individual carbon atom or have 1～4 carbon atom alkoxyl phenyl, not there is the phenyl of substituent group and have 7～10 At least one in the aralkyl of individual carbon atom.R²～R⁴Represent selected from hydrogen atom independently of one another, there is 1～4 carbon atom Alkyl, there is the alkoxyl of 1～4 carbon atom, replace and have the phenyl of the alkoxyl with 1～4 carbon atom, not there is replacement At least one in the phenyl of base, the aralkyl with 7～10 carbon atoms and halogen atom.Ar represents have substituent group or not Having the arlydene of substituent group, D represents and identical for the D group in formula (A), and c represents that 1 or 2, s represent 0 or 1, and t table Show the integer of 0～3.

Herein, the Ar in formula (7) is represented by following structural formula (8) or (9).

In formula (8) and (9), R⁵And R⁶Independently of one another represent select free hydrogen atom, have 1～4 carbon atom alkyl, Have the alkoxyl of 1～4 carbon atom, replacement has the phenyl of the alkoxyl with 1～4 carbon atom, does not have substituent group One in the group of phenyl, the aralkyl with 7～10 carbon atoms and halogen atom composition, and t represents the integer of 0～3.

Additionally, in formula (7), Z ' represents divalent organic linking group, but preferably arbitrary by with in following formula (10)～(17) Plant and represent.It addition, s represents 0 or 1.

In formula (10)～(17), R⁷And R⁸Represent the alkane selecting free hydrogen atom, there is 1～4 carbon atom independently of one another Base, there is the alkoxyl of 1～4 carbon atom, replace and have the phenyl of the alkoxyl with 1～4 carbon atom, not there is substituent group Phenyl, the aralkyl with 7～10 carbon atoms and halogen atom composition group in one, W represents divalent group, q and r Represent the integer of 1～10, and t independently of one another " represent the integer of 0～3.

W in formula (16) and (17) can be any one in the divalent group of following formula (18)～(26).But, in formula (25), in, u represents the integer of 0～3.

Additionally, in formula (A), the Ar when k is 0⁵It is to there is substituent group or not there is the aryl of substituent group, this aryl Example is included in Ar¹～Ar⁴Description in the aryl that enumerates.It addition, when k is 1, Ar⁵It is to there is substituent group or not there is replacement The arlydene of base, the example of this arlydene includes as from Ar¹～Ar⁴The aryl that enumerated of description in remove in desired position The arlydene removing a hydrogen atom and obtain and those arlydene enumerated.

Hereinafter, it is shown that the instantiation of the compound (compound of (I)) represented by formula (A).It addition, by formula (A) compound represented is not limited to this.

First, it is shown that there is the instantiation of compound of a reactive functional groups containing carbon-carbon double bond, but also It is not limited to this.

The following instantiation showing the compound with two reactive functional groups containing carbon-carbon double bond, but also It is not limited to this.

The instantiation of compound with three reactive functional groups containing carbon-carbon double bond be illustrated below, but not It is limited to this.

Below, display has the instantiation of the compound of 4～6 reactive functional groups containing carbon-carbon double bond, but It is not limited to this.

(I) compound synthesizes the most in the following manner.

I.e., such as closed as the halogenide of the alcohol of precursor and corresponding methacrylic acid or methacrylic acid by condensation Become the compound of (I).Such as have in the case of benzyl alcohol structure at the alcohol as precursor, by making alcohol and such as metering system Acid hydroxy methacrylate etc. has the acrylic acid of hydroxyl to carry out being dehydrated/being etherified synthesizing specific charge transport material.

The route of synthesis of exemplary compounds iv-4 and exemplary compounds iv-17 by illustrated below as an example.

In above figure, Compound represents compound.

(I) other compounds such as come according to the route of synthesis of compound iv-4 and the route of synthesis of compound iv-17 Synthesis.

As the compound of (I), as it has been described above, from the viewpoint of the mechanical strength improving gained film, it is possible to use tool There is the compound of more than four reactive functional groups containing carbon-carbon double bond.

Additionally, as the compound of (I), have more than four reactive functional groups containing carbon-carbon double bond compound and The compound with one to three reactive functional groups containing carbon-carbon double bond can be applied in combination.Made by such combination With, while the deterioration of suppression charge transport properties, have adjusted film strength.

There is the compound of more than four reactive functional groups containing carbon-carbon double bond and there is one to three containing carbon The compound combination of the reactive functional groups of carbon double bond is used as in the case of the compound of (I), has more than four containing carbon carbon The content of the compound of the reactive functional groups of double bond can be more than 5 weight % of the total content of the compound of (I), particularly It is more than 20 weight %.

It follows that describe other compounds of (I).

(I) compound can be the polymer containing the part-structure represented by below general formula (B) and (C) respectively.

In formula (B) and (C), R¹、R²And R³Represent hydrogen atom independently of one another or there is the alkyl of 1～4 carbon atom, X Represent the divalent organic group with 1～20 carbon atom independently of one another with Y, a represents 0 or 1, and CT represents have electric charge The organic group of transporting skeleton.

Herein, the end group of the polymer containing the part-structure represented by below general formula (B) and (C) respectively has logical Cross the structure that Raolical polymerizable is formed in terminating reaction.

In formula (B), CT the example of the organic group with charge-transporting skeleton represented includes above-mentioned electric charge Transporting skeleton, but its preference includes having triarylamine skeleton, benzidine skeleton, aromatic yl paraffin skeleton, has aryl and take The ethylene skeleton of Dai Ji, stilbene skeleton, anthracene skeleton and the organic group of hydrazone skeleton.Wherein, more preferably there is triarylamine skeleton, connection Aniline skeleton and the organic group of stilbene skeleton.

In formula (B) and (C), X and Y the example of the divalent organic group represented include having selected from alkylidene ,-C (= O)-,-O-C (=O)-, aromatic rings and the divalent organic group of during there is the linking group of combination of the above one.It addition, by X The divalent organic group represented with Y does not the most have hydroxyl.

The instantiation of the divalent organic group represented by X includes-C (=O)-O-(CH₂)_n-(wherein, n represent 0 or 1～ The integer of 10) etc..

The instantiation of the divalent organic group represented by Y includes-(CH)_n-(wherein, n represents the integer of 1～10) ,- (CH₂)_n-O-C (=O)-(wherein, n represents 0 or the integer of 1～10, and " (CH₂)_n" part hydrogen atom can be taken by hydroxyl Generation) ,-(CH₂)_n-Ar-(wherein, Ar represents the arlydene with 1～3 aromatic rings, and n represent 0 or the integer of 1～10) ,- Ar-O-(CH₂)_n-O-C (=O)-(wherein, Ar represents the arlydene with 1～3 aromatic rings, and n represents 0 or 1～10 Integer) etc..

The instantiation of the part-structure represented by formula (B) includes but not limited to having structure.Additionally, at " (X)_a" hurdle In, the situation being designated as "-" represents the situation of a=0, and the situation being designated as group represents the situation of a=1, i.e. by CT and X mono- Act the group represented.

It follows that the instantiation of the structure represented by formula (C) includes following structure, but implement to be not limited to this.

Wherein, following general structure (D) those dissolubility with excellence and the film property represented, thus be preferred 's.

In formula (D), R¹、R²And R³Representing hydrogen atom independently of one another or have the alkyl of 1～4 carbon atom, X represents There is the divalent organic group of 1～20 carbon atom, Y ' represent-C (=O)-,-CH₂-or-(CH₂)₂-, a and b is independently of one another Represent 0 or 1, and CT represents the organic group with charge-transporting skeleton.

M and n represents the integer of more than 5 independently of one another, and meets 10 ＜ m+n ＜ 200 and 0.2 ＜ m/ (m+n) ＜ The condition of 0.95, but from the viewpoint of intensity, flexibility and electrical property, preferred condition is 15 ＜ m+n ＜ 2000 and 0.3 ＜ m/ (m+n) ＜ 0.95, more preferably 20 ＜ m+n ＜ 2000 and 0.4 ＜ m/ (m+n) ＜ 0.95.

It addition, in formula (D), X the organic group with divalent organic group and the electric charge represented by CT that represent are defeated The property sent skeleton, has and identical for X and the CT definition in formula (B) and (C).

The polymer comprising the part-structure each represented by formula (B) and (C) is such as prepared according to known method, described Known method for example, use the compound represented by formula (A) as monomer, with methacrylic acid, acrylic acid, (+)-2,3-Epoxy-1-propanol Based compound and derivant etc. thereof carry out copolymerization.

Additionally, comprise the polymer of the part-structure each represented by formula (B) and (C) except by formula (B) and (C) table With monovalence monomer copolymerization, thus dissolubility and flexibility can also be provided outside those shown.

The example of monofunctional monomer includes such as Isobutyl 2-propenoate, tert-butyl acrylate, Isooctyl acrylate monomer, acrylic acid Lauryl, stearyl acrylate base ester, isobornyl acrylate, cyclohexyl acrylate, acrylic acid 2-methoxy acrylate, acrylic acid first Epoxide triglycol ester, acrylic acid 2-ethoxy ethyl ester, acrylic acid tetrahydro furfuryl ester, benzyl acrylate, acrylic acid ethyl card Must alcohol ester, acrylate, 2-hydroxy acrylate, acrylic acid 2-hydroxy propyl ester, acrylic acid 4-hydroxybutyl, propylene Acid methoxy poly (ethylene glycol) ester, methacrylic acid methoxyl group macrogol ester, acrylic acid phenoxy group macrogol ester, metering system Acid phenoxy group macrogol ester, hydroxy ethyl o-phenyl phenol ester or acrylic acid o-phenyl phenol (+)-2,3-Epoxy-1-propanol ether-ether etc. third Olefin(e) acid ester or methacrylate；And the such as styrene derivative such as styrene, α-methyl styrene or 4-methyl styrene.

From the viewpoint of providing dissolubility and flexibility, relative to the m in formula (D), the use when these monomer copolymerizations Amount (1) preferably meets condition 1/m ＜ 0.3, more preferably 1/m ＜ 0.2.

Additionally, the compound of these (I) may be used singly or two or more in combination.

[Electrophtography photosensor]

The Electrophtography photosensor of this illustrative embodiments has the photosensitive layer being positioned on conductive base, described photosensitive Layer comprises by being polymerized at least one by leading to the charge transport material containing mercapto that formula (I) represents and at least one has not The compound of saturated bond and the polymer that formed.

It addition, by using cross-linkable monomer self as multifunctional charge-transporting monomer, electric charge can not reduced Intensity is provided during the concentration of transporting composition.

In the Electrophtography photosensor of this illustrative embodiments, preferably include to comprise by containing that logical formula (I) represents The layer of the charge transport material of mercapto is as outmost surface layer, and described outmost surface layer can also be to form electrofax The random layer of the uppermost layer of photoreceptor self, and be configured to operate as the layer of protective layer or be used as charge transport layer Layer.

Additionally, be used as in the case of the layer of protective layer at outmost surface layer, the lower floor of protective layer can have and includes electricity Lotus transfer layer and the photosensitive layer of charge generation layer, or there is the photosensitive layer of single-layer type.

It is used as in the case of the layer of protective layer at outmost surface layer, conductive base includes photosensitive layer and is used as outermost The protective layer of surface layer, wherein protective layer can have and comprises being formed arbitrarily with lower floor: described layer includes containing by using The compositions of the polymer that the charge transport material containing mercapto represented by logical formula (I) is formed or its cured product.

Additionally, be used as in the case of the layer of charge transport layer at outmost surface layer, conductive base includes electric charge produces Generating layer and be used as the charge transport layer of outmost surface layer, wherein charge transport layer can have and comprises being formed arbitrarily with lower floor: Described layer includes containing by using the charge transport material containing mercapto represented by logical formula (I) and at least one to contain not The compositions of the polymer that the compound of saturated bond is formed or the layer of its cured product.

Furthermore, it is possible to mix such as mercapto, unsaturated bond etc. not there is the charge transport material of reactivity.

Hereinafter, this illustrative embodiments when outmost surface layer is used as protective layer will be described in detail with reference to the attached drawings Electrophtography photosensor.It addition, in accompanying drawing, identical or suitable part is represented by identical symbol, and omits retouching of repetition State.

Fig. 1 is the schematic sectional view of the preference of the Electrophtography photosensor showing this illustrative embodiments.

Fig. 2 to 3 is the schematic cross-sectional diagram of the Electrophtography photosensor showing other illustrative embodiments of the present invention.

Electrophtography photosensor 7A shown in Fig. 1 is so-called function divergence type photoreceptor (or laminated-type photoreceptor), And there is following structure, described structure arranges on conductive base 4 priming coat 1, and sequentially forms electricity on priming coat 1 Lotus produces layer 2, charge transport layer 3 and protective layer 5.In Electrophtography photosensor 7A, photosensitive layer is defeated by charge generation layer 2 and electric charge Layer 3 is sent to form.

Electrophtography photosensor 7B shown in Fig. 2 is function divergence type photoreceptor, itself and the electrofax shown in Fig. 1 Photoreceptor 7A is similar to, and has the charge generation layer 2 and charge transport layer 3 being functionally separated.

Electrophtography photosensor 7B shown in Fig. 2 has following structure, arranges in described structure on conductive base 4 Priming coat 1, and on priming coat 1, sequentially form charge transport layer 3, charge generation layer 2 and protective layer 5.Electronic photographic sensitive In body 7B, photosensitive layer is made up of charge transport layer 3 and charge generation layer 2.

Electrophtography photosensor 7C shown in Fig. 3 contains charge generating material in same layer (single-layer type photosensitive layer 6) And charge transport material.Electrophtography photosensor 7C shown in Fig. 3 has following structure: arrange the end on conductive base 4 Coating 1, and on priming coat 1, sequentially form single-layer type photosensitive layer 6 and protective layer 5.

Additionally, in Electrophtography photosensor 7A, 7B and 7C shown in Fig. 1,2 and 3, arrange protective layer 5 as away from The outmost surface layer formed away from the farthest side of conductive base 2, and this outmost surface layer has above-mentioned structure.

It addition, in Electrophtography photosensor shown in Fig. 1,2 and 3, priming coat 1 can be formed with or without.

Hereinafter, as representative example, based on the Electrophtography photosensor 7A shown in Fig. 1, each element is described.

-protective layer-

First, the protective layer 5 as the outmost surface layer in Electrophtography photosensor 7A is described.Protective layer 5 is that electronics shines Outmost surface layer in phase photoreceptor 7A, and preferably by by be polymerized at least one by lead to that formula (I) represents containing mercapto Charge transport material and the polymer that at least one has the compound of unsaturated bond and is formed formed.

As curing, carry out radical polymerization by heat, light, radiation etc..If reaction being adjusted to the most fast Carry out fastly, then can suppress the generation of the uneven of film or fold, it is therefore preferred at the bar that free radical slowly occurs It is polymerized under part.In consideration of it, preferably readily regulate the thermal polymerization of rate of polymerization.

Non-reacted charge transport material

For constituting the film of protective layer (outmost surface layer) 5, non-reacted charge transport material can be applied in combination.Non- Reactive charge transport material does not have a reactive group of responsible electric charge conveying, therefore, by defeated for non-reacted electric charge Sending the situation that material is used in protective layer (outmost surface layer) 5, the concentration of charge-transporting composition substantially increases, thus effectively Further improve electrical property.Furthermore it is possible to add non-reacted charge transport material to reduce crosslink density, thus adjust Joint intensity.

As non-reacted charge transport material, it is possible to use known charge transport material, specifically, three are used Amines, diphenyl amine compound, aromatic yl paraffin compounds, have aryl substituent ethylene compounds, Stilbene compound, anthracene compounds, hydrazone compounds etc..

Wherein, from the viewpoint of mobility, the compatibility etc., preferably there is triphenylamine skeleton.

Based on the total inclusion admittedly for cambial coating fluid, the amount of non-reacted charge transport material is preferably 0 weight Measure %～30 weight %, more preferably 1 weight %～25 weight %, and then more preferably 5 weight %～25 weight %.

Other additives

Such as, for such as regulating the purpose of film property, flexibility, lubricity and adhesiveness, protective layer (outmost surface is constituted Layer) 5 cured film can be added with other coupling agent, especially with the coupling agent of fluorine.As these compounds, use various Silane coupler and the hard varnish of commercially available silicone.Further, it is possible to use the organosilicon compound containing free-radical polymerised group Thing or fluorochemical.

The example of silane coupler includes vinyl trichlorosilane, vinyltrimethoxy silane, vinyl triethoxyl Silane, γ-glycidoxypropyl diethoxy silane, γ-glycidoxypropyltrimewasxysilane, γ- Glycidoxypropyltrimewasxysilane, γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy silicane, Gamma-amino hydroxypropyl methyl dimethoxysilane, N-β-(amino-ethyl)-γ aminopropyltriethoxy silane, tetramethoxy-silicane Alkane, MTMS, dimethyldimethoxysil,ne etc..

The example of commercially available hard varnish includes that KP-85, X-40-9740 and X-8239 are (by Shin-Etsu Chemical Co., Ltd. manufactures) and AY42-440, AY42-441 and AY49-208 (all being manufactured by Dow Corning Toray Co., Ltd) Deng.

It addition, for providing water repellency etc., fluorochemical can be added, the example of fluorochemical include (ten three fluoro-1, 1,2,2-tetrahydrochysene octyl group) triethoxysilane, (3,3,3-trifluoro propyl) trimethoxy silane, 3-(seven fluorine isopropoxies) propyl group Triethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyl triethoxysilane, 1H, 1H, 2H, 2H-perfluoro decyl triethoxysilicane Alkane and 1H, 1H, 2H, 2H-perfluoro capryl triethoxysilane etc..

Silane coupler can use with any amount, but the amount of fluorochemical is preferably the most fluorine-containing compound by weight Less than 0.25 times.Furthermore, it is possible to reactive F compound etc. disclosed in mixing Japanese Unexamined Patent Publication 2001-166510 publication.

Silicon compound and the example of fluorochemical containing free-radical polymerised group include Japanese Unexamined Patent Publication 2007- Compound etc. disclosed in No. 11005 publications.

In the cured film constituting protective layer (outmost surface layer) 5, preferably add resist degradation agent.

As resist degradation agent, the preferably agent of Hinered phenols resist degradation and hindered amines resist degradation agent, it is also possible to use any The antioxidant known, such as organic sulfur class antioxidant, phosphite (ester) class antioxidant, dithiocarbamates resist Oxidant, Thiourea antioxidant, benzimidazole antioxidant etc..

The addition of resist degradation agent is preferably below 20 weight %, below more preferably 10 weight %.

The example of hindered phenol anti-oxidants include IRGANOX 1076, IRGANOX 1010, IRGANOX 1098, IRGANOX 245, IRGANOX 1330, IRGANOX 3114, IRGANOX 1076 and 3,5-di-t-butyl-4-xenol Deng.

The example of hindered amines antioxidant includes SANOL LS2626, SANOL LS765, SANOL LS770, SANOL LS744, TINUVIN 144, TINUVIN 622LD and MARK LA57, MARK LA67, MARK LA62, MARK LA68 and MARK LA63, the example of thioether antioxidants includes SUMILIZER TPS and SUMILIZER TP-D, phosphate (ester) class The example of antioxidant include MARK 2112, MARK PEP-8, MARK PEP-24G, MARK PEP-36, MARK 329K, MARK HP-10 etc..

Additionally, constitute the cured film of protective layer (outmost surface layer) 5 can be added with conductive particle or organic or Inorganic particle.

The example of granule includes silicon-containing particles.Silicon-containing particles refers to the silicon granule as component, and its tool Body example includes silica sol and organic silicon granule.Silica sol as silicon-containing particles selected from mean diameter is The silicon dioxide of 1nm～100nm, preferably 10nm～30nm, and in being scattered in acidity or alkaline water dispersion liquid or point Dissipate and use after in the organic solvents such as such as alcohol, ketone, ester.Silica sol can be commercially available prod.

In protective layer, the solid content of silica sol is not particularly limited, but relative to total inclusion admittedly of protective layer 5, should Content is preferably 0.1 weight %～50 weight %, more preferably 0.1 weight %～30 weight %.

Organic silicon granule as silicon-containing particles is selected from silicone resin particles, organic silicon rubber granule and surface by organic The treated silica dioxide granule that silicon processes, and commercially available organic silicon granule can be used.

These organic silicon granules are spherical, and mean diameter is preferably 1nm～500nm, more preferably 10nm～ 100nm。

Relative to total inclusion admittedly of protective layer 5, the amount of organic silicon granule is preferably 0.1 weight %～30 weight %, more excellent Elect 0.5 weight %～10 weight % as.

Additionally, other examples of described granule include such as tetrafluoroethene, trifluoro-ethylene, hexafluoropropene, fluorothene, inclined two The fluorine granules such as fluorothene, such as " The Proceedings of The 8^thPolymer Material Forum, Lecture " The granule of the resin by fluororesin and the monomer copolymerization with hydroxyl are obtained of the grade described in page 89, and such as ZnO-Al₂O₃、SnO₂-Sb₂O₃、In₂O₃-SnO₂、ZnO₂-TiO₂、ZnO-TiO₂、MgO-Al₂O₃、FeO-TiO₂、TiO₂、SnO₂、 In₂O₃, the granule of the metal oxide semiconductor such as ZnO, MgO.It addition, in order to granule dispersion being used various known point Powder.

Furthermore it is possible to add the oil such as such as organic silicone oil.

The example of organic silicone oil includes: such as dimethyl polysiloxane, diphenylpolysiloxane, phenyl methyl siloxane etc. Organic silicone oil；Such as amino modified polysiloxane, epoxy-modified polysiloxanes, carboxy-modified polysiloxanes, carbinol-modified poly- Siloxanes, acrylic modified polysiloxanes, sulfhydryl modified polysiloxanes, phenol-modified polysiloxanes isoreactivity organosilicon Oil；Such as hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane Etc. ring-type dimethicone；Such as 1,3,5-trimethyl-1,3,5-triphenyl cyclotrisiloxane, 1,3,5,7-tetramethyls- 1,3,5,7-tetraphenyl cyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1, the ring-type first such as 3,5,7,9-pentapheneyl cyclopentasiloxanes Base phenyl ring siloxane；The cyclic phenyl cyclosiloxane such as such as hexaphenyl cyclotrisiloxane；Such as 3-(3,3,3-trifluoro propyl) The fluorine-containing cyclosiloxane such as methyl cyclotrisiloxane；Such as methylhydrogensiloxane mixture, pentamethyl cyclopentasiloxane, phenyl hydrogen Change the cyclosiloxane of the containing hydrogenated silicyls such as cyclosiloxane；Such as five vinyl pentamethyl cyclopentasiloxanes etc. are containing vinyl Cyclosiloxane.

Furthermore, it is possible to add metal, metal-oxide, white carbon black etc..The example of metal include aluminum, zinc, copper, chromium, nickel, silver, Rustless steel etc., and on it, deposition has the plastic grain of above-mentioned metal.The example of metal-oxide include zinc oxide, titanium oxide, Stannum oxide, stibium oxide, Indium sesquioxide., bismuth oxide, the Indium sesquioxide. of doped tin, antimony dopant or the doping stannum oxide of tantalum, the oxygen of antimony dopant Change zirconium etc..

These can be used alone, it is also possible to is used in combination.When being used in combination, they are permissible Mix simply, it is also possible to make solid solution or molten product.The mean diameter of conductive particle is preferably below 0.3 μm, special You Xuanshi be below 0.1 μm.

(compositions)

Protective layer 5 formation compositions is preferably prepared, described molten with lysate (protective layer formation coating fluid) Solve in liquid at least one by leading to the charge transport material containing mercapto that formula (I) represents and at least one has unsaturated bond Compound dissolution is in a solvent.

Protective layer formation coating fluid can not contain solvent, or can also comprise solvent when necessary, such as toluene, two The aromatic solvents such as toluene；The ketones solvents such as such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Ketohexamethylene；Such as ethyl acetate, second The esters solvents such as acid butyl ester；Such as oxolane, twoThe ether solvents such as alkane；The cellosolve classes such as such as glycol monoethyl ether are molten Agent；And the such as alcohols solvent such as isopropanol, butanol, these solvents can be used alone or be used as mixed solvent.

Additionally, when coating fluid is to be prepared by the reaction of mentioned component, can be by the mixing of each composition and to dissolve, But it is preferred that the condition room temperature (20 DEG C)～100 DEG C, more preferably 30 DEG C～80 DEG C is little to their heating 10 minutes～100 Time so more preferably 1 hour～50 hours.Now, ultrasonic irradiation is further preferably used.

(preparation of protective layer 5)

By such as knife coating, bar rubbing method, spraying process, dip coating, pearl coating, air knife coating method, curtain coating method, ink-jet The conventional coating process such as rubbing method, (is that electric charge is defeated by protective layer formation coating solution at coating surface in the case of Fig. 1 Send layer 3) on.

Afterwards, the film obtained is applied optical, electrical sub-bundle or heat, so that membrane fussion and solidification.

When making membrane fussion and solidification by heat, heating condition is preferably more than 50 DEG C.Particularly, heating-up temperature is preferably 100 DEG C～180 DEG C.

When making membrane fussion and solidification by light, can shine by using the such as known method such as mercury lamp, metal halide lamp Penetrate light, to obtain cured film.

In above-mentioned polymerization and curing reaction, it is preferably less than 10% in vacuum or oxygen concentration, more preferably less than 5%, enter And more preferably less than 2%, the inert gas atmosphere of the low oxygen concentration of most preferably below 500ppm reacts, thus can To carry out chain reaction without making to be inactivated by optical, electrical sub-bundle or thermogenetic free radical.

In this illustrative embodiments, particularly preferred free radical produces the relatively slow solidification side carried out by heat Method.

The thickness of protective layer 5 is preferably 3 μm～40 μm, more preferably 5 μm～35 μm.

Electrophtography photosensor 7A above by reference to shown in Fig. 1 illustrates each layer in function divergence type photoreceptor layers Constitute, but this composition can also be applied to the function divergence type Electrophtography photosensor 7B shown in Fig. 2.Additionally, shown in Fig. 3 In the case of the single-layer type photosensitive layer 6 of Electrophtography photosensor 7C, implementation below is preferred.

Namely be based on total inclusion, the electricity in single-layer type photosensitive layer 6 admittedly of protective layer (outmost surface layer) 5 formation compositions Lotus produces the content of material and is preferably 5 weight %～50 weight %, preferably 10 weight %～40 weight %, and particularly preferably 15 Weight %～35 weight %.

As the method forming single-layer type photosensitive layer 6, it is possible to use form charge generation layer 2 or the side of charge transport layer 3 Method.The thickness of single-layer type photosensitive layer 6 is preferably 5 μm～50 μm, more preferably 10 μm～40 μm.

Additionally, describe the embodiment that outmost surface layer is protective layer 5 in embodiment of above, but, do not having In the case of the layer of matcoveredn 5 is constituted, layer is positioned at the charge transport layer of outmost surface in constituting can be outmost surface layer.? Outmost surface layer is in the case of charge transport layer, and the thickness of layer is preferably 7 μm～70 μm, more preferably 10 μm～60 μm.

Non-reacted adhesive resin

When the charge transport material containing mercapto is also used in resin, it is possible to use such as polyester resin, Polyacrylate resin, methacrylic resin, acrylic resin, Corvic, polyvinylidene chloride resin, polyphenyl second The known non-reacted adhesive resin such as olefine resin.

Total inclusion admittedly based on the compositions for forming film, the total content of described non-reacted adhesive resin is preferred It is 0 weight %～60 weight %, more preferably 0 weight %～55 weight %, and then more preferably 0 weight %～50 weight %.

Reactive compounds

In the case of solidification, can also comprise in the charge transport material containing mercapto represented by logical formula (I) Reactive compounds, and especially, for improving intensity, be preferably blended in same a part and there is two or more double bond Monomer, oligomer or polymer also make it solidify.

Example as the monofunctional monomer of reactive compounds includes Isobutyl 2-propenoate, tert-butyl acrylate, propylene Acid different monooctyl ester, lauryl acrylate, stearyl acrylate base ester, isobornyl acrylate, cyclohexyl acrylate, acrylic acid 2-methoxy Base ethyl ester, methoxyethyl triglycol ester, acrylic acid 2-ethoxy ethyl ester, acrylic acid tetrahydro furfuryl ester, acrylic acid benzene first Ester, acrylic acid ethyl carbitol ester, acrylate, 2-hydroxy acrylate, acrylic acid 2-hydroxy propyl ester, acrylic acid 4-hydroxybutyl, methoxyethyl macrogol ester, methacrylic acid methoxyl group macrogol ester, the poly-second of acrylic acid phenoxy group Diol ester, methacrylic acid phenoxy group macrogol ester, hydroxy ethyl o-phenyl phenol ester, acrylic acid o-phenyl phenol contract Water glycerol ether-ether, styrene etc..

Example as the bifunctional monomer of reactive compounds includes two (methyl) acrylic acid binaryglycol ester, two (first Base) polyalkylene glycol acrylate ester, two (methyl) acrylic acid polypropylene glycol ester, two (methyl) acrylic acid DOPCP, two (first Base) acrylic acid 1,6-hexanediol ester, divinylbenzene, diallyl phthalate etc..

As the example of the trifunctional monomer of reactive compounds include trimethylolpropane tris (methyl) acrylate, three (methyl) acrylate, pentaerythritol, aliphatic three (methyl) acrylate, triethylene cyclohexane etc..

Example as four functional monomers of reactive compounds includes four (methyl) acrylate, pentaerythritol, double three hydroxyls Methylpropane four (methyl) acrylate, aliphatic four (methyl) acrylate etc..

As monomers more than five senses of reactive compounds example five (methyl) acrylic acid dipentaerythritol ester, six (methyl) acrylic acid dipentaerythritol ester, and there is polyester backbone, carbamate skeleton or (methyl) third of phosphine nitrile skeleton Olefin(e) acid ester.

Additionally, the example as the reactive polymer of reactive compounds includes Japanese Unexamined Patent Publication 5-216249 public affairs Report, Japanese Unexamined Patent Publication 5-323630 publication, Japanese Unexamined Patent Publication 11-52603 publication, Japanese Unexamined Patent Publication 2000-264961 public affairs Those disclosed polymer such as report and Japanese Unexamined Patent Publication 2005-2291 publication.

Using in the case of reactive compounds, it can be used alone or uses with two or more mixture. Total inclusion admittedly based on the compositions for forming film, the consumption of described reactive compounds is preferably below 60 weight %, more It is preferably below 55 weight %, and then below more preferably 50 weight %.

Polymerization and solidification

Using the lysate being wherein dissolved with the charge transport material containing mercapto, and making each one-tenth in lysate Lease making polymerization, to obtain in the case of cured film, uses heat, light, radiation etc. during polymerization.

Using in the case of light and heat carry out being polymerized and solidify, polymerization initiator is optional, but can make to use up Curing catalysts or thermal polymerization.As light-cured catalyst and thermal polymerization, known photocuring is used to be catalyzed Agent or thermal polymerization.As radiation, then preferred electron bundle.

-electronic beam curing-

Using in the case of electron beam, accelerating potential is preferably below 300kV, preferably below 150kV.It addition, spoke Penetrate dosage and be preferably 1Mrad～100Mrad, more preferably 3Mrad～50Mrad.When accelerating potential is set as below 300kV Time, it is suppressed that electron beam irradiation is for the infringement of photoreceptor characteristic.It addition, when radiation dose is set as more than 1Mrad, hand over Connection can fully be carried out, and when radiation dose is set as below 100Mrad, it is suppressed that the deterioration of photoreceptor.

Radiation is entered in the inert atmosphere such as nitrogen, argon under the oxygen concentration of below 1000ppm, preferably below 500ppm OK, radiation during or after irradiation, can heat at 50 DEG C～150 DEG C.

-photocuring-

As light source, it is possible to use high voltage mercury lamp, low pressure mercury lamp, metal halide lamp etc., and the logical filter of band can be used The optical filters such as mating plate select preferred wavelength.Can be with unrestricted choice radiated time and light intensity, such as, illumination (365nm) is excellent Elect 300mW/cm as²Above and 100mW/cm²Hereinafter, and such as, with ultraviolet light with 600mW/cm²Carry out situation about radiating In, radiation can carry out 5 seconds～360 seconds.

The example of intramolecular cracking type light-cured catalyst includes benzyl ketal class light-cured catalyst, alkyl phenyl ketone Class light-cured catalyst, aminoalkyl-phenones class light-cured catalyst, phosphinoxides light-cured catalyst, titanocenes class light are solid Change catalyst, oximes light-cured catalyst etc..

More specifically, the example of benzyl ketal class light-cured catalyst includes 2,2-dimethoxy-1,2-diphenyl Second-1-ketone.

It addition, the example of alkyl phenyl ketones light-cured catalyst includes 1-hydroxy-cyciohexyl phenyl ketone, 2-hydroxyl-2- Methyl isophthalic acid-phenyl acrylate-1-ketone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-acrylate-1-ketone, 2-hydroxyl-1- { 4-[4-(2-hydroxy-2-methyl propiono) benzyl] phenyl }-2-methylpropane-1-ketone, 1-Phenylethanone. and 2-phenyl-2-are (right Tosyloxy) 1-Phenylethanone..

The example of aminoalkyl-phenones class light-cured catalyst includes to dimethylamino benzoylformaldoxime, to dimethylamino Propiophenone, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholinyl acrylate-1-ketone, 2-benzyl-2-dimethylamino-1-(4- Quinoline is for phenyl)-butanone-1,2-dimethylamino-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-fourth Ketone etc..

The example of phosphinoxides light-cured catalyst include TMDPO, double (2, 4,6-trimethylbenzoyls) phenyl phosphine oxide etc..

The example of titanocenes class light-cured catalyst includes double (η 5-2,4-cyclopentadiene-1-base)-bis-(2,6-bis-fluoro-3- (1H-pyrroles's-1-base) phenyl) titanium etc..

The example of oximes light-cured catalyst includes 1,2-acetyl caproyl, 1-[4-(thiophenyl)-2-(O-benzoyl oxime)] second Ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime) etc..

The example inhaling Hydrogen light-cured catalyst includes that benzophenone light-cured catalyst, thioxanthene ketone photocuring are catalyzed Agent, benzil class light-cured catalyst, Michler's keton (Michler ' s ketone) class light-cured catalyst etc..

More specifically, the example of benzophenone light-cured catalyst includes 2-benzoylbenzoic acid, 2-chlorodiphenyl first Ketone, 4,4 '-dichloro benzophenone, 4-benzoyl-4 '-methyldiphenyl thioether, p, p '-bis-diethylamino benzophenone etc..

The example of thioxanthene ketone light-cured catalyst includes 2,4-diethyl thioxanthene-9-one, CTX, 2-isopropyl Thiaxanthone etc..

The example of benzil class light-cured catalyst include benzil, (±)-camphorquinone, to anisil etc..

These Photoepolymerizationinitiater initiaters may be used singly or two or more in combination.

-heat cure-

The example of thermal polymerization includes V-30, V-40, V-59, V601, V65, V-70, VF-096, VE-73, VAm- 110 and VAm-111 (all being manufactured by Wako Pure Chemical Industries), and such as OTazo-15, OTazo- 30, the azo-initiator such as AIBN, AMBN, ADVN and ACVA (all being manufactured by Otsuka Chemical Co., Ltd.)；With And PERTETRA A, PERHEXA HC, PERHEXA C, PERHEXA V, PERHEXA 22, PERHEXA MC, PERBUTYL H, PERCUMYL H、PERCUMYL P、PERMENTA H、PEROCTA H、PERBUTYL C、PERBUTYL D、PERHEXYL D、 PEROYL IB、PEROYL 355、PEROYL L、PEROYL SA、NYPER BW、NYPER BMT-K40/M、PEROYL IPP、 PEROYL NPP、PEROYL TCP、PEROYL OPP、PEROYL SBP、PERCUMYL ND、PEROCTA ND、PERHEXYL ND、PERBUTYL ND、PERBUTYL NHP、PERHEXYL PV、PERBUTYL PV、PERHEXA 250、PEROCTA O、 PERHEXYL O、PERBUTYL O、PERBUTYL L、PERBUTYL 355、PERHEXYL I、PERBUTYL I、PERBUTYL E, PERHEXA 25Z, PERBUTYL A, PERHEXYL Z, PERBUTYL ZT and PERBUTYL Z is (by NOF Corporation manufacture), KAYAKETAL AM-C55, TRIGONOX 36-C75, LAUROX, PERCADOXL-W75, PERCADOX CH-50L、TRIGONOX TMBH、KAYACUMENE H、KAYABUTYL H-70、PERCADOX BC-FF、 KAYAHEXA AD、PERCADOX 14、KAYABUTYL C、KAYABUTYL D、KAYAHEXA YD-E85、PERCADOX 12- XL25、PERCADOX 12-EB20、TRIGONOX 22-N70、TRIGONOX 22-70E、TRIGONOX D-T50、TRIGONOX 423-C70、KAYAESTER CND-C70、KAYAESTER CND-W50、TRIGONOX 23-C70、TRIGONOX 23-W50N、 TRIGONOX 257-C70、KAYAESTER P-70、KAYAESTER TMPO-70、TRIGONOX 121、KAYAESTER O、 KAYAESTER HTP-65W、KAYAESTER AN、TRIGONOX 42、TRIGONOX F-C50、KAYABUTYL B、 KAYACARBON EH-C70、KAYACARBON EH-W60、KAYACARBON I-20、KAYACARBON BIC-75、 TRIGONOX 117 and KAYALENE 6-70 (being manufactured by Kayaku Akzo Co., Ltd.), UPEROX 610, LUPEROX 188、LUPEROX 844、LUPEROX 259、LUPEROX 10、LUPEROX 701、LUPEROX 11、LUPEROX 26、 LUPEROX 80、LUPEROX 7、LUPEROX 270、LUPEROX P、LUPEROX 546、LUPEROX 554、LUPEROX 575、LUPEROX TANPO、LUPEROX 555、LUPEROX 570、LUPEROX TAP、LUPEROX TBIC、LUPEROX TBEC、LUPEROX JW、LUPEROX TAIC、LUPEROX TAEC、LUPEROX DC、LUPEROX 101、LUPEROX F、 LUPEROX DI, LUPEROX 130, LUPEROX 220, LUPEROX 230, LUPEROX 233 and LUPEROX 531.

Wherein, if the molecular weight of azo type polymerization initiator is more than 250, under low temperature, reaction also is able to do not producing not Carry out in the case of uniformity, thereby promote the formation of the high-strength membrane that inhomogeneities is suppressed.Azo type polymerization causes The molecular weight of agent is preferably more than 250, and more preferably more than 300.

Heating low at preferably below 1000ppm, more preferably below 500ppm under nitrogen, argon isoreactivity atmosphere Oxygen concentration is carried out, and temperature is preferably 50 DEG C～170 DEG C, and then more preferably 70 DEG C～150 DEG C, the time be preferably 10 minutes～ 120 minutes, more preferably 15 minutes～100 minutes.

Always containing of total inclusion, light-cured catalyst or the thermal polymerization admittedly being formed relative in the lysate of layer Amount is preferably 0.1 weight %～10 weight %, more preferably 0.1 weight %～8 weight %, particularly preferably 0.1 weight %～5 Weight %.

-conductive base-

The example of conductive base 4 include using such as aluminum, copper, zinc, rustless steel, chromium, nickel, molybdenum, vanadium, indium, gold, platinum or its The metallic plate of the metals such as alloy, metal drum and metal tape.The example of conductive base 4 also includes being coated with on it, deposit or being laminated Have the paper of following material, plastic foil, a band etc.: the such as conductive compound such as electric conductive polymer and Indium sesquioxide., such as aluminum, palladium and Metal or its alloys such as gold.

Herein, term " electric conductivity " refers to that specific insulation is less than 10¹³Ω·cm。

When Electrophtography photosensor 7A is used in laser printer, preferably the surface of conductive base 4 is carried out slightly Roughening is to make it have the center line average roughness Ra of 0.04 μm～0.5 μm, thus prevents formed when irradiating laser to do Relate to striped.When using incoherent light as light source, the rough surfaceization preventing interference fringe is dispensable.

The preferred embodiment making the method for rough surface includes by the grinding agent being suspended in water is ejected into support Upper and carry out wet type honing, wherein make support under stress with the abrasive stones contact rotated with carry out continuously grinding be not in the mood for grind Mill, anodized etc..

Additionally, as the other method of rough surface, further preferably make using the following method: form resin on matrix surface Layer, in described resin bed, electric conductivity or semiconduction granule are dispersed in resin, come real from there through the granule being dispersed in layer Now it is roughened rather than makes conductive base 4 rough surface.

Herein, during the rough surfaceization carried out by anodic oxidation is processed, oxygen is formed on aluminum surfaces by anodic oxidation Compound film, carries out anodization to the aluminum as anode in described anodic oxidation in electrolyte solution.The example of electrolyte solution Including sulfuric acid solution, oxalic acid solution etc..But, have when the porous anodic oxide film that formed by anodic oxidation is the most modified Chemism, is easily contaminated, and resistance is big with environmental change.It is therefore preferable that carry out encapsulation process, at described sealing In reason, by the hydration reaction in pressurized steam or boiling water (wherein can add the slaines such as such as nickel salt) by anodic oxidation Thing changes into more stable hydrous oxide, causes volumetric expansion, and seals the pore of anodic oxide coating.

The thickness of anodic oxide coating is preferably 0.3 μm～15 μm.

Furthermore, it is possible to conductive base 4 to be carried out acidic aqueous solution process or boehmite process.Use includes phosphoric acid, chromium The process of the acidic treatment liquid of acid and Fluohydric acid. is carried out as follows:

First, mixed phosphate, chromic acid and Fluohydric acid. are to prepare acidic treatment liquid, and mixing ratio is preferably 10 weight %～11 weights Measure the phosphoric acid of %, 3 weight %～the chromic acid of 5 weight % and 0.5 weight %～the Fluohydric acid. of 2 weight %.Total sour composition dense Degree preferably 13.5 weight %～18 weight %.Treatment temperature is preferably 42 DEG C～48 DEG C, by the treatment temperature that holding is higher, Thicker film can be more quickly formed.The thickness of film is preferably 0.3 μm～15 μm.

Boehmite processes to be preferably as follows and carries out: impregnated 5 minutes～60 in the pure water that temperature is 90 DEG C～100 DEG C by matrix Minute, or by making the heating steam of matrix and 90 DEG C～120 DEG C contact 5 minutes～60 minutes.Film thickness is preferably 0.1 μm～5 μm.Can use and there is relatively low film deliquescent electrolyte solution film is carried out further anodized, described electricity Electrolyte solution such as adipic acid, boric acid, borate, phosphate, phthalate, maleate, benzoate, tartaric acid Salt, citrate etc..

-priming coat-

Priming coat 1 is such as made up of the adhesive resin containing inorganic particle.

The powder resistivity (specific insulation) that inorganic particle preferably has is about 10²Ω cm～10¹¹Ω·cm。

The preferred embodiment of the inorganic particle with above resistance value includes the nothings such as stannum oxide, titanium oxide, zinc oxide, zirconium oxide Machine granule, and zinc oxide is preferably used.

Additionally, inorganic particle can be by the inorganic particle that surface processes.Can will carry out different surface treatment Granule or there is the granule of different-grain diameter to be used in combination.

The specific surface area of inorganic particle is analyzed to measure by BET and is preferably 10m²/ more than g.

The equal particle diameter of body of inorganic particle is preferably 50nm～2000nm (preferably 60nm～1000nm).

Furthermore it is preferred that comprise acceptor compound and described inorganic particle simultaneously.

Described inorganic particle is not particularly limited, as long as it provides desirable characteristics, its preference includes electron transport Property material, the most such as quinones such as chloranil, bromine quinone, four cyano quinone bismethane compounds, such as 2,4,7-trinitro-s Fluorenone, 2, the Fluorenone compounds such as 4,5,7-tetranitros-9-Fluorenone, such as 2-(4-xenyl)-5-(4-tert-butyl-phenyl)-1, 3,4-Diazole, 2, double (the 4-naphthyl)-1,3,4-of 5-Diazole, 2, double (the 4-naphthyl)-1,3,4-of 5-Diazole etc.Diazoles Compound, xanthones compound, thiophene compound and such as 3,3 ', 5, the diphenoquinone compound such as 5 '-tetra-tert diphenoquinone, And particularly preferred example includes the compound with anthraquinone ring.And then preferred example includes having anthraquinone ring Acceptor compound, such as hydroxyanthraquinone compounds, amino anthraquinones compounds, hydroxy amino anthraquinone analog compound, and its Instantiation includes anthraquinone, alizarin, quinizarin, anthrarufin, alizarinopurpurin etc..

The content of acceptor compound is unrestricted, as long as being obtained in that in the range of required character, but preferably It is 0.01 weight % based on inorganic particle～20 weight %, more preferably 0.05 weight %～10 weight %.

Can simply acceptor compound be added in priming coat formation coating fluid, maybe can be pre-attached to nothing The surface of machine granule.

The example of the method that acceptor compound is attached to the surface of inorganic particle includes wet method and dry method.

When carrying out surface process according to dry method, stir the same of inorganic particle using the agitator with big shearing force Time, directly it is added dropwise to Receptor compound spurt into wherein in inorganic particle or together with dry air and nitrogen, or Person instills with the form of Receptor compound dissolution solution in organic solvent or enters wherein with dry air and nitrogen jet. Add or injection preferably temperature below the boiling point of solvent is carried out.Add or after injection acceptor compound, more than 100 DEG C At a temperature of bakee inorganic particle further.Baking can be carried out in the scope of any temperature and time.

Additionally, in wet method, utilize stirring, ultrasound wave, sand mill, burnisher, ball mill etc. to be existed by inorganic particle dispersion In solvent, it is subsequently adding acceptor compound, and mixture is stirred further or disperses, remove solvent subsequently, the most right Granule carries out uniform treatment.By filtering or solvent being distilled off.After removing solvent, can the temperature more than 100 DEG C dry Roasting.As long as required electrofax characteristic can be obtained, then can roasting in the range of any temperature and time.In wet method In, can remove, before adding surface conditioning agent, the moisture contained in inorganic particle, for example, it is possible to by processing with molten on surface In agent, agitating heating granule is to remove moisture, or by being azeotroped off removing moisture with described solvent.

Additionally, before adding acceptor compound, inorganic particle can be carried out surface process.Surface conditioning agent can be It is obtained in that any reagent of desirable characteristics by it, and is selected from known materials.The example of described reagent includes that silane is even Connection agent, titanate esters (salt) class coupling agent, aluminum class coupling agent, surfactant etc..Wherein, silane coupler is preferably used, because This reagent can provide good electrofax characteristic.Additionally it may be desirable to use the silane coupler with amino.

The silane coupler with amino can be any compound, as long as being obtained in that required Electrophtography photosensor Character, and its instantiation include but not limited to γ aminopropyltriethoxy silane, N-β-(amino-ethyl)-γ- TSL 8330, N-β-(amino-ethyl)-gamma-amino hydroxypropyl methyl dimethoxysilane, the double (β-hydroxyl second of N, N- Base)-γ aminopropyltriethoxy silane etc..

Additionally, silane coupler can use with two or more mixture.Can be with the silane coupler group with amino Close the example of silane coupler used include but not limited to vinyltrimethoxy silane, γ-methacryloxypropyl- Three ('beta '-methoxy ethyoxyl) silane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyl Trimethoxy silane, vinyltriacetoxy silane, γ mercaptopropyitrimethoxy silane, gamma-amino propyl triethoxy Silane, N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane, N-β-(amino-ethyl)-gamma-amino hydroxypropyl methyl two Methoxy silane, N, N-double (beta-hydroxyethyl)-γ aminopropyltriethoxy silane, γ-r-chloropropyl trimethoxyl silane etc..

Additionally, the surface treatment method using these surface conditioning agents to carry out can be any known method, and permissible Use dry or wet.Interpolation and the surface using coupling agent etc. to carry out that can carry out acceptor compound process simultaneously.

Silane coupler is unrestricted relative to the amount of the inorganic particle comprised in priming coat 1, as long as it is to obtain The amount of required electrofax characteristic, but it is preferably from about 0.5 relative to the amount of silane coupler described in described inorganic particle Weight %～10 weight %.

Additionally, priming coat 1 can contain adhesive resin.

As the adhesive resin contained in priming coat 1, it is possible to use good film can be formed and realize required character Any known resin, and the example includes known fluoropolymer resin compound, such as, such as polyvinyl butyral resin etc. Acetal resin；Polyvinyl alcohol resin, casein, polyamide, celluosic resin, gelatin, polyurethane resin, polyester resin, Methacrylic resin, acrylic resin, Corvic, vinylite, Chlorovinyl-acetate vinyl-horse Come anhydride resin, organic siliconresin, organosilicon-ol acid resin, phenol resin, phenolic resin, melmac, carbamate Resin etc.；With zirconium chelate, titanium chelate, aluminium chelate compound, Titanium alkoxides compound, organic titanic compound, silane coupler etc..

It addition, as the adhesive resin contained in priming coat 1, it is possible to use the electric charge with charge-transporting group is defeated The property sent resin；With electroconductive resins such as polyanilines.Wherein, resin insoluble in upper strata coating solvent is preferably used, and special Phenol resin, phenolic resin, melmac, base Ethyl formate resin, epoxy resin etc. are not preferably used.It is being applied in combination this In the case of a little resins, mixing ratio can be determined on demand.

In priming coat formation coating fluid, the inorganic particle that its surface is added with acceptor compound (gives Receptor The metal-oxide of matter) with the ratio of adhesive resin, or the ratio of inorganic particle and adhesive resin can be being obtained in that Suitably determine in the range of the Electrophtography photosensor characteristic needed.

Additionally, priming coat 1 can use various additive.

The example of additive includes that known materials, described known materials include: such as condensation polycyclic electron transport pigment or Electron-transporting properties pigment, zirconium chelate, titanium chelate, aluminium chelate compound, the Titanium alkoxides compounds such as azo electron transport pigment, have Machine titanium compound, silane coupler etc..As it has been described above, silane coupler can be used for inorganic particle is carried out surface process, but This reagent can also add further in priming coat formation coating fluid as additive.

Instantiation as the silane coupler of additive includes vinyltrimethoxy silane, γ-methacryl Epoxide propyl group-three ('beta '-methoxy ethyoxyl) silane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-shrink are sweet Oil epoxide propyl trimethoxy silicane, vinyltriacetoxy silane, γ mercaptopropyitrimethoxy silane, gamma-amino third Ethyl triethoxy silicane alkane, N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane, N-β-(amino-ethyl)-gamma-amino Hydroxypropyl methyl dimethoxysilane, N, N-double (beta-hydroxyethyl)-γ aminopropyltriethoxy silane, γ-chloropropyl trimethoxy Base silane etc..

It addition, the example of zirconium chelate includes butanol zirconium, ethyl acetoacetate zirconium, triethanolamine zirconium, acetopyruvic acid Butanol zirconium, ethyl acetoacetate close butanol zirconium, zirconium acetate, oxalic acid zirconium, zirconium lactate, phosphonic acids zirconium, zirconium caprylate, zirconium naphthenate, Laurel Acid zirconium, zirconium stearate, isostearic acid zirconium, methacrylic acid butanol zirconium, stearic acid butanol zirconium, isostearic acid butanol zirconium etc..

The example of titanium chelate includes tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, metatitanic acid four (2- Ethylhexyl) ester, acetylacetonate titanium, poly-acetylacetonate titanium, the octylene ester of glycolic close titanium, the ammonium salt of lactic acid titanium, lactic acid Titanium, lactic acid titanium ethyl ester, triethanolamine close titanium, multi-hydroxy stearic acid titanium etc..

The example of aluminium chelate compound includes aluminium isopropylate, diisopropyl acid only son's epoxide aluminum, butanoic acid aluminum, diisopropyl acid diethyl second Ethyl acetoacetic acid aluminum, three (oacetic acid) aluminum etc..

These compounds can be used alone or mixture or condensation polymer as multiple compounds uses.

For preparing the solvent of priming coat formation coating fluid, can be suitably selected from known organic solvent, such as alcohols molten Agent, aromatic solvents, halogenated hydrocarbon solvent, ketones solvent, ketols solvent, ether solvent, esters solvent etc..

As solvent, specifically, such as, use conventional organic solvent, such as methanol, ethanol, normal propyl alcohol, isopropanol, N-butyl alcohol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, Ketohexamethylene, methyl acetate, ethyl acetate, N-butyl acetate, twoAlkane, oxolane, dichloromethane, chloroform, chlorobenzene, toluene etc..

Additionally, these solvents can be used alone or use as two or more mixture.When two or more solvents mix During conjunction, it is possible to any mixed solvent of dissolved adhesive resin can serve as stand-by solvent.

As the method for dispersed inorganic particles when preparing priming coat formation coating fluid, it is possible to use such as roller mill, ball Any known methods such as mill, vibratory milling, burnisher, sand milling, colloid mill, coating vibrating machine.

It addition, as preparing the coating process of priming coat 1, use such as knife coating, bar rubbing method, spraying process, Any kind of common methods such as dip coating, pearl coating, air knife coating method, curtain coating method.

Then, the priming coat formation coating fluid being achieved in that is used to form priming coat 1 on conductive base.

Additionally, the Vickers hardness of priming coat 1 (Vickers hardness) preferably more than 35.

Furthermore it is possible to the thickness of priming coat 1 is set as any thickness, as long as being obtained in that required character, but Thickness is preferably more than 15 μm, more preferably 15 μm～50 μm.

Additionally, the surface roughness (10 mean roughness) of priming coat 1 to be preferably regulated as (1/4) n of laser wavelength lambda (wherein n represents the refractive index on upper strata)～(1/2) λ.

The granules such as resin can also be added to adjust its surface roughness in priming coat.The resin particle used includes Machine silicon resin particle, crosslinked polymethylmethacrylaparticles resin particle etc..

Furthermore it is possible to the surface of priming coat is ground, to adjust its surface roughness.As Ginding process, permissible Use polishing (buffing), blasting treatment, wet type honing, milled processed etc..Using such as LED, organic EL pattern matrix etc. During incoherent light source, it is possible to use smooth surface.

Priming coat 1 can be obtained by the priming coat formation coating fluid being coated on conductive base 4 is dried, But it is dried generally by carrying out evaporation solvent at a temperature of film can be formed.

-charge generation layer-

Charge generation layer 2 is the layer containing charge generating material and adhesive resin.It addition, charge generating layers 2 can be made Formed for the deposition film without adhesive resin.Especially, when using the such as incoherent light source such as LED, organic EL pattern matrix Time, it is preferred.

The example of charge generating material includes the such as AZOpigments such as bisazo or trisazo pigment, such as dibromo anthanthrene The fused aromatic pigment such as quinone, perylene pigment, pyrrolo-pyrrole pigments, phthalocyanine color, zinc oxide and tripartite's selenium.Wherein, For the laser explosure in corresponding near infrared region, metal phthalocyanine pigment and nonmetal phthalocyanine pigment are preferably used as electric charge and produce material Material.In particular it is preferred that the medium gallium opened such as Japanese Unexamined Patent Publication 5-263007 publication and Japanese Unexamined Patent Publication 5-279591 publication Gallium chlorine phthalocyanine disclosed in hydroxyl phthalocyanine, Japanese Unexamined Patent Publication 5-98181 publication etc., Japanese Unexamined Patent Publication 5-11172 publication and Disclosed in dichloro stannum phthalocyanine disclosed in Japanese Unexamined Patent Publication 5-11173 publication etc. and Japanese Unexamined Patent Publication 4-189873 publication Titanyl phthalocyanine.Additionally, for the laser explosure near ultraviolet band, more preferably use such as dibromo anthanthrone etc. to condense virtue Fragrant race pigment, thioindigo class pigment, porphyrazine compound, zinc oxide, tripartite's selenium, Japanese Unexamined Patent Publication 2004-78147 publication and Japan Disazo pigment disclosed in JP 2005-181992 publication.Additionally, using the centre of luminescence with 450nm～780nm During the incoherent light sources such as the LED of wavelength, organic EL pattern matrix, it is possible to use charge generating material, but from the sight of resolution Point sets out, and being used as thickness at photosensitive layer is in the case of the thin film of below 20 μm, and the field intensity in photosensitive layer is higher, and is prone to occur Cause owing to electric charge injects from matrix charged lowly, it is, the image deflects of referred to as stain.This is using such as tripartite Become notable in the case of the charge generating material being prone to generation dark current of the p-type semiconductor such as selenium, phthalocyanine color.On the contrary, exist Use in the case of the n-type semiconductor such as such as fused aromatic pigment, perylene pigment, AZOpigments, generate dark hardly Electric current, even the thinnest film also is able to suppression and is referred to as the image deflects of stain.Have been found that by use have 450nm～ The incoherent light sources such as the LED of the centre of luminescence wavelength of 780nm, organic EL pattern matrix form smooth matrix and priming coat, go forward side by side One step uses N-shaped charge generating material, it is possible to obtain such image: even if when photosensitive layer is made for the thin film of below 20 μm This image also will not cause image deflects, and long-time in there is higher resolution.The concrete reality of N-shaped charge generating material Example includes but not limited to following material.It addition, use normally used time-of-flight method to be entered by the polarity of the photoelectric current flowed The judgement of row N-shaped, wherein the flowing type easier than hole as carrier electrons is then considered as N-shaped.

In above figure, Structural Formula represents structural formula

The adhesive resin used in charge generation layer 2 can selected from the insulative resin of wide scope, or be selected from organic Photoconductivity polymer, such as poly-N-vinyl carbazole, polyvinyl anthracene, polyvinyl pyrene, polysilane etc..Adhesive resin Preference include polyvinyl butyral resin, the polyarylate resin condensation polymer etc. of aromatic binary carboxylic acid (bis-phenol with), poly- Carbonate resin, polyester resin, phenoxy resin, vinyl chloride vinyl acetate copolymer, polyamide, acrylic resin, poly- Acrylamide resin, polyvinylpyridine resin, celluosic resin, carbamate resins, epoxy resin, casein, poly-second Enol resin, polyvinylpyrrolidone resin etc..These resins may be used singly or in combination of two or more.Electric charge produces Green material is preferably 10: 1～1: 10 with the mixing ratio of adhesive resin.Term " insulating properties " referred to herein as specific insulation is 10¹³More than Ω cm.

Charge generation layer 2 can use charge generation layer formation coating fluid to be formed, and in described coating fluid, electric charge produces Green material and adhesive resin are dispersed in given solvent.Additionally, charge generation layer can also be as not comprising adhesive resin Deposition film formed, and particularly, fused aromatic pigment and perylene pigment are preferably for this deposition film.

Example for scattered solvent includes methanol, ethanol, normal propyl alcohol, n-butyl alcohol, benzyl alcohol, methyl cellosolve, second Base cellosolve, acetone, methyl ethyl ketone, Ketohexamethylene, methyl acetate, n-butyl acetate, twoAlkane, oxolane, dichloromethane, Chloroform, chlorobenzene, toluene etc..These solvents can be used alone, it is also possible to is used in combination.

It addition, as dispersion charge generating material and the method for adhesive resin in a solvent, use such as ball milling dispersion The common methods such as method, burnisher dispersion method, sand milling dispersion method.By these process for dispersing, it is possible to prevent electric charge to generate material Crystal formation changes because of dispersion.

It addition, effectively, treat that the mean diameter of scattered charge generating material is below 0.5 μm, preferably 0.3 μm with Under, below more preferably 0.15 μm.

Additionally, for forming charge generation layer 2, use conventional coating process, such as knife coating, Meyer rod (Meyer bar) Rubbing method, spraying process, dip coating, pearl coating, air knife coating method, curtain coating method etc..

The thickness of the charge generation layer 2 so obtained is preferably 0.1 μm～5.0 μm, more preferably 0.2 μm～2.0 μm.

-charge transport layer-

Charge transport layer 3 shown in Fig. 1 is by containing charge transport material and adhesive resin or carrying containing electric charge Property polymeric material and formed.

The example of charge transport material includes such as quinones (such as, 1,4-benzoquinone, chloranil, bromine quinone, anthraquinone etc.)；Four Cyano group benzoquinone bismethane compounds, fluorenone compound (such as, 2,4,7-trinitro-fluorenone), xanthones compound, hexichol The electron transport compounds such as ketone compounds, cyano vinyl based compound, ethylene compounds；Such as triaryl amine Compound, diphenyl amine compound, aromatic yl paraffin compounds, have the ethylene compounds of aryl substituent, stilbene compound, The cavity conveying compounds such as anthracene compounds, hydrazone compounds.These charge-transporting materials can be used alone, or two kinds Combination of the above uses, but is not limited to this.

From the viewpoint of charge mobility, charge transport material is preferably the triarylamine represented by following formula (a-1) and spreads out Biological and by the benzidine derivative represented with following formula (a-2).

In structural formula (a-1), R⁹Represent hydrogen atom, methyl ,-C (R¹⁰)=C (R¹¹)(R¹²) or-CH=CH-CH=C (R¹³) (R¹⁴).L represents 1 or 2.Ar⁶And Ar⁷Represent independently of one another and there is substituent group or not there is the aryl of substituent group ,-C₆H₄-C (R¹⁰)=C (R¹¹)(R¹²) or-C₆H₄-CH=CH-CH=C (R¹³)R¹⁴, and R¹⁰、R¹¹、R¹²、R¹³And R¹⁴Independently of one another Represent hydrogen atom, there is substituent group or not there is the alkyl of substituent group or there is substituent group or not there is the aryl of substituent group.

Herein, the example of the substituent group of each above-mentioned group includes halogen atom, the alkyl with 1～5 carbon atom, has The alkoxyl of 1～5 carbon atom and replacement have the amino with substituent group of the alkyl with 1～3 carbon atom.

In structural formula (a-2), R¹⁵And R^15’Represent hydrogen atom, halogen atom independently of one another, there is 1～5 carbon atom Alkyl or there is the alkoxyl of 1～5 carbon atom.R¹⁶、R^16’、R¹⁷And R^17’Represent that hydrogen atom, halogen are former independently of one another Son, have 1～5 carbon atom alkyl, have 1～5 carbon atom alkoxyl, replace have the alkane with 1 or 2 carbon atom The amino of base, there is substituent group or do not have the aryl of substituent group ,-C (R¹⁸)=C (R¹⁹)(R²⁰) or-CH=CH-CH=C (R²¹) (R²²), and R¹⁸、R¹⁹、R²⁰、R²¹And R²²Represent hydrogen atom independently of one another, there is substituent group or do not have the alkyl of substituent group, Or there is substituent group or do not have the aryl of substituent group；And m and n represents the integer of 0～2 independently of one another.

In the triarylamine derivatives represented by formula (a-1) and the benzidine derivative represented by formula (a-2), preferably have There is "-C₆H₄-CH=CH-CH=C (R¹³)(R¹⁴) " triarylamine derivatives and there is "-CH=CH-CH=C (R²¹)(R²²)” Benzidine derivative because they are at charge mobility, to the adhesiveness of protective layer with prevent because the vestige of image in the early time draws Residual image (hereinafter also referred to as " ghost image (ghosting) ") aspect risen is excellent.

Example for the adhesive resin of charge transport layer 3 includes polycarbonate resin, polyester resin, polyarylate tree Fat, methacrylic resin, acrylic resin, Corvic, polyvinylidene chloride, polystyrene resin, poly-acetic acid second Alkene ester resin, SB, vinylidene chloride-acrylonitrile copolymer, vinyl chloride vinyl acetate copolymer, Chlorovinyl-acetate vinyl-copolymer-maleic anhydride, organic siliconresin, silicone alkyd, phenolic resin, styrene-ol Acid resin, poly-N-vinyl carbazole, polysilane etc..Can use at Japanese Unexamined Patent Publication 8-176293 publication and 8-208820 Polyesters polymer charge transporting material etc. described in number publication.Wherein, optimization polycarbonate resin and polyarylate resin.

These adhesive resins may be used singly or two or more in combination.Charge transport material and binding agent tree The mixing ratio of fat is preferably 10: 1～1: 5.

Particularly, comprise by containing reactive charge transport material and Merlon to provide on charge transport layer 3 The protective layer (outmost surface layer) of the cured film that the compositions of resin prepares, preferably makes the binding agent used in charge transport layer 3 The viscosity-average molecular weight that resin has is 50, more than 000, more preferably 55, more than 000.

It addition, the upper limit of viscosity-average molecular weight of the adhesive resin used in charge transport layer 3 is preferably 100,000 with Under.

Herein, in this illustrative embodiments, the viscosity-average molecular weight of adhesive resin is to use capillary viscosity meter to obtain The value obtained.

Additionally, be in the case of charge transport layer at outmost surface layer, gluing all of the adhesive resin contained in priming coat Molecular weight is the most within the above range.

Additionally, as charge transport material, it is also possible to use polymer charge conveying material.Carry as polymer charge Material, it is possible to use there is the known materials of charge-transporting, such as poly-N-vinyl carbazole, polysilane etc..Particularly preferred It it is the disclosed polyesters polymer charge conveying material such as Japanese Unexamined Patent Publication 8-176293 publication and 8-208820 publication.High Molecule charge conveying material can independent film forming, but can also mix with above-mentioned adhesive resin thus form film.

Charge transport layer 3 can use the coating fluid containing mentioned component to be formed.

Example for the solvent of charge transport layer formation coating fluid includes conventional organic solvent, such as, such as benzene, first The aromatic hydrocarbon such as benzene, dimethylbenzene, chlorobenzene, the such as ketone such as acetone, 2-butanone, the halo fat such as such as dichloromethane, chloroform, dichloroethanes Fat hydrocarbon, the such as cyclic ethers such as oxolane, ether or linear.These solvents can be used alone or make with two or more combinations With.Known method can be used to make mentioned component disperse.

In order to by charge transport layer formation coating solution on charge generation layer 2, it is possible to use conventional coating side Method, such as knife coating, Meyer rod coating method, spraying process, dip coating, pearl coating, air knife coating method, curtain coating method etc..

The thickness of charge transport layer 3 is preferably 5 μm～50 μm, more preferably 10 μm～30 μm.

As charge transport layer, it is possible to use the surface layer material of this illustrative embodiments.

Handle box and the image shape of the Electrophtography photosensor which use this illustrative embodiments are described below Forming apparatus.

The handle box of this illustrative embodiments be configured to from image forming apparatus dismounting and at least include with The Electrophtography photosensor of this illustrative embodiments of upper description is as sub-image holding member, and described image forming apparatus will be logical Cross development be positioned at the electrostatic latent image on sub-image holding member surface and the toner image that obtains is transferred to record medium thus Image is formed on record medium.

Additionally, the electronics that the image forming apparatus of this illustrative embodiments is configured to include this illustrative embodiments shines Phase photoreceptor, the charging device that Electrophtography photosensor is charged, the surface of charged Electrophtography photosensor is made to expose Light thus formed from the teeth outwards electrostatic latent image exposure device, use developing agent make latent electrostatic image developing to form toner image Developing unit and toner image is transferred to record medium transfer device.It addition, the image of this illustrative embodiments Formation equipment can be the tandem type of the photoreceptor with multiple toner corresponding to each color, in this case, preferably Be all of photoreceptor Electrophtography photosensor that is this illustrative embodiments.Further, it is possible to use turn in the middle of using The intermediate transfer mode of print medium carrys out transfer toner image.

Fig. 4 is the structural representation of the image forming apparatus showing this illustrative embodiments.As shown in Figure 4, image shape Forming apparatus 100 includes the handle box 300 equipped with Electrophtography photosensor 7, exposure device 9, transfer device 40 and intermediate transfer Medium 50.It addition, in image forming apparatus 100, exposure device 9 is arranged through the opening of handle box 300 and irradiates electronics photograph Phase photoreceptor 7, transfer device 40 is arranged to via intermediate transfer medium 50 relative with Electrophtography photosensor 7, and middle turn Print medium 50 is arranged to partly contact with Electrophtography photosensor 7.

Handle box 300 in Fig. 4 is integrally supported the Electrophtography photosensor 7 being in housing, charging device 8, is shown Image device 11 and cleaning device 13.Cleaning device 13 has cleaning doctor (parts to be cleaned).Cleaning doctor 131 be configured to The surface contact of Electrophtography photosensor 7.

Additionally, show the example of cleaning device 13, this cleaning device 13 is equipped with on the surface of oriented photoreceptor 7 offer profit The fiber component 132 (roll forming) of lubrication prescription 14, and employ fiber component 133 (flat scopiform) with secondary, but these Parts can use, it is also possible to does not uses.

As charging device 8, it is, for example possible to use use electric conductivity or semiconduction charging roller, charging brush, charging film, The contact-type charging device of charging rubber scraper, charging valve etc..Known non-contact type charging device can also be used, the most non- Contact-type roll-type charging device, the gate type corona tube (scorotron) utilizing corona discharge or corona tube charging device.

Additionally, although it is not shown, be to improve the stability of image, sense can be arranged around at Electrophtography photosensor 7 Body of light heater block, thus increases the temperature of Electrophtography photosensor 7 and reduces relative humidity.

The example of exposure device 9 includes can making to use up the exposure of the surface to photoreceptor 7 to form the optics of required image Instrument, described light such as semiconductor laser, LED light, liquid crystal light valve light etc..The wavelength of light source to be used is at the spectrum of photoreceptor In the range of sensitivity district.As semiconductor laser, it is mainly used near 780nm the near infrared light with oscillation wavelength.But It is that the wavelength of light source is not limited to above-mentioned wavelength, it is also possible to the laser and the oscillation wavelength that use oscillation wavelength to be 600nm magnitude exist Blue laser near 400nm～450nm.Furthermore it is possible to the surface emitting type LASER Light Source carrying out multi beam output is forming colour It is effective during image.Particularly, centre of luminescence wavelength is that the incoherent exposure light source of 450nm～780nm is for obtaining Gao Pin It is preferred for matter image.

Additionally, the total film thickness of the photosensitive layer in Electrophtography photosensor is below 20 μm, exposure device 9 preferably has non-phase Dry exposure light source.It addition, in the illustrative embodiments being more highly preferred to, utilize the electrofax that incoherent exposure light source exposes The area of the exposure spot of photosensitive surface is 1000 μm²Hereinafter, the centre of luminescence wavelength of incoherent exposure light source be 450nm～ 780nm。

It follows that description photohead.

Figure 10 is the diagram showing photohead, and Figure 11 is the figure showing state when being exposed photoreceptor with photohead Show.As shown in FIG. 10 and 11, each photohead such as includes organic EL device array (light-emitting device array 60B) and image unit (lens 70).

Light-emitting device array 60B such as include the luminescence unit that is made up of organic EL element (light-emitting component 60A) and its on The installation base plate (the light-emitting device array substrate 61 corresponding in Figure 10) of organic EL element is installed.

Organic EL element array (light-emitting device array 60B) and image unit (lens 70) by holding member remain every Open so that the optical distance between luminescence unit (light-emitting component 60A) and the light incident surface 70A of image unit is image unit Operating distance.

Herein, the operating distance of image unit refers to focus the entering to image unit of the lens 70 used in image unit Penetrate the distance between the 70A of face.

It addition, in image unit, the light that luminescence unit sends is incident from light incident surface 70A, and simultaneously from light emission Surface 70B exports, thus in predetermined position shooting.It is, by picking up what light-emitting component 60A launched on photoreceptor 30 Light, photoreceptor 30 exposes to form sub-image (Figure 11).

Herein, organic EL element array (light-emitting device array 60B) is described.

Organic EL element array can be such as so-called bottom emissive type, i.e. the light that luminescence unit is launched is caused peace Dress substrate (light-emitting device array substrate 61) side, but top emission structure also can use.

Luminescence unit is such as made up of one group of single light-emitting component 60A.Luminescence unit 60A is (luminous along installation base plate Cell array substrate 61) longitudinally (tandem) arrangement or arrange in zigzag in wire, thus constitute luminescence unit.By one group The luminescence unit that light-emitting component 60A is constituted is at least long as the image forming area of photoreceptor 30.

It follows that describe image unit (lens 70).

Image unit is such as made up of the array of multiple lens, is wherein arranged with a plurality of rod lens.As lens arra, Specifically, such as, (SLA:SELFOC is Nippon Sheet Glass to the most referred to as SELFOC lens arra The registered trade mark of Co., Ltd.) the index of refraction decentralized lens arra of distribution, but the combination of cylindrical lens can also be used. It addition, micro lens can be connected to single light source organic EL element.

As developing unit 11, it is possible to use wherein show with magnetic or non-magnetic mono-component developing agent or double composition Shadow agent contacts or does not contact for the conventional developing unit forming image.Described developing unit is not particularly limited, as long as its There is above-mentioned functions, and suitable selection can be carried out according to earmarking.The example includes wherein using brush or roller etc. The known developing unit that single component developing agent or tow-component developer are applied on photoreceptor 7.Wherein, it is preferably used and makes development Agent keeps the developing unit of developer roll in its surface.

Hereinafter, the toner used in developing unit 11 is described.

The average shape factor ((ML that the toner used in the image forming apparatus of this illustrative embodiments has²/A × π/4 × 100, wherein ML represents the greatest length of granule, and A represents the projected area of granule) it is 100～150, preferably 105～145, more preferably 110～140.Additionally, the equal particle diameter of the body of toner is preferably 3 μm～12 μm, more preferably 3.5 μm ～9 μm.

The method preparing toner is not particularly limited, but can use the tone being such as prepared by the following method Agent: mediate comminuting method, wherein mixes and mediates adhesive resin, coloring agent, antitack agent and optional charge control agent etc., go forward side by side Row is pulverized and classification；Changed by the method for the shape mediating the granule that comminuting method obtains by mechanical impact force or heat energy；Breast Liquid syndication aggregation method, the dispersion liquid wherein obtained by the polymerizable monomer by emulsion polymerization adhesive resin colours with containing The dispersion liquid mixing of agent, antitack agent and optional charge control agent and other reagent, then carries out assembling, heat and fuse to obtain Obtain toner particles；Suspension polymerization, wherein by be used for the polymerizable monomer obtaining adhesive resin with containing coloring agent, antiseized The solution suspension of agent and optional charge control agent and other reagent is in aqueous solvent and is polymerized；Dissolve suspension method, its In make adhesive resin and the solution suspension containing coloring agent, antitack agent and optional charge control agent and other reagent in aqueous To form granule in solution, etc..

In addition it is possible to use such as prepare the known methods such as the method for the toner with nucleocapsid structure, in described method Use the toner particles obtained by said method as core, make aggregated particle adhere to it further, then carry out heating and Merge.Additionally, as the preparation method of toner particles, from the viewpoint of controlling shape and particle diameter distribution, preferably in aqueous Suspension polymerization, emulsion syndication aggregation method and the dissolving suspension method carried out in solvent, and particularly preferably emulsion syndication aggregation method.

Toner master batch preferably comprises adhesive resin, coloring agent and antitack agent, and if desired, possibly together with silicon dioxide And charge control agent.

The example of the adhesive resin used in toner master batch includes single polymers or the copolymer of following compound: such as The phenylethylene such as styrene, chlorostyrene；The monoolefines such as such as ethylene, propylene, butylene, isoprene；Such as vinyl acetate, The vinyl acetate such as propionate, vinyl benzoate, vinyl butyrate；Such as acrylic acid methyl ester., ethyl acrylate, acrylic acid fourth Ester, dodecylacrylate, 1-Octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, methyl The alpha-methylene aliphatic monocarboxylic acid ester such as butyl acrylate, lauryl methacrylate；Such as vinyl methyl ether, ethylene The vinyl ethers such as benzyl ethyl ether, vinyl butyl ether；And such as ethenyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl The vinyl ketones such as alkenyl ketone；With the polyester resin synthesized by dicarboxylic acids and glycol are carried out copolymerization.

The example of common adhesive resin include polystyrene, styrene-alkyl acryl ate copolymer, styrene- Methacrylate copolymer, SAN, SB, styrene-maleic acid Anhydride copolymer, polyethylene, polypropylene, polyester resin etc..Other example includes polyurethane, epoxy resin, organic siliconresin, polyamides Amine, modified rosin, paraffin etc..

As the crystalline resin used in toner master batch, particularly preferred crystalline polyester resin, it is considered to during its fusing point Preferred aliphat crystalline resin.Because the intermolecular cohesiveness that aliphatic crystalline resin has is less, so also needing to Using the anti-adhesion effects of antitack agent, this reduces, by being applied to, the binding agent comprised in stratum nucleare for further providing for high glaze image The situation of the viscosity of resin.

-adhesive resin: (crystallinity) polyester resin-

The crystalline polyester resin used in toner and every other polyester resin are by polybasic carboxylic acid composition and polynary Alcohol composition synthesizes.Additionally, in this illustrative embodiments, as polyester resin, it is possible to use commercially available prod, or can also Use sintetics.

The example of polybasic carboxylic acid composition includes aliphatic dicarboxylic acid, as oxalic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, pungent two Acid, Azelaic Acid, decanedioic acid, 1,9-nonane dicarboxylic acid, 1,10-decane dicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1, the 14-tetradecane Dicarboxylic acids, 1,18-octadecane dicarboxylic acids etc.；The aromatic dicarboxylic acid of binary acid, as phthalic acid, M-phthalic acid, to benzene Dioctyl phthalate, naphthalene-2,6-dicarboxylic acids, malonic acid, mesaconic acid etc., and their anhydride or lower alkyl esters, but do not limit In this.

The example of carboxylic acid more than tricarboxylic acid or ternary includes 1,2,4-benzene tricarbonic acids, 1,2,5-benzene tricarbonic acids, 1,2, 4-naphthalene tricarboxylic acids and anhydride thereof and lower alkyl esters.These materials can be used alone, or two or more is used in combination.

Additionally, as acid composition, in addition to above aliphatic dicarboxylic acid or aromatic dicarboxylic acid, further preferably include tool There is sulfonic dicarboxylic acid component.The dicarboxylic acid component with sulfonic acid group enables the coloured materials such as such as pigment preferably Dispersion aspect is effective.Additionally, when by water by all resins emulsifying or suspend prepare granule time, sulfonic deposit Can as mentioned below carry out emulsifying or suspension when not using surfactant.

The example with sulfonic dicarboxylic acids includes 2 sulfotere phthalic acid sodium, 5-sulfoisophthalic acid sodium, sulphur Base sodium succinate etc., but it is not limited to this.Other examples also include its lower alkyl esters and anhydride etc..Based on constituting the complete of polyester Portion carboxylic acid composition, the content of the carboxylic acid composition with more than the binary of sulfonic acid group or binary is 1 mole of %～15 moles of %, excellent Elect 2 moles of %～10 moles of % as.If content is 1 mole of more than %, it is thus achieved that emulsified particles stability in time, and such as Really content is 15 moles of below %, it is suppressed that the crystalline reduction of polyester resin and the alloying process of granule after coagulation In, it is easy to the diameter of regulation toner.

Additionally, it is further preferred that also comprise in addition to above-mentioned aliphatic dicarboxylic acid or aromatic dicarboxylic acid and there is double bond Dicarboxylic acid component.Owing to radical crosslinking can be carried out by utilizing its double bond, the dicarboxyl with double bond is therefore preferably used Acid prevents heat during fix steps to be stained.The example of this dicarboxylic acids includes but not limited to fumaric acid, maleic acid, 3-hexene two Acid, 3-octendioic acid etc..Other examples include its lower member ester and anhydride etc..Wherein, it is contemplated that cost can be mentioned and include rich horse Acid, maleic acid etc..

As polyol component, aliphatic diol is preferred, and comprises the straight chain of the chain with 7～20 carbon atoms Type aliphatic diol is preferred.When aliphatic diol is straight chain type, the decline of the degree of crystallinity of polyester resin is suppressed, And the reduction of fusing point is also suppressed, therefore further improve the anticaking capacity of toner, image preservability and low-temperature fixing Property.When carbon number is more than 7, when with aromatic dicarboxylic acid polycondensation, fusing point will not rise so high, and therefore obtains low-temperature fixability, And when carbon number is more than 20, it is easy to obtain this material.More preferably carbon number is less than 14.

The example of the aliphatic diol used in the synthesis of the crystallized polyurethane resin preferably used in toner includes, but Be not limited to ethylene glycol, 1,3-PD, BDO, 1,5-PD, 1,6-hexanediol, 1,7-heptandiol, 1,8-pungent two Alcohol, 1,9-nonanediol, decamethylene-glycol, 1,11-undecyl glycol, 1,12-dodecanediol, 1,13-tridecyl two Alcohol, 1,14-myristyl glycol and 1,18-octadecyl glycol, 1,14-20 carbon decanediol etc..Wherein, it is easy to get when consideration During property, 1,8-ethohexadiol, 1,9-nonanediol and decamethylene-glycol are preferred.

The example of polyhydric alcohol more than trihydroxylic alcohol or ternary includes glycerol, trimethylolethane, triethylol propane, season Penta tetrol etc..These materials can be used alone, or two or more is used in combination.

In polyol component, the content of aliphatic diol composition is preferably 80 moles of more than %, and more preferably 90 rub You are more than %.If the content of aliphatic diol composition is 80 moles of more than %, the crystalline decline of polyester resin is suppressed, And the reduction of fusing point is also suppressed.Therefore, the anticaking capacity of toner, image preservability, low-temperature fixability obtain further Improve.

It addition, if desired in order to adjust acid number, hydroxyl value etc., it is also possible to use such as the monoacid such as acetic acid, benzoic acid and The such as monohydric alcohol such as Hexalin, benzyl alcohol.

Additionally, the ester concentration as determined by formula (7) that the crystalline polyester resin used in toner preferably has is 0.01～0.12:

M=K/A (7)

In formula (7), M represents that ester concentration, K represent the number of the ester group in crystalline polyester, and A represents composition crystalline polyester The atomic number of polymer chain.

By suppressing to be 0.01～0.12 by the ester concentration of crystalline polyester, it is possible to improve the agglomeration resistance of toner further Property, image preservability and low-temperature fixability, additionally it is possible to improve charging property.

If the ester concentration of crystalline polyester is more than 0.01, then charging property is good, and the fusing point of crystalline polyester is not Can become is too high, and the lower limit of the ester concentration that suppression low-temperature fixability declines is more preferably more than 0.04.

Additionally, if ester concentration is less than 0.12, it is suppressed that the decline of charging property, therefore, the fusing point of crystalline polyester is not Mutagens obtains too low, and inhibits fixing picture steadiness and the reduction of powder anticaking capacity.The upper limit of ester concentration is preferably Less than 0.10.

Additionally, " ester concentration " is a finger of the content ratio of the ester group in the polymer of instruction crystalline polyester resin Mark.In other words, the ester bond that " number of the ester group in polymer " represented by K in above formula refers to comprise in whole polymer Number.

" constituting the atomic number of the polymer chain of polymer " that A in formula (7) represents is the polymer chain constituting polymer The sum of atom, this number including participating in all atoms of ester bond, but do not include the branched moiety of other constituting parts Atomic number.

It is to say, by from participating in the carboxyl of ester bond and the carbon atom of alcohol radical and oxygen atom, (oxygen in an ester bond is former Subnumber is 2), and such as in aromatic rings, the six carbon atom constituting polymer chain counts for calculating atomic number, and such as In aromatic rings or alkyl, constitute the atom in the hydrogen atom of polymer chain or its substituent group or atom group do not carry out counting with For calculating.

-adhesive resin: noncrystallizable polymer-

Example for the noncrystallizable polymer resin of toner includes conventionally known thermoplastic binder resins etc., Its instantiation includes such as homopolymer or copolymer to the styrene or derivatives thereof such as chlorostyrene, α-methyl styrene (styrene resin)；Such as acrylic acid methyl ester., ethyl acrylate, n-propyl, n-butyl acrylate, acrylic acid 12 Arrcostab, 2-EHA, methyl methacrylate, ethyl methacrylate, n propyl methacrylate, methyl-prop Olefin(e) acid dodecyl ester, 2-Ethylhexyl Methacrylate etc. have the homopolymer of the ester of vinyl or copolymer is (vinyl-based Resin)；The homopolymer of the such as vinyl such as acrylonitrile, methacrylonitrile nitrile or copolymer (vinyl group resin)；Such as second The homopolymer of the vinyl ethers such as enylmethyl ether, vinyl isobutyl ether or copolymer (vinyl group resin)；Such as ethylene The homopolymer of the vinyl ketones such as ylmethyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone or copolymer (vinyl-based tree Fat)；The homopolymer of the olefines such as such as ethylene, propylene, butadiene, isoprene or copolymer (olefine kind resin)；Such as The non-vinyl condensation trees such as epoxy resin, polyester resin, polyurethane resin, polyamide, celluosic resin and polyether resin Fat, these non-vinyl condensation resins and the graft polymers etc. of vinyl monomer.These resins can be used alone or two Plant combination of the above to use.In these resins, particularly preferred vinyl group resin and polyester resin.

In the case of vinyl group resin, ionic surfactant etc. is used to carry out emulsion polymerization or crystal seed polymerization, The most easily preparing particulate resin dispersion, therefore this is favourable.The example of vinyl monomer includes vinyl-based high score Son acid such as acrylic acid, methacrylic acid, maleic acid, cinnamic acid, fumaric acid, vinyl sulfonic acid, Ethylenimine, vinylpyridine and Vinyl amine, and it is used as the monomer of the raw material of vinyl polymer alkali.

Additionally, above resin particle preferably comprises vinyl monomer as monomer component.Vinyl-based at these In monomer, in order to easily carry out being reacted to form the acid of vinyl group resin preferred vinyl family macromolecule, specifically, in order to The regulation degree of polymerization and glass transition point particularly preferably such as acrylic acid, methacrylic acid, maleic acid, cinnamic acid and fumaric acid etc. There is the carboxyl separation property vinyl monomer as separation property group.

Additionally, the example of common coloring agent include the such as Magnaglo such as magnetic iron ore and ferrite, white carbon black, aniline blue, Alizarin oil blue (chalcoyl blue), chrome yellow, ultramarine blue, Du Pont's oil red, D C Yellow No. 10, protochloride methyl blue, phthalocyanine blue, malachite Greenweed hydrochlorate, dim, rose-red, C.I. pigment red 4 8:1 C.I. pigment red 122, C.I. paratonere 57:1, C.I. pigment yellow 97, C.I. pigment yellow 17, C.I. pigment blue 15: 1, C.I. pigment blue 15: 3 etc..

The example of common antitack agent includes low molecular weight polyethylene, low-molecular-weight polypropylene, Fischer-Tropsch wax, lignite wax, bar Western palm wax, rice bran wax, candelilla wax etc..

It addition, as charge control agent, it is possible to use any of reagent, such as Azo metal complex, bigcatkin willow The metal complex of acid and the resin type charge control agent with polar group.Toner is prepared when preparation method by wet method Time, it is contemplated that control ionic strength and alleviate contaminated wastewater, it is possible to use being not readily dissolved in the material of water.It addition, toner is permissible It is the magnetic toner containing magnetic material, or the non magnetic toner without magnetic material.

By using Henschel mixer, V-type blender etc. above-mentioned toner master batch and additive to be mixed, can prepare aobvious The toner used in image device 11.When preparing toner master batch by wet method, additive can be added by wet method.

The toner used in developing unit 11 can comprise the granule with fluorine element.

The example of the granule with fluorine element include perfluorocarbon that fluorine is combined with graphite, polyflon (PTFE), Perfluoro alkoxy-fluororesin (PFA), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF) and polyvinyl fluoride (PVF), mean diameter is preferably 0.1 μm～4 μm.Furthermore, it is possible to become there is the granule of same particle size by the particulate abrasive with above-mentioned chemical constitution.Toner Addition is preferably 0.05 weight %～2.0 weight %, more preferably 0.1 weight %～1.5 weight %.If addition is More than 0.05 weight %, coefficient of friction will not be too high, it is suppressed that the generation of ghost image, and if time content is below 2.0 weight %, Inhibit the generation of opposite polarity toner.

Furthermore it is possible to addition lubricant particle.The example of lubrication base granule includes such as graphite, molybdenum bisuphide, Talcum, fat The kollags such as race is sour, the slaine of aliphatic acid, the such as low-molecular-weight polyolefin such as polypropylene, polyethylene and polybutene, all Such as fluorine-containing granules such as PTEF and PFA, there is during heating the organosilicon of softening point, such as oleamide, erucyl amide, castor oil acid The aliphatic amide such as amide and stearic amide；Such as Brazil wax, rice bran wax, candelilla wax, Japan wax and Jojoba oil In plant wax, the animal class wax such as such as Cera Flava；Such as lignite wax, ceresine, pure white ceresine (ceresine), paraffin, microwax With mineral and petroleum-type waxes such as Fischer-Tropsch waxes；And the modified product of these materials.They can be used alone, it is also possible to two kinds with On be applied in combination.The mean diameter of lubricant particle is preferably 0.1 μm～10 μm, can will have the granule of above-mentioned chemical constitution Grind to form the granule with same particle size.Described granule content in toner is preferably 0.05 weight %～2.0 weight %, More preferably 0.1 weight %～1.5 weight %.

In the toner that can use in developing unit 11, addition inorganic particle, organic granular, inorganic particle are attached to Composite particles etc. on organic granular, to remove deposit or deterioration thing from the surface of Electrophtography photosensor.

As inorganic particle, various inorganic oxide, nitride, carbide etc. are preferably used, such as silicon dioxide, oxidation Aluminum, titanium oxide, zirconium oxide, Barium metatitanate., aluminium titanates, strontium titanates, magnesium titanate, zinc oxide, chromium oxide, cerium oxide, stibium oxide, oxidation Tungsten, stannum oxide, tellurium oxide, manganese oxide, boron oxide, carborundum, boron carbide, titanium carbide, silicon nitride, titanium nitride, boron nitride etc..

In addition it is possible to use the following substances above-mentioned inorganic particle of process: such as butyl titanate, metatitanic acid four monooctyl ester, isopropyl Base three isostearoyl base titanate esters, isopropyl tridecyl benzenesulfonyl titanate esters, double (dioctylphyrophosphoric acid ester) fluoroacetic acid ester The titanium coupling agents such as titanate esters；Such as γ-(2-amino-ethyl) TSL 8330, γ-(2-amino-ethyl) amino Hydroxypropyl methyl dimethoxysilane, γ-methacryloxypropyl trimethoxy silane, N-β-(N-vinyl benzene methyl ammonia Base ethyl) gamma-amino propyl trimethoxy silicane hydrochlorate, hexamethyldisiloxane, MTMS, butyl front three TMOS, trimethoxysilane, hexyl trimethoxy silane, octyl group trimethoxy silane, decyl trimethoxy silicon Alkane, dodecyltrimethoxysilane, phenyltrimethoxysila,e, o-methyl-phenyl-trimethoxy silane, p-methylphenyl three The silane couplers such as methoxy silane.Organic silicone oil, such as aluminium stearate, zinc stearate and hard is utilized it is also preferable to use The slaine of the senior aliphatic acids such as fat acid calcium carries out the inorganic particle of hydrophobization process.

The example of organic granular includes styrene resin particles, styrene acrylic resin granule, polyester resin particle, ammonia Carbamate resin particle etc..

Particle diameter in terms of number average bead diameter is preferably 5nm～1000nm, more preferably 5nm～800nm, even more preferably from being 5nm～700nm.When mean diameter is not less than lower limit, granule tends to the abrasiveness with excellence.On the other hand, when flat When all particle diameter is less than higher limit, granule tends to suppress the surface of Electrophtography photosensor to be scratched.Above-mentioned granule and lubrication The total content of agent granule is preferably more than 0.6 weight %.

As other inorganic oxide added in toner particles, it is contemplated that powder flowbility and Charge controlled, excellent The little inorganic oxide particles that choosing uses primary particle size to be below 40nm, and in view of reducing adhesiveness and Charge controlled, excellent The particle diameter inorganic oxide more than described little inorganic oxide is added in choosing.Known inorganic oxide particles can be used, but For accurate Charge controlled, preferred compositions uses silicon dioxide and titan oxide particles.

Increase dispersibility additionally, little inorganic particle to be carried out surface process and enhance the effect of powder flowbility.Separately Outward, further preferably add the such as carbonate such as calcium carbonate, magnesium carbonate and the such as inorganic mineral such as brucite and cerium oxide to put to remove Electricity product.

Additionally, electrophotography color toner can use with carrier combinations.The example of carrier includes iron powder, glass Pearl, ferrite powder, nikel powder and surface are coated with the carrier of resin.Furthermore it is possible to suitably determine the mixed of toner and carrier Composition and division in a proportion.

As the method cleaning the toner remained on photoreceptor, use the cleaning doctor method utilizing rubber scraper, because of Miniaturization device can be manufactured for this.

For improving the wearability of cleaning doctor, the unit removing discharging product to be increased, or carrier collection can be increased Unit is to collect the microgranule load occurring the edge caused because of the attachment on image bearing member surface to be caused to crush along with BCO Body.BCO refers to Bead Carry Over, refers to owing to electrostatic attraction causes Component Vectors to be transferred to photoreceptor (image maintaining part Part) phenomenon on surface.

It addition, for the wearability improving cleaning doctor, it is possible to use high rigidity or high modulus material are protected as with image Hold the material of the part of component contact.This high modulus material can serve as monolayer rubber scraper, but it is said that in general, in some situation But middle wearability obtains improving elastic reduction.Elastic reduction shows due to rubber-like loss of properties, and therefore elongation becomes difficulty. Because elongation difficulty, along with the generation of BCO, the foreign body such as the such as carrier fragment being embedded in image holding member surface passes through During contact portion between edge and the image holding member surface of cleaning doctor, foreign body chases after the power making edge deformation from material, Thus in some cases in order to prevent marginal end from can not deform, blade edge is easily broken.

Further, since high-modulus (high rigidity) material has higher permanent elongation, permanent strain is (forever in some cases Deformation for a long time) may deteriorate.Therefore, if the amount of permanent strain increases, then can not maintain contact pressure, result is in some cases Cleaning may be caused bad.

For preventing the edge of above cleaning doctor from crushing, when foreign body passes through edge and the image holding member of cleaning doctor During contact portion between surface, marginal end is made up of the low-durometer material allowing this marginal end deformation (elongation), and this is favourable 's.It addition, from the viewpoint of preventing above permanent strain, low-durometer material is also advantageous.

But, owing to using these low-durometer material that wearability can be made to deteriorate, it is impossible to maintain clean-up performance for a long time.

Therefore, cleaning doctor is by the ground floor contacted with photosensitive surface and the back layer structure not contacted with photosensitive surface Become, and the material of ground floor preferably meet following formula (1)～(3):

Formula (1) 3.92≤M≤29.42

Formula (2) 0 ＜ α≤0.294

Formula (3) S >=250

(in formula (1)～(3), M represents 100% modulus (MPa), and α represents on load-deformation curve, from 100% strain To 200% strain, the change (Δ stress) of stress and the ratio { Δ stress/Δ dependent variable of the change (Δ dependent variable) of dependent variable =(dependent variable be stress-strain amount when 200% be stress when 100%)/(200-100) } (MPa/%), S represents basis The elongation at break (%) that JIS K6251 (using dumbbell shape #3 test film) measures).

Herein, cleaning doctor can have the second layer as back layer is arranged on what the surface with parts to be cleaned contacted Double-deck composition on the dorsal part of ground floor, or include that the back layer of the such as multilamellar such as the second layer, third layer is arranged on ground floor The composition of dorsal part.It addition, hereinafter, it is described in detail further to have and includes ground floor and the double-deck structure of the second layer as back layer The cleaning doctor become.

-ground floor-

The material of the ground floor owing to contacting with parts surface to be cleaned meets formula (1), and therefore scraper shows good clear Clean performance and have excellence wearability.

If 100% modulus M is 3.92MPa (40kgf/cm²More than), then obtain wearability, and remain long-term good Good clean-up performance.On the other hand, if 100% modulus M is 29.42MPa (300kgf/cm²) below, then the material of ground floor Will not be really up to the mark, cleaning doctor has the performance servo-actuated relative to parts to be cleaned, and has played good spatter property.It addition, press down Make the impaired of parts surface to be cleaned.

Additionally, 100% modulus M is preferably 5MPa～20MPa, more preferably 6.5MPa～15MPa.

Additionally, due to the material of ground floor meets formula (2) and (3), therefore resistance to rupture is excellent.

If the α shown in formula (2) is less than 0.294, then obtain the flexibility of ground floor material.Therefore, occur as BCO Time, the foreign body etc. such as embed, anchored on image holding member surface is present in the foreign body on parts surface to be cleaned, especially It is the foreign body embedding, anchoring on image holding member surface, iterates through contacting between parts to be cleaned and cleaning doctor Part, even if thus when the marginal end of cleaning doctor ground floor is applied to stand higher stress repeatedly, this stress also has been able to Imitate scattered mode to deform, thus inhibit edge to crush within the relatively short time.Accordingly, because inhibit the most broken Broken, thus the clean-up performance that long term maintenance is excellent.

It addition, α is preferably less than 0.2, more preferably less than 0.1, α are preferably closer to as the 0 of lower physical limit value.

When the elongation at break S shown in formula (3) is more than 250%, though the foreign body on parts surface to be cleaned with When strength collides the marginal end of ground floor, it is also possible to suppression edge within the relatively short time crushes.Thus, owing to inhibiting Edge within the relatively short time crushes, thus the clean-up performance that long term maintenance is excellent.

It addition, elongation at break S is preferably more than 300%, more preferably more than 350%.Crush in view of edge, preferably Bigger elongation at break S.But, when elongation at break S is less than 500%, (viscous to the following on band cleaning member surface Attached property) will not be excessive, and inhibit the increase of frictional force with parts to be cleaned, thus inhibit the mill of ground floor marginal end Consumption (edge abrasion).Thus, it is contemplated that edge wear away, elongation at break S is preferably less than 500%, more preferably 450% with Under, it is even more preferably less than 400%.

Additionally, the peripheral temperature around the cleaning doctor of image forming apparatus, i.e. ambient temperature during use is the most about It it is 10 DEG C～60 DEG C.Thus, when the glass transition temperature Tg of the material of the ground floor contacted with parts surface to be cleaned is the highest In use time ambient temperature time, cleaning doctor keeps its rubber-like character, thus maintains the contact pressure of cleaning doctor.Cause And, the lower limit (10 DEG C) of the ambient temperature when glass transition temperature Tg of the material of ground floor preferably no more than uses.

It addition, when the glass transition temperature Tg of the material of the ground floor contacted with parts surface to be cleaned is less than 10 DEG C Time, owing to glass transition temperature Tg is relatively low, resilience R of described material reduces.Therefore, if resilience R is more than 10%, Adhesion and the slip behavior of ground floor marginal end will not be the most slow, it is suppressed that maintain certain deformation state with surface when contacting Rub the appearance of part of parts surface to be cleaned simultaneously.

When deformed shape is adhered and slip behavior releases, limit while maintaining the marginal end shape of ground floor Acies not friction surface, thereby inhibiting plastic deformation local occur.When suppressing the generation of plastic deformation of this local, the The reduction of the adhesiveness between marginal end and the surface of parts to be cleaned of a layer is suppressed, thus inhibits cleaning bad Occur.In order to suppress the plastic deformation of this local, preferably adhere and slip behavior always occurs at the marginal end of ground floor.In order to Making adhesion and slip behavior always occur at the marginal end of ground floor, (this temperature is essentially environment when using to be 10 DEG C in temperature The lower limit of temperature) more than environment in, resilience R is preferably more than 10%, more preferably more than 15%, even more preferably It is more than 20%.

It addition, resilience R measures according to above-mentioned JIS K6255 (1996).

Additionally, modulus M shown in formula (1) uses dumbbell shape #3 test film at 500mm/min according to JIS K6251 (1993) Draw speed under measure and by 100% strain time stress obtain.As measurement apparatus, use by Toyo Seiki The STROGRAPH AE ELASTOMER that Seisakusho, Ltd. manufacture.

It addition, the α value shown in formula (2) is obtained by load-deformation curve.Dependent variable and stress are by following step and side Method obtains.That is, according to JIS K6251 (1993), survey under the draw speed of 500mm/min with dumbbell shape #3 test film Amount, α is obtained by stress when 100% strain and 200% strain.As measurement apparatus, use by Toyo Seiki The STROGRAPH AE ELASTOMER that Seisakusho, Ltd. manufacture.

Additionally, in one aspect of the invention, the vitrification of the material of the ground floor contacted with parts surface to be cleaned The glass transition temperature of transition temperature and soft segment material described later and hard segment materials measures temperature at use viscoelastometer and divides After Saning, determine as the peak temperature of tan δ (loss angle tangent).

Herein, the value of tan δ is obtained by following storage elastic modelling quantity and loss elastic modulus.When will be as stationary vibration Sinusoidal wave strain when putting on linear elastomer, stress is represented by formula (4).

|E^*| it is referred to as complex elastic-modulus.Additionally, according to rheology theory, elastomer components and viscoid composition respectively with Formula (5) and formula (6) represent.In described formula, E ' represents storage elastic modelling quantity and E " represent loss elastic modulus.δ represents stress And the phase angle between Ying Bian, and it is referred to as " mechanical loss angle ".

The value of tan δ is by the E shown in formula (7) "/E ' expression, and it is referred to as " loss angle tangent ".When loss angle tangent is higher Time, linear elasticity parts have the character close to caoutchouc elasticity.

Formula (4) σ=| E^*|γcos(ωt)

Formula (5) E '=| E^*|cosδ

Formula (6) E "=| E^*|sinδ

Formula (7) tan δ=E "/E '.

The value of tan δ within the temperature range of-60 DEG C～100 DEG C 5% static strain and the sinusoidal wave stretching vibration of 10Hz Lower RHEOPECTROLER DVE-V4 (being manufactured by Rheology Co., Ltd.) measures.

As it has been described above, the material of the ground floor used in cleaning doctor has the wearability of excellence and resistance to broken simultaneously Property, and maintain good clean-up performance.

Therefore, when there is BCO, also it is unnecessary to the foreign body such as embedding, anchoring on image holding member surface Etc. the foreign body being present on parts surface to be cleaned, particularly embed and set foreign body on a surface, respond and The isolated system for improving wearability or crush resistance arranged in image forming apparatus, thus, it is possible to avoiding device is big Type and the increase of cost.

Further, since cleaning doctor service life increase, be thus susceptible to realize equipped with cleaning doctor handle box or The long service life of cleaning device, and it is easily achieved the decline maintaining cost.Particularly, if equipped with the table with improvement The handle box of both the image holding member of face wearability and cleaning doctor or cleaning device, above-mentioned advantage can obtain further Strengthen.

The material meeting formula (1)～(3) is not particularly limited, as long as it is elastomeric material.But, specifically This material can be the elastomeric material comprising hard segment and soft chain segment.When elastomeric material comprises hard segment and soft chain segment simultaneously Time, elastomeric material is content with very little physical property defined in formula (1)～(3), and can realize higher with high level simultaneously Wearability and higher crush resistance.

Additionally, " hard segment " refer to constitute the former material with " soft chain segment " more relative than the material constituting the latter more firmly and structure The material becoming the latter is softer than the material constituting the former.

The glass transition temperature of the elastomeric material comprising hard segment and soft chain segment is preferably-50 DEG C～30 DEG C, more excellent Elect-30 DEG C～10 DEG C as.If glass transition temperature is less than 30 DEG C, the most in some cases at actually used cleaning doctor Within the temperature range of to be prevented from cleaning doctor frangible.And if glass transition temperature is more than-50 DEG C, then actually used Within the temperature range of obtain enough hardness and stress.

Thus, in order to realize above-mentioned glass transition temperature, the material of the hard segment constituting elastomeric material (hereinafter has Time be referred to as " hard segment materials ") glass transition temperature be preferably 30 DEG C～100 DEG C, more preferably 35 DEG C～60 DEG C, constitute The glass transition temperature of the material (hereinafter sometimes called " soft segment material ") of the soft chain segment of elastomeric material be preferably- 100 DEG C～-50 DEG C, more preferably-90 DEG C～-60 DEG C.

Additionally, have in the case of hard segment materials and the soft segment material of described glass transition temperature, firmly using The weight ratio (hereinafter sometimes referred to " hard segment materials ratio ") of the gross weight of segment material and hard segment materials and soft segment material Be preferably 46 weight %～96 weight %, more preferably 50 weight %～90 weight %, be even more preferably 60 weight %～ 85 weight %.

If hard segment materials ratio is more than 46 weight %, then ensure that the wearability of ground floor marginal end, and inhibit The generation of abrasion, thus, in some cases can the good clean-up performance of long term maintenance.If hard segment materials ratio is 96 weights Amount below %, then the marginal end of ground floor will not be really up to the mark, and obtains flexibility and extensibility, and and then inhibits broken Occur, therefore, it is possible to the clean-up performance that long term maintenance is good.

The combination of hard segment materials and soft segment material is not particularly limited, and material can be selected from conventionally known resinous wood Material is so that a kind of material is harder than another kind of material, but preferably following combination.

It is to say, as hard segment materials, polyurethane resin is preferably used.In this case, the weight of polyurethane resin Average molecular weight is preferably 1,000～4, and 000, more preferably 1,500～3,500.

It is 1 in weight average molecular weight, in the case of more than 000, owing to constituting the elastic reduction of the polyurethane resin of hard segment, Inhibit cleaning bad when using cleaning doctor at low ambient temperatures.On the other hand, in the feelings that weight average molecular weight is 4, less than 000 In condition, the permanent strain of the polyurethane resin constituting hard segment will not become too high, and the marginal end of ground floor is able to maintain that to be treated The contact pressure of cleaning member.Result, it is suppressed that clean bad.

Additionally, the example that will act as the polyurethane resin of hard segment materials includes by Daicel Chemical The PLACCEL 205 and PLACCEL 240 etc. that Industries, Ltd. manufacture.

It addition, the pressure that cleaning doctor applies is preferably set to 1.7gf/mm～6.5gf/mm, more preferably 2.0gf/mm ～6.0gf/mm.If pressure is more than lower limit, even if then using high rigidity scraper also to be able to suppress the cleaning of toner not Good, and if pressure is below higher limit, then will not be excessively serious with the friction of photoreceptor, therefore inhibit the increase of moment of torsion, sense The abrasion of body of light, the generation etc. of the ghost image caused because of the broken generation of the striped caused and the friction of photoreceptor of blade edge.

The example of transfer device 40 includes known transfer charger, such as, uses connecing of band, roller, film, rubber scraper etc. Touch transfer charger, and utilize the gate type corona tube transfer charger of corona discharge, corona tube transfer charger etc..

As intermediate transfer medium 50, use and be endowed the such as polyimides, polyamidoimide of semiconduction, poly-carbon The ribbons such as acid esters, polyarylate, polyester, rubber.It addition, in addition to the form of band, intermediate transfer medium 50 may also take on The form of drum.

In addition to above-mentioned device, image forming apparatus 100 may be fitted with such as carrying out photoreceptor 7 light-remove The optical discharge apparatus of electricity.

Fig. 5 is that the tandem type image of the handle box showing the Electrophtography photosensor using this illustrative embodiments is formed The schematic sectional view of the illustrative embodiments of equipment 120.

Fig. 5 is the figure (signal of the another exemplary embodiment of the image forming apparatus showing this illustrative embodiments Property sectional view).Image forming apparatus 120 is equipped with the tandem type full-colour image of four handle boxes 300 and forms equipment.At image In formation equipment 120, four handle boxes 300 configure on intermediate transfer device 50 in parallel with each other, an electronic photographic sensitive Body can be used for a kind of color.Additionally, image forming apparatus 120 is in addition to being tandem type, have and image forming apparatus 100 phase Same composition.

When the Electrophtography photosensor of this illustrative embodiments is used for tandem type image forming apparatus, four photosensitive The electrical property of body is stable, and this can be provided for a long term the high image quality with excellent color balance.

Additionally, in the image forming apparatus (handle box) of this illustrative embodiments, developing unit (developing cell) is excellent Choosing includes the developer roll keeping body as developing agent, and it is contrary with the direct of travel of Electrophtography photosensor (direction of rotation) (rotation) is moved in direction.Such as, developer roll has for developing agent is kept cylindric developing sleeve in its surface, and Developing unit also has the amount controlling parts in order to control to supply the developing agent to developing sleeve.Developer roll edge when developing unit The direction contrary with the direction of rotation of Electrophtography photosensor when moving (rotation), the surface of Electrophtography photosensor is developed The toner friction held between sleeve pipe and Electrophtography photosensor.

It addition, in the image forming apparatus (handle box) of this illustrative embodiments, prevent discharging product from sinking from for a long time From the viewpoint of Ji, between developing sleeve and photoreceptor, it is preferably spaced 200 μm～600 μm, more preferably 300 μm～500 μ m.Additionally, be preferably spaced 300 μm between developing sleeve and control scraper (for controlling the control parts of the amount of developing agent) ～1000 μm, more preferably 400 μm～750 μm.

Additionally, the absolute translational speed (processing speed) of developing roller surface is preferably the translational speed of photosensitive surface 1.5 times～2.5 times, more preferably 1.7 times～2.0 times.

It addition, in the image forming apparatus (handle box) of this illustrative embodiments, developing unit (developing cell) is wrapped Include the developing agent holding body with magnetisable material, and preferably develop with the two-component developing agent containing magnetic carrier and toner Electrostatic latent image.

[organic EL device]

It follows that description organic EL device.

The organic EL device of this illustrative embodiments have by use wherein be dissolved with by containing that formula (1) ' represents The film having the lysate of the charge transport material of mercapto and formed.

When as organic EL device or solaode, can so that single or multiple lift to use, and can be used for any In Ceng.

As an example of organic EL device, organic electroluminescent device will be described in detail with reference to the attached drawings.

Fig. 7～9 is the schematic cross-sectional of the embodiment of the organic electroluminescent device showing this illustrative embodiments Figure, wherein 21 represent substrate, and 22 represent anode, and 23 represent hole injection layer, and 24 represent hole transporting layer, and 25 represent luminescent layer, 26 represent electron supplying layer, and 27 represent negative electrode, but, the structure of element is not limited to this.

Substrate 21 is the support of organic electroluminescent device, and uses quartz, glass plate, metallic plate, metal forming, moulds Material film, sheet material etc..In particular it is preferred to the transparent conjunction such as glass plate or such as polyester, polymethacrylates, Merlon, polysulfones Resin substrate.

In the case of using synthetic resin board, should be noted that barrier properties for gases.To this end, wherein at synthetic resin substrate The method of the silicon dioxide film that one or both sides arrange densification is also one of method for optimizing.

Anode 22 is arranged on the base plate (21.Anode 22 plays the effect that hole is injected hole injection layer 23.This anode 22 leads to Often by metal-oxide, water, such as Hydro-Giene (Water Science). such as the oxides of the such as metal such as aluminum, gold, silver, nickel, palladium, platinum, indium and/or stannum Formed Deng metal halide or white carbon black etc..The formation of anode 22 is generally by sputtering method or vacuum deposition method etc. in many cases Formed.It addition, by the granule etc. of the granule of metallic particles, Hydro-Giene (Water Science). etc., white carbon black or the conductive metal oxides such as such as silver It is scattered in binder resin solution suitably, and is coated with on the base plate (21 to form anode 22.Anode 22 is also by other The lamination of material is formed.

The thickness of anode 22 is different according to the required transparency, but the generally the most higher transparency, therefore may be used See that the absorbance of light is typically more than 60%, preferably more than 80%, now thickness is typically 10nm～1000nm, preferably 20nm～500nm.

In the case of anode is opaque, such as, anode can be provided with metal deposition film etc. for such as from one The laser generation of end or the purpose that reflects between two electrodes, or substrate 21 can also be used in anode 22.It addition, other Conductive material can also be laminated on anode 22.

In the component structure of Fig. 7～9, illustrated, anode 22 is arranged Hole injection layer 23.

In this illustrative embodiments, the charge transport material containing mercapto represented by formula (1) ' by use And the layer formed is formed by vacuum deposition method or rubbing method, and in the case of solidification, preferably rubbing method.Such as, will retouch State the situation making this layer be formed as hole injection layer as an example.

In the charge transport material containing mercapto represented by formula (1) ' of scheduled volume, it may be necessary to add not As the adhesive resin of hole trap, coating modifying agent, chain polymerization monomer, oligomer etc..It is also preferred that use at end There is the charge transport material of alkoxysilyl, and for various purposes, other silane coupler, aluminum can be added occasionally Connection agent, titanate (ester) coupling agent etc..Preparation is wherein dissolved with the coating fluid of these compounds, by such as spin-coating method and dip-coating Coating solution on anode 22, and is dried to form hole injection layer 23 by methods etc..

The thickness of the hole injection layer 23 being consequently formed is typically 5nm～3000nm, preferably 10nm～2000nm.

Hole injection layer 23 arranges luminescent layer 25.In luminescent layer 25, from being provided with between electroluminescent electrode Negative electrode 27 injected electrons and be transferred from the hole of hole injection layer 23 with efficiently in conjunction with, and further by by tying again Close and effective luminescent material formation luminescent layer 25.The example of the material meeting this condition includes the aluminium complex of 8-hydroxyquinoline (Japanese Laid-Open Patent Publication 59-194393 publication), metal complex (Japanese Unexamined Patent Publication 6-322362 of 10-hydroxy benzo [h] quinoline Number publication), bis styryl benzene derivatives (Japanese Unexamined Patent Publication 1-245087 publication and Japanese Unexamined Patent Publication 2-222484 public affairs Report), bisstyryl arylene derivatives (Japanese Unexamined Patent Publication 2-247278 publication), the gold of (2-hydroxy phenyl) benzothiazole Belong to complex (Japanese Unexamined Patent Publication 8-315983 publication), thiophene coughs up derivant etc..

These light emitting layer materials are generally laminated on hole injection layer 23 by vacuum deposition method or rubbing method.Make In the case of rubbing method, the solvent of essentially insoluble solution hole injection layer 23 is preferably used, but this exemplary embodiment party In formula, it is in the case of three-dimensional cross-linked at priming coat, high to the toleration of solvent, therefore can select solvent from broad range.

For improving the luminous efficiency of element and changing the color of sent light simultaneously, make device with the aluminum of 8-hydroxyquinoline Complex as material of main part, and such as doped with the laser fluorescence dyestuffs such as such as coumarin (J.Appl.Phys., volume 65, Page 3610, (1989)).

Such as, material of main part can be the metal complexs such as the aluminium complex of such as 8-hydroxyquinoline, and based on this main body Naphthonaphthalene derivant (the Japanese Unexamined Patent Publication 4-335087 public affairs such as the such as rubrene of material doped 0.1 weight %～10 weight % Report), quinacridone derivative (Japanese Unexamined Patent Publication 5-70773 publication), the fused polycycle aromatic rings such as such as perylene (Japan Unexamined Patent 5-198377 publication).With fluorescent dyes such as naphthonaphthalene derivant, quinacridone derivative or such as perylenes The method of the material of main part of doping luminescent layer includes co-electrodeposition method and in advance with the method in predetermined concentration mixed deposit source.

As it has been described above, the example of polymerism emitting layer material includes the most poly-(supportting styrene), poly-[2-methoxyl group-5- The support of (2-ethyl hexyl oxy)-Isosorbide-5-Nitrae-styrene], the polymeric material such as poly-(3-alkylthrophene) and by make luminescent material and The polymer mixed such as electron transfer material and such as polyvinylcarbazole and the system that obtains.

Similar to hole injection layer 23, by the such as method such as spin-coating method and dip coating, these materials are coated on hole and note Enter to form thin film on layer, and using in the case of rubbing method, essentially insoluble solution hole injection layer 23 is preferably used Solvent, but in the exemplary embodiment, when priming coat is three-dimensional cross-linked, high to the toleration of solvent, therefore solvent Can extensively select.

The thickness of the luminescent layer 25 being consequently formed is 10nm～200nm, preferably 30nm～100nm.

When carrying out the operation of function divergence type, such as, as shown in Figure 8, hole transporting layer 24 is arranged on hole injection layer 23 He Between luminescent layer 25, or as it is shown in figure 9, electron supplying layer 26 is arranged between luminescent layer 25 and negative electrode 27.Fig. 8's and 9 In function divergence type element, as the material for hole transporting layer 24, preferably there is the high hole from hole injection layer 23 Injection efficiency and can effectively carry the material of institute's injected holes.The example of hole transporting material includes e.g. connecting Have 1, the aromatic diamine compound (Japanese Unexamined Patent Publication of the tertiary aromatic amine of double (4-bis--p-methylphenyl aminophenyl) hexamethylene of 1-etc. Clear 59-194393 publication), containing at least two tertiary amine have replacement have the nitrogen-atoms of at least two condensed aromatic ring also It is aromatic amine (the Japanese Unexamined Patent Publication 5-234681 public affairs of representative with 4,4 '-bis-[N-(1-naphthyl)-N-phenyl amino] biphenyl Report), for triphenylbenzene derivatives and have the aromatic triamine (U.S. Patent No. 4,923, No. 774) of star burst structure, such as N, N '-diphenyl-N, N '-bis-(3-aminomethyl phenyl) xenyl-4, the aromatic diamine (U.S. Patent No. 4,764,625 such as 4 '-diamidogen Number), as triphenylamine derivant (Japanese Unexamined Patent Publication 4-129271 publication) the most asymmetric for whole molecule, On pyrenyl, replacement has the compound (Japanese Unexamined Patent Publication 4-175395 publication) of multiple fragrance diaminourea, has by ethylidene even The aromatic diamine (Japanese Unexamined Patent Publication 4-264189 publication) of the tertiary aromatic amine unit connect, such as N, N '-diphenyl-N, N '- Double (3-aminomethyl phenyl) xenyl-4,4 '-diamidogen etc. replaces on pyrenyl the compound of multiple aromatic series diamino group, have The aromatic diamine (Japanese Unexamined Patent Publication 4-290851 publication) of cinnamenyl structure, be there is the virtue wherein connected by thienyl The fragrant aromatic diamine (Japanese Unexamined Patent Publication 4-304466 publication) of cinnamenyl structure of tertiary amine unit, star burst type aromatic series three Amine (Japanese Unexamined Patent Publication 4-308688 publication), benzyl phenyl compound (Japanese Unexamined Patent Publication 4-364153 publication), by passing through The compound (Japanese Unexamined Patent Publication 5-25473 publication) of tertiary amine composition of fluorenyl connection, triamine compound (Japanese Unexamined Patent Publication 5- No. 239455 publications), duplex pyridinylamino biphenyl (Japanese Unexamined Patent Publication 5-320634 publication), N, N, N-triphenylamine derive Thing (Japanese Unexamined Patent Publication 6-1972 publication), there is fenAromatic diamine (the Japanese Unexamined Patent Publication 7-138562 public affairs of piperazine structure Report), diamino-phenyl phenanthridine derivatives (Japanese Unexamined Patent Publication 7-252474 publication), silicon nitrogen silane compound (U.S. Patent No. 4, No. 950,950), dimethyl silyl dimethylamine (silanamine) derivant (Japanese Unexamined Patent Publication 6-49079 publication), phosphine amine derive Thing (Japanese Unexamined Patent Publication 6-25659 publication) etc..As required, these compounds can be used alone or mix with two or more Compound uses.In addition to above-mentioned compound, the example for the material of hole transporting layer 24 also include polyvinylcarbazole or Polysilane, polyphosphazene (Japanese Unexamined Patent Publication 5-310949 publication), polyamide (Japanese Unexamined Patent Publication 5-310949 publication), poly-second Thiazolinyl triphenylamine (Japanese Unexamined Patent Publication 7-53953 publication), there is polymer (Japanese Unexamined Patent Publication 4-of triphenylamine skeleton No. 133065 publications) and the polymeric material such as polymethacrylates containing aromatic amine.

Hole transporting material is pressed on hole injection layer 23 to form hole defeated by vapour deposition process or rubbing method Send layer 24.In the case of rubbing method, it may be necessary to the additives such as adhesive resin and such as coating modifying agent are added In one or more hole transporting material, dissolve to prepare coating fluid, be then coated with by methods such as such as spin-coating methods Cloth is on hole injection layer 23, and is dried to form hole transporting layer 24.Using in the case of rubbing method, be preferably used The solvent of essentially insoluble solution hole injection layer 23, but in this illustrative embodiments, be three-dimensional cross-linked at priming coat In situation, high to the toleration of solvent, therefore solvent can select from broad range.

Herein, the example of adhesive resin includes Merlon, polyarylate, polyester etc..Therefore, the interpolation of adhesive resin Amount is preferably generally below 50 weight %.

In using vacuum deposition method situation, hole transporting material is put into the crucible being arranged in Dewar vessel.With Dewar vessel is evacuated to about 10 by suitably pump^-4The pressure of Pa.Then crucible is heated, make hole transporting material evaporate, from And on the substrate 21 being oppositely arranged with crucible, forming hole transporting layer 24, described substrate 21 has anode 22 and is formed thereon Hole injection layer 23.The thickness of the hole transporting layer 24 being consequently formed is 10nm～300nm, preferably 30nm～100nm.

It is said that in general, generally use vacuum deposition method.

Additionally, the requirement to the compound for electron supplying layer 26 is that electronics easily injects from negative electrode 27, therefore have Higher electron transport ability.The example of electron transport materials is as above as described by luminescent material, including including 8-hydroxyl quinoline The aluminium complex of quinoline,Oxadiazole derivative (Appl.Phys.Lett., volume 55, page 1489,1989), it is scattered in and such as gathers System in the resins such as methyl methacrylate (PMMA), phenanthroline derivative (Japanese Unexamined Patent Publication 5-331459 publication), 2- The tert-butyl group-9,10-N, N '-dicyan anthraquinone diimine, n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, n-type zinc selenide etc..

The thickness of electron supplying layer 26 is typically 5nm～200nm, preferably 10nm～100nm.

27 functions that electronics is injected luminescent layer 25 of negative electrode.As the material as negative electrode 27, use for anode 22 Material.But, in order to effectively inject electronics, preferably there is the metal of less work content, it is possible to use suitable metal such as It is stannum, magnesium, indium, calcium, aluminum, silver etc. or its alloy.Its instantiation includes having such as magnesium silver alloy, magnesium indium alloy, aluminum lithium closes The electrode of the low work content alloys such as gold.

In the scope that the thickness of negative electrode 27 is generally mentioned when anode 22 as described above.

The purpose of negative electrode 27 formed by low work function metal for protection, effectively lamination have higher work content and Metal level stable in air.For this purpose it is proposed, use the metals such as such as aluminum, silver, copper, nickel, chromium, gold, platinum.Additionally, following methods Also it is effective: insert by LiF, MgF to the interface between luminescent layer 25 or electron supplying layer 26 and negative electrode 27₂Or Li₂O etc. The ultrathin insulating film (0.1nm～5nm) made (Appl.Phys.Lett., volume 70, page 152,1977；Japanese Unexamined Patent Publication 10-74586 publication；IEEE Trans.Electron.Devices, volume 44, page 1245,1997).

One example of the component structure used in Fig. 7～9 individually this illustrative embodiments, but this exemplary enforcement Mode is not limited to any one during these describe.It is, for example possible to use the structure contrary with Fig. 7, i.e. layer the most successively Pressure negative electrode 27, luminescent layer 25, hole injection layer 23 and anode 22, and as it has been described above, (one of them is the most saturating at two substrates Bright) between the organic electroluminescent device of this illustrative embodiments can be set.Additionally, use that shown in Fig. 8 and 9 A bit, each composition layer can also be laminated according to contrary structure.Formed and wherein seal with the such as material such as resin, metal And the sealant being protected from air or aqueous corrosion is also effective, or offer can make element, and this works in vacuum system Structure be also effective.

Embodiment

Hereinafter, embodiment and comparative example will be described, but the present invention will be not limited to following instance.Additionally, unless separately make Illustrating, following " part " is based on weight portion.

[embodiment I-1: the synthesis of compound (13)]

In 500ml flask, load 20g represented by following structural formula (A) compound, 15g 3-mercaptopropionic acid, 0.5g P-methyl benzenesulfonic acid and 200ml toluene, use nitrogen displaced air subsequently, then, with Dean Stark trap (Dean- Stark trap) remove generate water while be heated to reflux 10 hours.After reaction, residue wet chemical washing, It is purified by distilled water wash, recycle silicon glue column chromatography, is derived from the compound (13) that 23g is grease.

Figure 12 shows the IR spectrum of the compound (13) of gained.

[embodiment I-2: the synthesis of compound (29)]

In 500ml flask, load 20g represented by following structural formula (B) compound, 15g 3-mercaptopropionic acid, 0.5g P-methyl benzenesulfonic acid and 200ml toluene, use nitrogen displaced air subsequently, then, removing generation with Dean Stark trap 10 hours it are heated to reflux while water.After reaction, residue wet chemical washs, uses distilled water wash, recycle silicon glue Column chromatography is purified, and is derived from the compound (29) that 20g is grease.

Figure 13 shows the IR spectrum of the compound (29) of gained.

[embodiment I-3: the synthesis of compound (14)]

In 500ml flask, load compound, 15g 2 mercaptopropionic acid that 20g represents by structural formula (A), 0.5g is to first Benzenesulfonic acid and 200ml toluene, use nitrogen displaced air, subsequently then, at the water generated with Dean Stark trap removing It is heated to reflux 10 hours simultaneously.After reaction, residue wet chemical washs, uses distilled water wash, recycle silicon glue post color Spectrum is purified, and is derived from the compound (14) that 26g is grease.

Figure 14 shows the IR spectrum of the compound (14) of gained.

[embodiment I-4]

(preparation of priming coat)

By 100 parts of zinc oxide (mean diameter 70nm: manufactured by Tayca Corporation: specific surface area value is 15m²/ G) mixing with 500 parts of oxolane stirrings, (KBM503, by Shin-Etsu Chemical to be added to 1.3 parts of silane couplers Co., Ltd. manufactures), then stirring 2 hours.Then, toluene decompression is distilled out, bakees 3 hours at 120 DEG C, thus obtain use The zinc oxide that silane coupler is surface-treated.

By 110 parts of surface treated zinc oxide and 500 parts of oxolane stirring mixing, it is added to by by 1.0 parts Alizarin is dissolved in 50 parts of oxolanes the solution obtained, and then stirs 5 hours at 50 DEG C.Then, divided by filtration under diminished pressure From being added with the zinc oxide of alizarin, and at 60 DEG C of drying under reduced pressure, thus obtain the zinc oxide being added with alizarin.

By 38 parts by 60 parts being added with the zinc oxide of alizarin, 13.5 parts of firming agent (blocked isocyanate, Sumidur 3175, Sumitomo-Bayer Urethane Co., Ltd. manufacture) and 15 parts of butyral resins (S-LEC BM-1, by Sekisui Chemical Co., Ltd. manufactures) it is dissolved in 85 parts of methyl ethyl ketones the solution and 25 parts of methyl second prepared Base ketone mixes, and utilizes the sand mill of 1mm φ bead to carry out disperseing 2 hours to obtain dispersion liquid by use subsequently.

The tin dilaurate dioctyl tin of as catalyst 0.005 part and 45 parts of organosilicons are added in the dispersion liquid obtained Resin particle (Tospal 145 is manufactured by GE Toshiba Silicone Co., Ltd.) is to obtain coating liquid for undercoat layer. It is the aluminium base of 1mm on by this coating solution at a diameter of 30mm, a length of 340mm, thickness by dip coating, and 170 DEG C temperature dry solidification 40 minutes and obtain the priming coat that thickness is 18 μm.

(preparation of charge generation layer)

Use and utilize the sand mill of 1mm φ bead, using include 15 parts as charge generation substance in Cuk α X-ray X-ray diffraction spectrum at least at Bragg angle (2 θ ± 0.2 °) place for 7.3 °, 16.0 °, 24.9 ° and 28.0 °, there is diffraction The hydroxy gallium phthalocyanine at peak, (VMCH, by Nippon for 10 parts of vinyl chloride vinyl acetate copolymer resins as adhesive resin Unicar Co., Ltd. manufacture) and 200 parts of n-butyl acetates mixture dispersion 4 hours.Add in the dispersion liquid obtained 175 parts of n-butyl acetates and 180 parts of methyl ethyl ketones, then stir to obtain charge generation layer coating fluid.This electric charge is produced It is to priming coat and dry at room temperature (20 DEG C), to form the charge generation layer that thickness is 0.2 μm that generating layer is coated with dip-coating with coating fluid.

(preparation of charge transport layer)

By 40 parts of N, N '-diphenyl-N, N '-xenyl-4, bis-(3-aminomethyl phenyl)-[1,1 '], 4 '-diamidogen (TPD), 10 (PC (Z): viscosity-average molecular weight is for part double (3,4-3,5-dimethylphenyl) xenyl-4-amine of N, N-and 55 parts of bisphenol Z polycarbonate resins 60,000) it is dissolved in 800 parts of chlorobenzenes, to obtain charge transport layer coating fluid.By this coating solution at charge generation layer On, then the temperature at 130 DEG C is dried 45 minutes, to form the charge transport layer that thickness is 15 μm.

(preparation of surface layer)

By 10 parts of compounds (13), (A-TMPT, by Shinnakamura for 10 parts of trimethylolpropane trimethacrylates Chemical Co., Ltd. manufactures) and 0.2 part of OTazo-15 (by Otsuka Chemical Co., Ltd., manufacture, molecular weight It is 354.4) it is dissolved in 30 parts of cyclopentanol, then it is coated on charge transport layer by spraying.Make this coating in room temperature (20 DEG C) air-dry 30 minutes, under the nitrogen that oxygen concentration is 200ppm, the speed with 10 DEG C/min is heated to 150 DEG C by room temperature, heating Process 150 DEG C carry out 1 hour to solidify, be consequently formed the protective layer that thickness is 10 μm, thus prepare embodiment I-4 Electrophtography photosensor.

The Electrophtography photosensor that will be in accordance with the description above manufacture is arranged on what Fuji Xerox Co., Ltd manufactured On ApeosPort-III C4400, and it is carried out continuously at low temperature and low humidity (8 DEG C, 20%RH) and hot and humid (30 DEG C, 85%RH) Hereinafter evaluate.

First, under low temperature and low humidity environment (8 DEG C, 20%RH), to page 10000 common paper, (paper P, by Fuji-Xerox's strain formula meeting Society manufactures (A4 size, horizontal paper feeding)) carry out image formation test, and evaluate image quality (the following weight of page 10000 paper Shadow, atomization, striped and image deterioration).Evaluate the page 1 after placing 24 hours under low temperature and low humidity environment (8 DEG C, 20%RH) The image quality of paper.Result shows in Table I-2.

After image quality under have rated low temperature and low humidity environment, right under hot and humid environment (30 DEG C, 85%RH) Page 10000 paper carry out image and form test, and evaluate the image quality of page 10000 paper.Then, evaluate at hot and humid environment The image quality of the page 1 paper after placing 24 hours under (30 DEG C, 85%RH).Result shows in Table I-3.

(evaluation of ghost image)

As shown in Fig. 6 (A), print pattern and the chart of gray area that image color is 50% of letter G, pass through mesh The state that letter G occurs in the gray area of 50% is evaluated depending on observing.

A: degree is to slightly from good, as shown in Fig. 6 (A).

B: the most visible, as shown in Fig. 6 (B).

C: high-visible, as shown in Fig. 6 (C).

(evaluation of atomization)

Use the sample identical with ghost image evaluation, evaluated the degree of adhesion of toner and white portion by visualization.

A: good.

B: manifested slight atomization.

C: manifested the atomization that image quality is had execution.

(evaluation of striped)

Use the sample identical with ghost image evaluation, evaluate striped by visualization.

A: good.

B: manifested part striped.

C: manifested the striped that image quality is had execution.

(evaluation of image deterioration)

Using the sample identical with ghost image evaluation, visualization evaluation image deteriorates.

A: good.

B: problem does not occurs during continuous printing test, but sample is placed and has manifested figure after (24 hours) in one day Image degradation.

C: manifested image deterioration during printing test continuously.

Measure residual voltage potential by the following method, and evaluate the increment of residual voltage potential before and after printing test.Electromotive force is passed Sensor be arranged on Fuji Xerox Co., Ltd manufacture ApeosPort-III C4400 on, and measure low temperature and low humidity (8 DEG C, The residual voltage potential on the Electrophtography photosensor surface before printing test is carried out under 20%RH).It follows that at low temperature and low humidity (8 DEG C, 20%RH) under carry out page 10000 printing test after measure the electrofax under low temperature and low humidity (8 DEG C, 20%RH) immediately Residual voltage potential on photosensitive surface.The difference of the residual voltage potential after the residual voltage potential at initial stage and page 10000 printing tests (residual voltage potential at the residual voltage potential-initial stage after page 10000 printing tests) is considered as increment.

Photoreceptor after using cutting knife that image is formed test cuts into square for 2mm 5 × 5 piece, 3M glueds joint band and attaches On block and peeled off, and count the quantity of residual block, thus evaluate the adhesiveness of protective layer.

Result shows in Table I-2.

A: residual block is more than 21.

B: residual block is 11～20.

C: residual block is less than 10.

Eddy current determinator (FISCHERSCOPE MMS) is utilized to measure the photoreceptor thickness at initial stage and at low temperature and low humidity Complete image under (8 DEG C, 20%RH) environment and under hot and humid (30 DEG C, 85%RH) environment and form the thickness after test, and And evaluation abrasion loss.

[embodiment I-5]

Until the preparation process of charge transport layer by with embodiment I-4 describes identical in the way of carry out.

(preparation of surface layer)

By 10 parts of compounds (13), (A-TMPT, by Shin Nakamura for 10 parts of trimethylolpropane trimethacrylates Chemical Co., Ltd. manufacture) and 0.5 part of 1-hydroxycyclohexylphenylketone (Irgacure 184, by Ciba Specialty Chemicals Inc. manufactures) it is dissolved in 30 parts of cyclopentanol, then it is coated on charge transport layer by spraying.Coating is in room Temperature (20 DEG C) air-dries 30 minutes, then carries out light irradiation under the nitrogen that oxygen concentration is 200ppm, and condition is as follows: metal halide Lamp 160W/cm, irradiation distance 120mm, exposure rate 500mW/cm², irradiation time 60 seconds, thus solidify this coated film.Described Film 130 DEG C be further dried 20 minutes be the surface layer of 5 μm to form thickness, thus prepare the photoreceptor of embodiment I-5.Logical It is evaluated by the method described in embodiment I-4 of crossing.

[embodiment I-6]

(preparation of surface layer)

By 10 parts of compounds (13) and 10 parts of trimethylolpropane trimethacrylates, (A-TMPT, by Shin Nakamura Chemical Co., Ltd. manufactures) it is dissolved in 30 parts of cyclopentanol, then it is coated on charge transport layer by spraying.Coating Air-dry 30 minutes in room temperature (20 DEG C), then with the speed sense of rotation body of light of 300rpm under the nitrogen that oxygen concentration is 20ppm Carrying out electron beam irradiation, condition is as follows simultaneously: irradiation distance is 30mm, and beam voltage is 90kV, and electron beam current is 2mA, the electron beam irradiation time is 1.0 seconds.Heat in 150 DEG C under the nitrogen that oxygen concentration is 20ppm immediately after irradiation And keep these conditions to complete curing reaction while 10 minutes, to form the surface layer that thickness is 5 μm, thus prepare embodiment The photoreceptor of I-6.By the method described in embodiment I-4, it is evaluated.

[embodiment I-7～I-18]

In addition to the compound (13) in embodiment I-4 is become those compounds shown in Table I-1, with enforcement Identical method described in example I-4 prepares photoreceptor, and is evaluated it.

[Comparative Example I-1]

The thickness of the charge transport layer in embodiment I-4 is become 25 μm, and is formed without surface layer, be derived from comparing The photoreceptor of example 1, and by the method described in embodiment I-4, it is evaluated.

[Comparative Example I-2]

In addition to the compound (13) in embodiment I-4 is become the compound (C) with following structural formula, with reality The identical method described in example I-4 of executing prepares photoreceptor, and is evaluated it.

Table I-1

As shown in Table I-2 and I-3, use the Electrophtography photosensor of embodiment, it is suppressed that after being repeatedly used for a long The reduction of image quality.

[embodiment I-19]

Plasma cleaner (being manufactured by SAMCO International, Inc., BP1) is used to utilize oxygen plasma Washing is provided with the glass substrate 30 seconds of the ito film that thickness is 150nm.

Will by making 10 parts of compounds (13), (A-TMPT, by Shin for 5 parts of trimethylolpropane trimethacrylates Nakamura Chemical Co., Ltd. manufactures) and 0.2 part of OTazo-15 (by Otsuka Chemical Co., Ltd., make Making, molecular weight is 354.4) it is dissolved in 50 parts of chloromethanes the solution obtained with the rotating speed spin coating of 300rpm, then at oxygen concentration For under the nitrogen of 150ppm in 160 DEG C heating 1 hour to solidify, being consequently formed thick film is that 600nm is (by contact pilotage type thickness Sensing equipment measure) hole injection layer.

It follows that using as three (8-hydroxyquinoline) aluminum (Alq) vacuum moulding machine of luminescent layer material at hole injection layer Up to thickness is 50nm, and depositing magnesium/silver alloy negative electrode to thickness the most thereon is 200nm, to prepare organic EL device.

Using the ITO electrode of organic EL element as anode, magnesium-alloy silver electrode, as negative electrode, applies 7V unidirectional current, logical Cross following methods and determine electric current density.Meanwhile, brightness is measured by the following method.It addition, measure work by the following method Brightness after 1000 hours, result shows in Table I-4.

Additionally, use organic EL luminous efficiency determinator (being manufactured by Tokyo Instruments, Inc.) in regulation extremely Electric current density, voltage and brightness is measured under the measuring condition of 25 DEG C.

Additionally, when for display or laser, organic EL element needs high electric current to inject, thus electric current density and brightness Measure under the applying voltage of 7V, additionally after driving 1000 hours with the applying voltage of 7V, measure brightness.

[embodiment I-20～I-28]

In addition to compound (13) is become those compounds shown in Table I-4, with described in embodiment I-19 Identical method measure organic EL element, and it is evaluated.Result shows in Table I-4.

[Comparative Example I-3]

Except applying wherein vacuum moulding machine N, N '-diphenyl-N, N '-bis-(3-aminomethyl phenyl)-[1,1 '] xenyl-4, 4 '-diamidogen (TPD) replaces the hole using compound (13) to be formed in embodiment I-19 to note to the hole injection layer of 600nm thickness Enter outside layer, with embodiment I-19 described in identical method measure organic EL element, and it is evaluated.Result shows Show in Table I-4.

Table I-4

As shown in Table I-4, the organic EL element of embodiment obtain the characteristics of luminescence for a long time with stability.

Method for preparing each layer in photoreceptor is described subsequently.

(preparation of priming coat)

[priming coat 1]

By 100 parts of zinc oxide (mean diameter 70nm: manufactured by Tayca Corporation: specific surface area 15m²/ g) with 500 parts of oxolane stirring mixing, (KBM503, by Shin-Etsu Chemical to be added to 1.3 parts of silane couplers Co., Ltd. manufactures), then stirring 2 hours.Then, toluene decompression is distilled out, bakees 3 hours at 120 DEG C, thus obtain use The zinc oxide that silane coupler is surface-treated.

The tin dilaurate dioctyl tin of as catalyst 0.005 part and 45 parts of organosilicons are added in the dispersion liquid obtained Resin particle (Tospal 145 is manufactured by GE Toshiba Silicone Co., Ltd.) is to obtain coating liquid for undercoat layer. It is the aluminium base of 1mm on by this coating solution at a diameter of 30mm, a length of 340mm, thickness by dip coating, and 170 DEG C temperature dry solidification 40 minutes and obtain the priming coat that thickness is 18 μm.The rough surface of the outer surface of the priming coat formed Degree (center line average roughness) Ra is 0.3 μm.

[priming coat 2]

Except without 45 parts of silicone resin particles (Tospal 145, by GE Toshiba Silicone Co., Ltd. manufacture) outward, with priming coat 1 described in identical method form priming coat 2.The table of the outer surface of the priming coat formed Surface roughness (center line average roughness) Ra is 0.1 μm.

[priming coat 3]

Will (trade name: Organotex ZC540, by Matsumoto Fine Chemical by 10 parts of organic zirconates Co., Ltd. manufactures), 2 parts of silane couplers (trade name: A1110 is manufactured by Nippon Unicar Co., Ltd.), 30 parts different The coating fluid that propanol and 30 parts of n-butyl alcohol are formed is coated on a diameter of 30mm by dip coating, a length of 340mm, thickness are On the aluminium base of 1mm, and 150 DEG C of dry solidifications 5 minutes to form the priming coat that thickness is 0.1 μm.The priming coat formed Surface roughness (center line average roughness) Ra of outer surface is 0.05 μm.

(preparation of charge generation layer)

[charge generation layer 1]

Use and utilize the sand mill of 1mm φ bead, using include 15 parts as charge generation substance in Cuk α X-ray X-ray diffraction spectrum at least at Bragg angle (2 θ+0.2 °) place for 7.3 °, 16.0 °, 24.9 ° and 28.0 °, there is diffraction maximum Hydroxy gallium phthalocyanine, (VMCH, by Nippon for 10 parts of vinyl chloride vinyl acetate copolymer resins as adhesive resin Unicar Co., Ltd. manufacture) and 200 parts of n-butyl acetates mixture dispersion 4 hours.Add in the dispersion liquid obtained 175 parts of n-butyl acetates and 180 parts of methyl ethyl ketones, then stir to obtain charge generation layer coating fluid.This electric charge is produced Generating layer with coating fluid dip-coating to priming coat, and 100 DEG C be dried 5 minutes, to form the charge generation layer that thickness is 0.2 μm.

[charge generation layer 2]

By 45g, through the embedding anthraquinone pigment of dibromoanthracene of sublimation purification, (CG-25, is manufactured by Clariant GmbH, the organic face of N-shaped Material) load in the container being made up of Achates that capacity is 0.25L together with the agate ball of 12 20-mm φ, and with planetary Ball mill (Fritsch P-5) is ground.In the rotary speed (revolution) that disc rotary speed (revolution) is 235rpm and tank For being ground under the grinding condition of 50rpm 8 hours.By 10 parts of embedding anthraquinone pigments of dibromoanthracene, 5 parts of Chlorovinyl-acetate vinyl Copolymer resin (VMCH is manufactured by Nippon Unicar Co., Ltd.) mixes with 100 parts of Ketohexamethylene, and use utilizes 1-mm The sand mill of φ bead disperses 4 hours.300 parts of Ketohexamethylene are added to the dispersion liquid obtained, is stirred subsequently, to obtain Obtain charge generation layer coating fluid.By the coating fluid dip-coating to priming coat of this charge generation layer, it is dried 5 minutes with shape at 100 DEG C The charge generation layer becoming thickness to be 0.5 μm.

[charge generation layer 3]

By Varian Model 3117 type vacuum coater by the dibromoanthracene embedding anthraquinone pigment (CG-through sublimation purification 25, Clariant GmbH manufacture, N-shaped organic pigment) it is deposited into the film that thickness is 0.1 μm, to form electric charge on priming coat Produce layer.Additionally, with 350 DEG C of heating CG-25 in tantalum boat, and the pressure of vacuum coater is made to be down to 10^-3Pas.It addition, by base Plate is placed on the position away from boat 16cm, and so that optical exciting layer is adhered to the speed of 6 angstroms per second.

[charge generation layer 4]

Bisbenzimidazole perylene pigment (CG-19, by Fuji Xerox Co., Ltd, manufactures, N-shaped organic pigment) is entered Row sublimation purification.Use planetary ball mill (use 44 20mm φ agate balls, and 3 25-mm φ agate balls, Achates tank Internal diameter is 10mm φ) grind bisbenzimidazole perylene pigment after 10g sublimation purification 27 hours.Micronized two obtained Benzimidazole perylene pigment shows strong peak, and particle diameter at 6.2 °, 12.3 ° and 27.0 ° in X-ray diffraction spectra It is 0.04 μ m 0.08 μm～0.05 μ m 0.1 μm.By 10 parts of bisbenzimidazole perylene pigments, 5 parts of vinyl chloride-acetic acid second Enoate copolymer resin (VMCH is manufactured by Nippon Unicar Co., Ltd.) mixes with 100 parts of Ketohexamethylene, and use utilizes 1- The sand mill of mm φ bead disperses 4 hours.300 parts of Ketohexamethylene are added to the dispersion liquid obtained, is stirred subsequently, with Obtain charge generation layer coating fluid.By the coating fluid dip-coating to priming coat of this charge generation layer, 100 DEG C be dried 5 minutes with Form the charge generation layer that thickness is 0.5 μm.

[charge generation layer 5]

By Varian Model 3117 type vacuum coater by the bisbenzimidazole perylene pigment through sublimation purification (CG-19, by Fuji Xerox Co., Ltd, manufactures, N-shaped organic pigment) is deposited into the film that thickness is 0.1 μm, with on priming coat Form charge generation layer.Additionally, with 350 DEG C of heating CG-19 in tantalum boat, and the pressure of vacuum coater is made to be down to 10^-3Pas。 It addition, place a substrate in the position away from boat 16cm, and so that optical exciting layer is adhered to the speed of 4 angstroms per second.

[charge generation layer 6]

Make 10 parts of disazo pigments (CG-4 by Fuji Xerox Co., Ltd, manufactures, N-shaped organic pigment), 5 parts of vinyl chloride- Vinyl acetate copolymer resin (VMCH is manufactured by Nippon Unicar Co., Ltd.) mixes with 100 parts of Ketohexamethylene, use The sand mill utilizing 1-mm φ bead disperses 4 hours.300 parts of Ketohexamethylene are added to the dispersion liquid obtained, carries out subsequently Stirring, to obtain charge generation layer coating fluid.By the coating fluid dip-coating to priming coat of this charge generation layer, it is dried 5 at 100 DEG C Minute it is the charge generation layer of 0.5 μm to form thickness.

[charge generation layer 7]

Make 10 parts of disazo pigments (CG-8 by Fuji Xerox Co., Ltd, manufactures, N-shaped organic pigment), 5 parts of vinyl chloride- Vinyl acetate copolymer resin (VMCH is manufactured by Nippon Unicar Co., Ltd.) mixes with 100 parts of Ketohexamethylene, use The sand mill utilizing 1-mm φ bead disperses 4 hours.300 parts of Ketohexamethylene are added to the dispersion liquid obtained, carries out subsequently Stirring, to obtain charge generation layer coating fluid.By the coating fluid dip-coating to priming coat of this charge generation layer, it is dried 5 at 100 DEG C Minute it is the charge generation layer of 0.5 μm to form thickness.

[charge generation layer 8]

Make 10 parts of disazo pigments (CG-11, by Fuji Xerox Co., Ltd, manufactures, N-shaped organic pigment), 5 parts of chloroethenes Alkene-vinyl acetate copolymer resin (VMCH is manufactured by Nippon Unicar Co., Ltd.) mixes with 100 parts of Ketohexamethylene, The sand mill utilizing 1-mm φ bead is used to disperse 4 hours.300 parts of Ketohexamethylene are added to the dispersion liquid obtained, subsequently It is stirred, to obtain charge generation layer coating fluid.By the coating fluid dip-coating to priming coat of this charge generation layer, at 100 DEG C It is dried 5 minutes to form the charge generation layer that thickness is 0.5 μm.

(preparation of charge transport layer)

[charge transport layer 1]

By 40 parts of N, N '-diphenyl-N, N '-xenyl-4, bis-(3-aminomethyl phenyl)-[1,1 '], 4 '-diamidogen (TPD), 10 (PC (Z): viscosity-average molecular weight is for part double (3,4-3,5-dimethylphenyl) xenyl-4-amine of N, N-and 55 parts of bisphenol Z polycarbonate resins 60,000) add to 800 parts of chlorobenzenes and dissolve wherein, to obtain charge transport layer coating fluid.By this coating solution On charge generation layer, then it is dried 45 minutes at 130 DEG C, to form the charge transport layer that thickness is 15 μm.

[charge transport layer 2]

Except by N, N '-diphenyl-N, N '-xenyl-4, bis-(3-aminomethyl phenyl)-[1,1 '], the amount of 4 '-diamidogen (TPD) It is set to 25 parts, and outside the amount of the charge transport material of following structural formula (C) is set to 20 parts, to describe with charge transport layer 1 Identical method form charge transport layer 2.

(preparation of surface layer)

[curing: heat cure]

By 10 parts of compounds (13) (containing the charge transport material of mercapto), 12 parts of trimethylolpropane trimethacrylates (A-TMPT is manufactured by Shinnakamura Chemical Co., Ltd., has the compound of unsaturated bond) and 0.2 part OTazo-15 (by Otsuka Chemical Co., Ltd., manufacturing, molecular weight is 354.4, polymerization initiator) is dissolved in 30 parts In cyclopentanol, then it is coated on charge transport layer by spraying.Coating layer air-dries 30 minutes in room temperature (20 DEG C), at oxygen concentration It is heated to 150 DEG C for speed with 10 DEG C/min under the nitrogen of 200ppm by room temperature (20 DEG C), then heats at 150 DEG C Process 1 hour to solidify, be consequently formed the protective layer that thickness is 5 μm.

It addition, in the case of heat cure, type and the ratio of material are become the numerical value shown in Table II-1～II-5, Solidify the most under these conditions.

[curing: photocuring]

By 10 parts of compounds (13) (containing the charge transport material of mercapto), 12 parts of trimethylolpropane trimethacrylates (A-TMPT is manufactured by Shinnakamura Chemical Co., Ltd., has the compound of unsaturated bond) and 0.5 part of 1-hydroxyl Butylcyclohexyl phenyl ketone (Irgacure 184 is manufactured by Ciba Specialty Chemicals Inc., polymerization initiator) is molten Solution, in 30 parts of cyclopentanol, is then coated on charge transport layer by spraying.Coating room temperature (20 DEG C) air-dry 30 minutes, so After under the nitrogen that oxygen concentration is 200ppm, carry out light irradiation, condition is as follows: metal halide lamp 160W/cm, irradiation distance 120mm, exposure rate 500mW/cm², irradiation time 60 seconds, thus solidify this coated film.Described film is further dried at 130 DEG C 20 minutes to form the surface layer that thickness is 5 μm.It addition, in the case of photocuring, type and the ratio of material are become table Numerical value shown in II-1, solidifies the most under these conditions.

[curing: electronic beam curing]

By 10 parts of compounds (13) (containing the charge transport material of mercapto) and 12 parts of trimethylolpropane tris acrylic acid Ester (A-TMPT is manufactured by Shinnakamura Chemical Co., Ltd., has the compound of unsaturated bond) is dissolved in 30 In part cyclopentanol, then it is coated on charge transport layer by Tsukiage rubbing method.Coating layer air-dries 30 in room temperature (20 DEG C) Minute, then under the nitrogen that oxygen concentration is 20ppm, while the speed sense of rotation body of light of 300rpm, carry out electron beam irradiation, Condition is as follows: irradiation distance is 30mm, and beam voltage is 90kV, and electron beam current is 2mA, and the electron beam irradiation time is 1.0 the second.I.e. it is engraved in after irradiation under the nitrogen that oxygen concentration is 20ppm and carries out heating and keep these conditions 10 minutes in 150 DEG C While complete curing reaction, to form the surface layer that thickness is 5 μm.

It addition, in the case of electronic beam curing, type and the ratio of material are become shown in Table II-1 and II-2 Numerical value, solidifies the most under these conditions.

[preparation of photoreceptor 1～35]

By the priming coat, charge generation layer and the charge transport layer that are suitable for described in use Table II-1 and II-2, go forward side by side One step uses surface layer formation material described in Table I-1 and II-2 (charge transport material containing mercapto, to have insatiable hunger Compound, additive and polymerization initiator with key) kind and ratio and the curing of surface layer, prepare photoreceptor 1 ～35.

[preparation of photoreceptor 36～57]

By using the priming coat being suitable for described in Table II-3 and charge generation layer, and it is formed without charge transport layer, and The surface layer formation material described in Table II-3 is used (charge transport material containing mercapto, to have unsaturation further The compound of key, additive and polymerization initiator) kind and ratio and the curing of surface layer, prepare photoreceptor 36～ 57。

Additionally, the thickness of surface layer is 18 μm.

[comparing with the preparation of photoreceptor 1～13]

By the priming coat, charge generation layer and the charge transport layer that are suitable for described in use Table II-4, and make further Kind with the surface layer formation material (there is the compound of unsaturated bond, additive and polymerization initiator) described in Table II-4 Class and ratio and the curing of surface layer, preparation is compared with photoreceptor 1～13.

[comparing with the preparation of photoreceptor 14～26]

By using the priming coat being suitable for described in Table II-5 and charge generation layer, and it is formed without charge transport layer, and The surface layer formation material described in Table II-5 is used (to have the compound of unsaturated bond, additive and polymerization to draw further Send out agent) kind and ratio and the curing of surface layer, preparation is compared with photoreceptor 14～26.

Additionally, in above table, abridge as follows:

A-TMPT: trimethylolpropane tris propionic ester, is manufactured by Shin Nakamura Chemical Co., Ltd

OTazo-15: by Otsuka Chemical Co., Ltd., manufactures, and molecular weight is 354.4

Irgacure 184:1-hydroxycyclohexylphenylketone, is manufactured by Ciba Specialty Chemicals Inc.

PTFE:Lubron L2, is manufactured by Daikin Industries Ltd.

The Electrophtography photosensor that will be in accordance with the description above manufacture is arranged on what Fuji Xerox Co., Ltd manufactured ApeosPort-III C4400 (initial exposure device emission wavelength: the iraser of 780nm, exposure spot: 65 μ m 55 μ M, area: 3600 μm²(it is defined as the 1/e of corresponding peak value²Width)) on transformation apparatus, then at low temperature and low humidity (8 DEG C, 20%RH) It is carried out continuously following evaluation with under hot and humid (30 DEG C, 85%RH).

[evaluating apparatus-1]

Not changing exposure device, using mean diameter is that the toner of 3.8 μm is as developing agent.

[evaluating apparatus-2]

The LED image rod using emission wavelength to be 780nm and area are 30 μ m 50 μm, and 1500 μm²(it is right to be defined as Answer the 1/e of peak value²Width)), regulate exposure device according to the resolution of image, thus prepare drive circuit.As development Agent, the toner using mean diameter to be 3.8 μm.

[evaluating apparatus-3]

The organic EL image rod, the exposure spot that use emission wavelength to be 580nm are 20 μ m 20 μm, area: 400 μm²(fixed Justice is the 1/e of corresponding peak value²Width)), regulate exposure device according to the resolution of image, thus prepare drive circuit.Make For developing agent, the toner using mean diameter to be 3.8 μm.

The following preparation of organic EL image rod.As shown in Figure 10, ITO is made on it as being formed on the glass substrate of substrate (indium tin oxide) wide with 20 μm and 20 μm pitch pattern and the anode that patterns.It follows that will be as hole by spin-coating method It is 10nm that the PEDOT/PSS (polyethylene dioxythiophene/polystyrene Sulfonate) of implanted layer is applied to thickness.It addition, pass through spin-coating method By by making MEH-PPV be dissolved in the coating solution obtained in monochlorobenzene on luminescent layer with 1 weight %, preparing thickness it is The film of 80nm.Finally, the mask using A/F to be 20 μm, it is sequentially depositing the Ca as negative electrode and the Al as reflecting layer, Thus it is vertical with exposure light source anode.Thus form the organic EL of multiple exposure along main scanning direction X configuration first Part.Preparation at glass substrate (enforcement substrate) has a side of light-emitting device array, SLA and glass substrate (enforcement substrate) every Open, and realized by SLA holding member, so that between organic electroluminescent device (luminescence unit) and the light entrance face of SLA Optical distance is the operating distance of image unit.

Thus, the record being prepared in photoreceptor is write the size of hot spot and is 20 μm and exposure center wavelength is the exposure of 580nm Head.

[embodiment II-1]

Use photoreceptor-1 and evaluating apparatus-1, carry out following printing test.

First, the image carrying out page 10000 paper under low temperature and low humidity (8 DEG C, 20%RH) environment forms test, and evaluates the The image quality of page 10000 paper (following ghost image, atomization, to the attachment of photosensitive surface and image deterioration).Then, evaluate The image quality of the page 1 paper after placing 24 hours under low temperature and low humidity (8 DEG C, 20%RH) environment.

Result shows in Table II-6～II-8.

After image quality under have rated low temperature and low humidity environment, enter under hot and humid environment (30 DEG C, 85%RH) The image of row page 10000 paper forms test, and evaluates the image quality of page 10000 paper.Then, evaluate at hot and humid environment The image quality of the page 1 paper after placing 24 hours under (30 DEG C, 85%RH).

Result shows in Table II-9～II-11.

(evaluation of ghost image)

As shown in FIG, pattern and the chart of gray area that image color is 50% of letter G is printed, by visually Observe and evaluate the state that letter G occurs in the gray area of 50%.

A: degree is from well to slightly, as shown in Figure 6A.

B: the most visible, as shown in Figure 6B.

C: high-visible, as shown in Figure 6 C.

(evaluation of atomization)

A: good.

B: manifested slight atomization.

C: manifested the atomization that image quality is had execution.

(evaluation to the attachment of photosensitive surface)

Use the sample identical with ghost image evaluation, by the visualization evaluation attachment to photosensitive surface.

A: good.

B: show part striped on image, can repair with the surface of the cloth wiping photoreceptor gently being impregnated with isopropanol Multiple.

C: manifested the striped that image quality is had execution, the most i.e. used and be impregnated with the cloth of isopropanol gently The surface of wiping photoreceptor also cannot be repaired.

(evaluation of image deterioration)

Use the sample identical with ghost image evaluation, deteriorated by visualization evaluation image.

A: good.

B: problem does not occurs when continuous printing test, but sample is placed and observes that image is bad after (24 hours) in one day Change.

C: show image deterioration during printing test continuously.

Measure development potential by the following method, and it is evaluated.

Pull down the developing cell of ApeosPort-III C4400, and electrometer is installed wherein.Then, by low temperature and low humidity The development potential at the initial stage of the printing test under (8 DEG C, 20%RH) is set as 250V.Afterwards, low temperature and low humidity (8 DEG C, 20% RH), after and completing printing test under hot and humid (30 DEG C, 85%RH), again pull down developing cell, and install wherein Electrometer.Then, the development potential under low temperature and low humidity (8 DEG C, 20%RH) is measured.

Result shows in Table II-6～II-8.

A: residual block is more than 21.

B: residual block is 11～20.

C: residual block is less than 10.

Eddy current determinator (Fischerscope MMS) is utilized to measure the thickness of photoreceptor at initial stage and low at low temperature Complete image under wet (8 DEG C, 20%RH) environment and under hot and humid (30 DEG C, 85%RH) environment and form the thickness after test, Thus evaluate abrasion loss.

[embodiment II-2～II-59]

Use the photoreceptor described in Table II-6～II-8 and the combination of evaluating apparatus, with the side identical with embodiment II-1 Method is evaluated.Result shows in Table II-6～II-11.

Particularly, those of in-service evaluation device-3, spot size is the least, it is thus achieved that the finest image quality.Separately Outward, owing to the control for interference fringe is optional, even if therefore relatively thin being not easy to of photosensitive layer is atomized, and can The image that long-term acquisition is stable.

[Comparative Example I I-1～II-26]

Use the comparison photoreceptor described in Table II-12 and II-13 and the combination of evaluating apparatus, with embodiment II-1 Identical method is evaluated.Result shows in Table II-12～II-15.

[reference example II-1 and II-2]

Use photoreceptor 7 and photoreceptor 9 and the combination of evaluating apparatus 1, comment with the method identical with embodiment II-1 Valency.Result shows in Table II-16 and II-17.Additionally, in addition to the assessment item of display in Table II-16 and II-17, also Observe the generation of interference fringe.

As shown in above table, use the Electrophtography photosensor of embodiment, it is suppressed that the image after being repeatedly used for a long The reduction of quality.

The purpose illustrating that and describing described above to exemplary embodiment of the invention is provided.It is not intended to poor Use up the most presently disclosed precise forms or limit the invention to disclosed precise forms.Obviously, many improvement and change Will be readily apparent to one having ordinary skill.Select and describe described embodiment to be able to explain best this Bright principle and practical use thereof, so that others skilled in the art are it will be appreciated that be applicable to the special-purpose estimated The various embodiments of the present invention and various improvement project.The scope of the present invention is limited by the claims below and equivalent thereof Fixed.

Claims

1. the charge transport material containing mercapto represented by below general formula (1):

F-[(G)_a1-(X)_a2-Y-SH]_b (1)

Wherein, F represents the organic group from charge-transporting compound, and G represents that the bivalence with 1～5 carbon atom is organic Group, X represents that Y represents have the two of 1～5 carbon atom selected from-CO-O-group ,-O-CO-group and the group of-O-group Valency organic group, a1 and a2 represents 0 or 1 independently of one another, and b represents 1,

Wherein, described formula (1) charge transport material containing mercapto represented is represented by below general formula (1) ':

F-[(G)_a-X-Y-SH]_b (1)'

Wherein, F represents the organic group from charge-transporting compound, and G represents that the bivalence with 1～5 carbon atom is organic Group, X represents-CO-O-group or-O-CO-group, and Y represents the divalent organic group with 1～5 carbon atom, a represent 0 or 1, and b represents 1.

2. the charge transport material containing mercapto as claimed in claim 1, wherein, in described formula (1), F is to have The organic group of hole transporting ability.

3. the charge transport material containing mercapto as claimed in claim 1, wherein, by containing that described formula (1) represents The charge transport material of mercapto is represented by below general formula (2):

Wherein, D represents by-(G)_a1-(X)_a2The conjugated group that-Y-SH represents, Ar¹～Ar⁴Represent that there is replacement independently of one another Base or not there is the aryl of substituent group, Ar⁵Represent have substituent group or do not have substituent group aryl or have substituent group or Not having the arlydene of substituent group, G represents the divalent organic group with 1～5 carbon atom, and X represents selected from-CO-O-group With the group of-O-CO-group, Y represents the divalent organic group with 1～5 carbon atom, and a1 represents 0 or 1, and a2 represents 1；Ar¹ ～Ar⁵In one to four have can with by-(G)_a1-(X)_a2The key that the conjugated group that-Y-SH represents combines, c1～c5 is each From representing the integer of 0 or 1 independently, and the summation of c1～c5 is 1；And k represents 0 or 1.

4. the charge transport material containing mercapto as claimed in claim 1, wherein, by containing that described formula (1) ' represents The charge transport material of mercapto is represented by below general formula (2) ':

Wherein, D represents by-(G)_aThe conjugated group that-X-Y-SH represents, Ar¹～Ar⁴Independently of one another represent have substituent group or Not there is the aryl of substituent group, Ar⁵Represent and there is substituent group or not there is the aryl of substituent group or there is substituent group or do not have The arlydene of substituted base, G represents the divalent organic group with 1～5 carbon atom, and X represents-CO-O-group or-O-CO- Group, Y represents the divalent organic group with 1～5 carbon atom, and a represents 0 or 1；Ar¹～Ar⁵In one have to four Can with by-(G)_aThe key that the conjugated group that-X-Y-SH represents combines, c1～c5 represents the integer of 0 or 1 independently of one another, and And the summation of c1～c5 is 1；And k represents 0 or 1.

5. the charge transport material lysate containing mercapto, by containing that below general formula (1) represents in this lysate The charge transport material of mercapto dissolves in a solvent:

F-[(G)_a1-(X)_a2-Y-SH]_b (1)

Wherein: the charge transport material containing mercapto represented by described formula (1) is represented by below general formula (1) ':

F-[(G)_a-X-Y-SH]_b (1)'

6. a photoelectric conversion device, described device includes wherein being dissolved with by containing that below general formula (1) represents by use The lysate of the charge transport material of mercapto and the film that formed:

F-[(G)_a1-(X)_a2-Y-SH]_b (1)

Wherein, described formula (1) charge transport material containing mercapto represented is the material represented by below general formula (1) ' Material:

F-[(G)_a-X-Y-SH]_b (1)'

7. photoelectric conversion device as claimed in claim 6, wherein, described film contain wherein be polymerized described containing mercapto The polymer of charge transport material.

8. an Electrophtography photosensor, described photoreceptor is included on conductive base to use and is wherein dissolved with by below general formula (1) lysate of the charge transport material containing mercapto represented and the layer that formed:

F-[(G)_a1-(X)_a2-Y-SH]_b (1)

F-[(G)_a-X-Y-SH]_b (1)'

9. an Electrophtography photosensor, described Electrophtography photosensor has conductive base and is positioned at described conductive base On photosensitive layer, described photosensitive layer contains by being polymerized at least one electric charge containing mercapto represented by below general formula (I) Conveying material and at least one polymer that there is the compound of unsaturated bond and formed:

F-[(G)_a1-(X)_a2-Y-SH]_b (I)

Wherein, F represents the organic group from charge-transporting compound, and G represents that the bivalence with 1～5 carbon atom is organic Group, X represents that Y represents the divalent organic group with 1～5 carbon atom selected from-CO-O-,-O-CO-and the group of-O-, its Can have-SH group alternatively base, a1 and a2 represents 0 or 1 independently of one another, and b represents 1,

Wherein, described logical formula (I) the charge transport material containing mercapto represented is represented by below general formula (1) ':

F-[(G)_a-X-Y-SH]_b (1)'

10. Electrophtography photosensor as claimed in claim 9, wherein, in described logical formula (I), F is to have cavity conveying energy The organic group of power.

11. Electrophtography photosensors as claimed in claim 9, wherein, described logical formula (I) the electricity containing mercapto represented Lotus conveying material is the charge transport material containing mercapto represented by below general formula (II):

Wherein, D represents by-(G)_a1-(X)_a2The conjugated group that-Y-SH represents, Ar¹～Ar⁴Represent that there is replacement independently of one another Base or not there is the aryl of substituent group, Ar⁵Represent have substituent group or do not have substituent group aryl or have substituent group or Not having the arlydene of substituent group, G represents the divalent organic group with 1～5 carbon atom, and X represents selected from-CO-O-and-O- The group of CO-, Y represents the divalent organic group with 1～5 carbon atom, and it can have-SH group alternatively base, a1 Representing 0 or 1, a2 represents 1；Ar¹～Ar⁵In one to four have can with by-(G)_a1-(X)_a2The combination that-Y-SH represents The key that group combines, c1～c5 represents the integer of 0 or 1 independently of one another, and the summation of c1～c5 is 1；And k represent 0 or 1。

12. Electrophtography photosensors as according to any one of claim 9～11, wherein, described in there is the change of unsaturated bond Compound is to have the monomer of charge-transporting skeleton, oligomer or polymer.

13. Electrophtography photosensors as according to any one of claim 9～11, wherein, described in there is the change of unsaturated bond Compound is to have two or more unsaturated bond in same molecule and do not have the monomer of charge-transporting skeleton, oligomer Or polymer.

14. Electrophtography photosensors as according to any one of claim 9～11, wherein, described photosensitive layer contains lubricant Granule.

15. 1 kinds of image forming apparatus, described image forming apparatus includes:

Electrophtography photosensor, described Electrophtography photosensor has the photosensitive layer being positioned on conductive base, described photosensitive layer Containing by be polymerized at least one charge transport material containing mercapto represented by below general formula (I) and at least one have The compound of unsaturated bond and the polymer that formed；

Charging device, is charged in the surface of described Electrophtography photosensor by described charging device；

Exposure device, described exposure device makes the surface of charged described Electrophtography photosensor expose with on said surface Form electrostatic latent image；

Developing unit, described developing unit makes described latent electrostatic image developing to form toner image；With

Transfer device, described toner image is transferred to offset medium by described transfer device:

F-[(G)_a1-(X)_a2-Y-SH]_b (I)

F-[(G)_a-X-Y-SH]_b (1)'

16. 1 kinds of handle boxes including Electrophtography photosensor,

Wherein, described Electrophtography photosensor includes the photosensitive layer being positioned on conductive base, and described photosensitive layer contains by poly- Close at least one charge transport material containing mercapto represented by below general formula (I) and at least one has unsaturated bond Compound and the polymer that formed, and

Wherein, described handle box can be dismantled from image forming apparatus:

F-[(G)_a1-(X)_a2-Y-SH]_b (I)

F-[(G)_a-X-Y-SH]_b (1)'