CN102163015B

CN102163015B - Electrophotographic photoreceptor, process cartridge, image forming apparatus, cured film, and organic electroluminescent device

Info

Publication number: CN102163015B
Application number: CN2010102885942A
Authority: CN
Inventors: 山田涉; 额田克己; 土井孝次; 宫本刚; 园部健矢
Original assignee: Fuji Xerox Co Ltd
Current assignee: Fujifilm Business Innovation Corp
Priority date: 2010-02-23
Filing date: 2010-09-15
Publication date: 2013-12-04
Anticipated expiration: 2030-09-15
Also published as: CN102163015A

Abstract

The invention relates to an electrophotographic photoreceptor, a process cartridge, an image forming apparatus, a cured film, and an organic electroluminescent device. An electrophotographic photoreceptor is disclosed, in which an outermost surface layer of the electrophotographic photoreceptor is made of a cured film of a composition including a compound represented by the following Formula (M1) and a charge transporting material having a chain polymerizable functional group.

Description

Electrophtography photosensor, handle box, image processing system, cured film and organic electroluminescent device

Technical field

The present invention relates to Electrophtography photosensor, handle box, image processing system, cured film and organic electroluminescent device.

Background technology

Generally speaking, electronic photographing device has following structure and process.Particularly, obtain image formed matter by following process: the surface charging by charhing unit to Electrophtography photosensor; Thereby by with imaging mode, the surface of the described Electrophtography photosensor through charging being exposed to light so that the electric discharge of described surface selectivity forms electrostatic latent image on described surface; By developing cell, thereby toner is attached on described sub-image and makes image development to form toner image; And by transfer printing unit, described toner image is transferred on transfer printing body.

In recent years, the Electrophtography photosensor consisted of organic photoconductive material (Organophotoreceptor) becomes main flow.

Various materials for the outmost surface layer of Electrophtography photosensor have been proposed.For example, those materials that the conductive powder that Jap.P. proposes in being dispersed in phenolics for No. 3287678 forms.Japanese kokai publication hei 12-019749 communique proposes those materials that consist of hybrid inorganic-organic materials.TOHKEMY 2005-234546 communique proposes those materials that consist of the chain polymerization material.TOHKEMY 2000-66424 communique proposes those materials that consist of acrylic material.

TOHKEMY 2004-240079 communique proposes those materials of by carrying out overshoot, inducing crosslinked radiation-initiated crosslinking agent and charge transport material to form.

TOHKEMY 2008-058779 communique proposes the Electrophtography photosensor consisted of hindered phenol, hindered amine and alkyl phenyl ketone antioxidant.

TOHKEMY 2008-233893 communique proposes the Electrophtography photosensor consisted of hindered phenol, hindered amine, alkyl phenyl ketone, benzophenone antioxidant and metal complex quencher.

TOHKEMY 2006-234943 communique proposes the Electrophtography photosensor consisted of the active oxygen quencher.

TOHKEMY 2005-345782 communique proposes the Electrophtography photosensor consisted of hindered phenol or amine etc.

TOHKEMY 2002-040686 communique proposes the Electrophtography photosensor consisted of halogen compounds.

The present invention has been proposed so that Electrophtography photosensor to be provided, described Electrophtography photosensor is compared as those Electrophtography photosensors of outmost surface layer material with not comprising by usining compound that following formula (M1) means and the combination of the charge-transporting material with chain polymerization functional group, the image retention (ghost image) that less appearance causes due to residual formerly image.

Summary of the invention

According to a first aspect of the invention, Electrophtography photosensor is provided, described Electrophtography photosensor at least comprises conductive base and is arranged on the photographic layer on described conductive base, wherein, the outmost surface layer of described Electrophtography photosensor is made by the cured film of following composition, and described composition comprises by the compound with shown in following formula (M1) and the charge-transporting material with chain polymerization functional group:

In formula (M1), X ¹⁰¹And X ¹⁰²Mean independently of one another hydrogen atom, halogen atom, there is the alkyl of 1～15 carbon atom, the alkoxy with 1～15 carbon atom, cyano group, phenoxy group, have 6～30 carbon atoms aryl ,-Y ¹⁰¹-X ¹⁰³(Y wherein ¹⁰¹Mean azo group or siloxy; X ¹⁰³Mean the aryl that there is the alkyl of 1～15 carbon atom, the alkoxy with 1～15 carbon atom, cyano group, phenoxy group or there are 6～30 carbon atoms), or the substituting group formed by these moiety combinations; R ¹⁰¹And R ¹⁰³Mean independently of one another hydroxyl or there is the alkoxy of 1～15 carbon atom; M11 and m13 mean integer 0 or 1 independently of one another; R ¹⁰²And R ¹⁰⁴Mean to have independently of one another the alkyl of 1～15 carbon atom; M12 and m14 mean

integer

0,1,2 or 3 independently of one another.

The accompanying drawing explanation

Describe illustrative embodiments of the present invention in detail based on the following drawings, wherein:

Fig. 1 is the part cross sectional representation that shows the Electrophtography photosensor of illustrative embodiments of the present invention;

Fig. 2 is the part cross sectional representation that shows the Electrophtography photosensor of illustrative embodiments of the present invention;

Fig. 3 is the part cross sectional representation that shows the Electrophtography photosensor of illustrative embodiments of the present invention;

Fig. 4 is the schematic diagram that shows the image processing system of illustrative embodiments of the present invention;

Fig. 5 is the schematic diagram that shows the image processing system of another illustrative embodiments of the present invention;

Fig. 6 A～6C is the schematic diagram that shows the standard of estimating ghost image.

Embodiment

Other aspects of the present invention are described below.

A second aspect of the present invention is Electrophtography photosensor as described as first aspect, and wherein, described charge-transporting material is at least one by the compound meaned with following formula (I).

In formula (I), F means to have the n valency organic group of cavity conveying; R means hydrogen atom or alkyl; L means divalent organic group; N means the integer more than 1; And j means 0 or 1.

A third aspect of the present invention is that wherein, the outmost surface layer of described Electrophtography photosensor is protective seam as first or the described Electrophtography photosensor of second aspect.

A fourth aspect of the present invention be as first to the described Electrophtography photosensor of either side in the third aspect, wherein, described photographic layer is the individual layer photographic layer, or comprises the stack-up type photographic layer of charge generation layer and charge transport layer.

A fifth aspect of the present invention is Electrophtography photosensor as described as fourth aspect, wherein, described charge transport layer is the outmost surface layer of the described Electrophtography photosensor made by the cured film of following composition, and described composition comprises by the described compound shown in formula (M1) and has the described charge-transporting material of chain polymerization functional group.

A sixth aspect of the present invention is that described Electrophtography photosensor also comprises the undercoat be arranged on described conductive base as the described Electrophtography photosensor of either side in first aspect to the five aspects.

A seventh aspect of the present invention is handle box, described handle box comprises the described Electrophtography photosensor of either side in first aspect to the six aspects, and at least one unit in the group of the freely following unit of choosing composition: for the charhing unit to described Electrophtography photosensor charging; For using toner will be formed on the developing cell of the latent electrostatic image developing on described Electrophtography photosensor; Remove unit with the toner that the toner for remaining in described Electrophtography photosensor surface is removed.

A eighth aspect of the present invention is image processing system, and described image processing system comprises: the described Electrophtography photosensor of either side in first aspect to the six aspects; For the charhing unit to described Electrophtography photosensor charging; Form unit for the electrostatic latent image that forms electrostatic latent image on the described Electrophtography photosensor through charging; Thereby for using toner will be formed on the developing cell of the latent electrostatic image developing formation toner image on described Electrophtography photosensor; With for described toner image being transferred to the transfer printing unit of transfer printing body.

A ninth aspect of the present invention is a kind of cured film of composition, and described composition comprises by the compound with shown in following formula (M1) and the charge-transporting material with chain polymerization functional group.

integer

0,1,2 or 3 independently of one another.

A tenth aspect of the present invention is as the 9th described cured film in aspect, and wherein, described charge-transporting material is at least one by the compound meaned with following formula (I).

A eleventh aspect of the present invention is organic electroluminescent device, and described organic electroluminescent device comprises anode, hole transporting layer, luminescent layer and negative electrode, and wherein, described hole transporting layer at least comprises the 9th aspect or the tenth described cured film in aspect.

The of the present invention first to the 6th aspect provides Electrophtography photosensor, described Electrophtography photosensor is compared as those Electrophtography photosensors of outmost surface layer material with not comprising by usining compound that following formula (M1) means and the combination of the charge-transporting material with chain polymerization functional group, the image retention (ghost image) that less appearance causes due to residual formerly image.

The of the present invention the 7th and eight aspect handle box and image processing system are provided, described handle box and image processing system and use do not comprise by usining compound that following formula (M1) means and the combination of the charge-transporting material with chain polymerization functional group to be compared as the situation of the Electrophtography photosensor of outmost surface layer material, the image retention (ghost image) that the less appearance of image is caused due to residual formerly image.

The the of the present invention the 9th and the tenth aspect provides cured film, described cured film is compared with not comprising those cured film by the combination of the compound meaned with following formula (M1) and the charge-transporting material with chain polymerization functional group, has durabilities such as solvent resistance and thermotolerance and good charge-transporting.

Electrophtography photosensor

The Electrophtography photosensor of this illustrative embodiments at least comprises conductive base and is arranged on the photographic layer on described conductive base.The outmost surface layer of described Electrophtography photosensor is made by the cured film of following composition, and described composition comprises by the compound shown in formula (M1) and the charge-transporting material with chain polymerization functional group.

The cured film that comprises following composition has high mechanical properties as the Electrophtography photosensor of outmost surface layer, but may cause the deteriorated of electrical properties, the image retention (ghost image) caused due to residual formerly image for example occurs, wherein said composition comprises the charge-transporting material with chain polymerization functional group.

In order to overcome the above problems, the Electrophtography photosensor of this illustrative embodiments comprises the outmost surface layer as the cured film of following composition, described composition comprises the charge-transporting material with chain polymerization functional group and the compound meaned by above-mentioned formula (M1), thereby prevents the image retention (ghost image) caused due to residual formerly image.Its reason is also unclear, but as follows by inference.

In the known charge-transporting material the having chain polymerization functional group process curing with form membrane, chain polymerization starts from the attack of the kation, negative ion or the radical pair chain polymerization functional group that for example, are produced by initiating agent and stimulation (heat, electron beam or light).Now, charge transport part (charge transport skeleton) in charge-transporting material also is subject to for example, attack by kation, negative ion or the free radical of initiating agent and stimulation (heat, electron beam or light) generation to a great extent, and this probably causes the deteriorated of electrical properties.By providing the stimulation under temperate condition can avoid described deteriorated, but cross-linking density may not can improve under such temperate condition, and this will cause the film strength deficiency.

On the other hand, under the existence of the compound meaned by formula (M1), kation, negative ion or the free radical for example, produced by initiating agent and stimulation (heat, electron beam or light) optionally attack chain polymerization functional group with the begin chain polymerization, thereby prevented the attack to the part of the charge transport in described charge-transporting material (charge transport skeleton), this probably contributes to formation to have intac charge-transporting and also has high-intensity cured film.Especially, the radical polymerization initiator that shows the living polymerization behavior can realize having more optionally chain polymerization.Cause chain polymerization by the selectivity attack to chain polymerization functional group, can prevent thus the attack to the part of the charge transport in charge-transporting material (charge transport skeleton).

For this reason, can think that the Electrophtography photosensor of this illustrative embodiments has prevented the appearance of the image retention (ghost image) that causes due to residual formerly image.As a result, the outmost surface layer consisted of the cured film of described composition shows high mechanical properties, and reuses for a long time the electrical properties and the deteriorated of image property that cause and suppressed.

In addition, result, comprise the handle box of Electrophtography photosensor of this illustrative embodiments and the image retention (ghost image) that image processing system makes the minimum appearance of image cause due to residual formerly image.Obtained stable image.

As mentioned above, the Electrophtography photosensor of this illustrative embodiments comprises the outmost surface layer of being made by the cured film of particular composition.Described outmost surface layer is preferably formed the upper surface of described Electrophtography photosensor, particularly preferably as protective seam or charge transport layer.

For example, when the protective seam, photographic layer is set on conductive base and, as the described protective seam of outmost surface layer, described protective seam is made by the cured film of particular composition when described outmost surface layer.

For example, when described outmost surface layer is taken on charge transport layer, charge generation layer is set on conductive base and, as the described charge transport layer of outmost surface layer, described charge transport layer is made by the cured film of particular composition.

Hereinafter, describe with reference to the accompanying drawings the Electrophtography photosensor related in the exemplary embodiment in detail, wherein the outmost surface layer is the layer as protective seam.

Fig. 1 is the schematic cross-section that has shown the preferred illustrative embodiment of the Electrophtography photosensor of mentioning in the exemplary embodiment.Each has shown the schematic cross-section of the Electrophtography photosensor of mentioning in another illustrative embodiments naturally Fig. 2 and Fig. 3.

The Electrophtography photosensor 7A shown in Fig. 1 is so-called function divergence type photoreceptor (or multi-layered type photoreceptor) and has following structure; wherein undercoat 1 is formed on conductive base 4, then form successively charge generation layer 2 thereon, charge transport layer 3 and protective seam 5.In Electrophtography photosensor 7A, photographic layer consists of charge generation layer 2 and charge transport layer 3.

The Electrophtography photosensor 7B shown in Fig. 2 is function divergence type photoreceptor, and wherein similar to the Electrophtography photosensor 7A shown in Fig. 1, function is distributed in charge generation layer 2 and charge transport layer 3.The Electrophtography photosensor 7C shown in Fig. 3 comprises charge generating material and charge-transporting material in same layer (single-layer type photographic layer 6 (charge generation/charge transport layer)).

The Electrophtography photosensor 7B shown in Fig. 2 has following structure, and wherein undercoat 1 is formed on conductive base 4, then form successively charge transport layer 3 thereon, charge generation layer 2 and protective seam 5.In Electrophtography photosensor 7B, photographic layer consists of charge transport layer 3 and charge generation layer 2.

In addition, the Electrophtography photosensor 7C shown in Fig. 3 has following structure, and wherein undercoat 1 is formed on conductive base 4, and forms successively single-layer type photographic layer 6 and protective seam 5 thereon again.

In the Electrophtography photosensor 7A～7C shown in Fig. 1～3, protective seam 5 is the outmost surface layers that are configured to apart from conductive base 4 farthest, and described outmost surface layer is made by the cured film of particular composition.

In the Electrophtography photosensor shown, can omit undercoat 1 in Fig. 1～3.

The Electrophtography photosensor 7A shown of take in Fig. 1 is typical example, and its component description is as follows.

Conductive base

Described conductive base can freely be selected from existing conductive base, for example, such as (thering is film on it, metals such as aluminium, nickel, chromium, stainless steel, or the film of aluminium, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide or tin indium oxide (ITO)) plastic foil, through the paper of electric conductivity imparting agent coating or dipping with through the plastic foil of the coating of electric conductivity imparting agent or dipping.Described matrix can be cylindrical shape, sheet shape or plate shape.

The conductive base particle preferably has and for example is less than 10 ⁷The specific insulation of Ω cm.

When described conductive base is metal tube, its surface can be unprocessed, or through processing such as mirror polish, etching, anodic oxidation, rough cut, centerless grinding, sandblast or wet type honings.

Undercoat

In case of necessity, be formed with undercoat, to prevent the lip-deep light reflection of conductive base, and unnecessary charge carrier flows into photographic layer by conductive base.

Undercoat for example by adhesive resin and optionally other adjuvants form.

The example of the adhesive resin contained in undercoat comprises known fluoropolymer resin compound, such as acetal resin (as polyvinyl butyral), polyvinyl alcohol resin, casein, polyamide, celluosic resin, gelatin, urethane resin, vibrin, methacrylic resin, acrylic resin, Corvic, vinylite, vinyl chloride-vinyl acetate-maleic resin, silicones, silicone alkyd resin, phenolics, phenol formaldehyde resin, melamine resin and carbamate resins; Charge transport resin with charge-transporting group; And electroconductive resin, such as polyaniline.Therein, insoluble resin in the coating solvent preferably used in upper strata.Especially preferred phenolics, phenol formaldehyde resin, melamine resin, carbamate resins and epoxy resin.

Undercoat can contain metallic compound, such as silicon compound, organic zirconate, organic titanic compound or organo-aluminum compound.

The ratio that there is no specified metal compound and binder resin, this ratio can be through selecting to realize the desired Electrophtography photosensor character obtained.

Undercoat can be containing the resin particle that is useful on the control surface roughness.The example of resin particle comprises (PMMA) resin particle of silicon resin particle and crosslinked poly-(methyl methacrylate).For the purpose of control surface roughness, polishing can be carried out by such as buff polishing, sandblast, wet type honing or grinding etc. in the surface that is arranged on the undercoat on conductive base.

For example, undercoat can at least contain adhesive resin and conductive particle.Described conductive particle preferably has and for example is less than 10 ⁷The specific insulation of Ω cm.

The example of conductive particle comprises metallic particles (for example aluminium, copper, nickel and silver-colored particle), conductive metal oxide particle (for example antimony oxide, indium oxide, tin oxide and Zinc oxide particles) and conductive material particle (carbon fiber, carbon black and powdered graphite particle).Therein, preferred conductive metal oxide particle.Described conductive particle can two or more being combined into be exercised use with it.

Described conductive particle can use hydrophobizers (for example, coupling agent) to carry out surface treatment, thus controlling resistance.

The content of described conductive particle for example is preferably 10 % by weight with respect to binder resin～80 % by weight, and 40 % by weight～80 % by weight more preferably.

The undercoat formation that employing contains mentioned component in solvent forms undercoat with coating fluid.

Comprise the medium decollator in undercoat formation with the example of the method for discrete particles in coating fluid, such as bowl mill, vibromill, masher, sand mill and horizontal sand mill, with without the medium decollator, such as stirrer, ultrasonic decollator, roller mill and high pressure homogenisers.Described high pressure homogenisers can be to collide to realize by liquid under high pressure-liquid collision or liquid-wall the collision type disperseed, or by under high pressure through fine channel, realizing the penetrating type disperseed.

Comprise dip-coating, the coating of upper pushing-type, the excellent coating that winds the line, spraying, scraper plate coating, scraper for coating and the coating of curtain formula for the example that undercoat formation is applied to the method for conductive base with coating fluid.

More than the thickness of undercoat is preferably 15 μ m, 20 μ m～50 μ m more preferably.

Although do not indicate, between undercoat and photographic layer, can form middle layer.The example of the adhesive resin contained in middle layer comprises: fluoropolymer resin compound, for example acetal resin (as polyvinyl butyral), polyvinyl alcohol resin, casein, polyamide, celluosic resin, gelatin, urethane resin, vibrin, methacrylic resin, acrylic resin, Corvic, vinylite, vinyl chloride-vinyl acetate-maleic resin, silicones, silicone alkyd resin, phenol formaldehyde resin and melamine resin; And the organometallics that contains zirconium, titanium, aluminium, manganese or silicon atom.These compounds can be used separately, or two or more potpourri or condensed polymers used with it.Wherein, preferably contain the organometallics of zirconium or silicon, because they have the low-residual electromotive force and have suppressed thus environment or reused the potential change caused.

The middle layer formation that employing contains mentioned component in solvent forms middle layer with coating fluid.

Comprise common method for being coated with middle layer formation with the example of the method for coating fluid, such as dip-coating, the coating of upper pushing-type, the excellent coating that winds the line, spraying, scraper plate coating, scraper for coating and the coating of curtain formula.

Except the spreadability that improves upper strata, the power block layer is also served as in middle layer.If film thickness is too large, it is too high that potential-energy barrier may become, thereby may cause desensitization and because the electromotive force that repeats to cause rises.Therefore, if form middle layer, middle layer preferably is set to have the thickness of 0.1 μ m～3 μ m, and in the case, middle layer can be used as undercoat.

Charge generation layer

Charge generation layer is comprised of for example charge generating material and adhesive resin.The example of charge generating material comprises phthalocyanine color, such as metal-free phthalocyanine, chlorine phthalocyanine gallium, hydroxyl phthalocyanine gallium, dichloro Tin Phthalocyanine and TiOPc.Object lesson comprises for CuK α characteristic x ray at least having 7.4 °, 16.6 °, 25.5 ° and the chlorine phthalocyanine gallium crystal of the strong diffraction peak located of the Bragg angle (2 θ ± 0.2 °) of 28.3 °, at least there are 7.7 ° for CuK α characteristic x ray, 9.3 °, 16.9 °, 17.5 °, 22.4 ° and the metal-free phthalocyanine crystal of the strong diffraction peak located of the Bragg angle (2 θ ± 0.2 °) of 28.8 °, at least there are 7.5 ° for CuK α characteristic x-ray, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and the hydroxyl phthalocyanine gallium crystal of the strong diffraction peak located of the Bragg angle (2 θ ± 0.2 °) of 28.3 °, at least there are 9.6 ° for CuK α characteristic x-ray, 24.1 ° and the TiOPc crystal of the strong diffraction peak located of the Bragg angle (2 θ ± 0.2 °) of 27.2 °.Other examples of charge generating material comprise quinone pigments, perylene dye, indigo pigment, bisbenzimidazole pigment, anthrone pigment and quinacridone pigment.These charge generating materials can be used alone or two or more being used in combination with it.

The example that forms the adhesive resin of charge generation layer comprises: polycarbonate resins such as bisphenol A-type or bisphenol Z type, acrylic resin, methacrylic resin, polyarylate resin, vibrin, Corvic, polystyrene resin, the acrylonitritrile-styrene resin resin, the acrylonitrile-butadiene copolymer resin, vinylite, vinyl-formal resin, polysulfone resin, the Styrene-Butadiene resin, vinylidene chloride-acrylonitrile compolymer resin, vinyl chloride-vinyl acetate-maleic resin, silicones, phenol formaldehyde resin, polyacrylamide resin, polyamide and poly N-vinyl carbazole resin.These binder resins can be used alone or two or more being used in combination with it.

The mixture ratio of charge generating material and adhesive resin is preferably for example 10:1～1:10.

The charge generation layer formation that employing contains mentioned component in solvent forms charge generation layer with coating fluid.

In charge generation layer formation, for example, with the example of the method for discrete particles in coating fluid (charge generating material), comprising: the medium decollator, such as bowl mill, vibromill, masher, sand mill and horizontal sand mill, with without the medium decollator, such as stirrer, ultrasonic decollator, roller mill and high pressure homogenisers.Described high pressure homogenisers can be to collide to realize by liquid under high pressure-liquid collision or liquid-wall the collision type disperseed, or by under high pressure through fine channel, realizing the penetrating type disperseed.

Comprise dip-coating, the coating of upper pushing-type, the excellent coating that winds the line, spraying, scraper plate coating, scraper for coating and the coating of curtain formula for the example that charge generation layer formation is applied to the method on undercoat with coating fluid.

The thickness of charge generation layer is preferably 0.01 μ m～5 μ m, more preferably 0.05 μ m～2.0 μ m.

Charge transport layer

Charge transport layer is comprised of charge-transporting material and optional adhesive resin.When described charge transport layer is the outmost surface layer as mentioned above, charge transport layer is made by the cured film of particular composition.

The example of described charge-transporting material comprises: the cavity conveying material, and Li is as oxadiazole derivative, as 2,5-bis-(p-diethylamino phenyl)-1,3,4-oxadiazole; Pyrazoline derivative, as 1,3,5-triphenyl-pyrazoline and 1-[pyridine radicals-(2)]-3-(p-diethylamino styryl)-5-(p-diethylamino styryl) pyrazoline; The tertiary amino-compound of aromatic series, as triphenylamine, N, N '-bis-(3,4-3,5-dimethylphenyl) xenyl-4-amine and three (p-aminomethyl phenyl) amino-4-amine and dibenzyl aniline; The tertiary amino-compound of aromatic series two, as N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenylbenzidine; 1,2,4-pyrrolotriazine derivatives, as 3-(4 '-dimethylaminophenyl)-5,6-bis-(4 '-methoxyphenyl)-1,2, the 4-triazine; Hydazone derivative, as 4-diethyl amino benzaldehyde-1,1-diphenyl hydrazone; Quinazoline derivant, as 2-phenyl-4-styryl-quinazoline; Benzofuran derivatives, as 6-hydroxyl-2,3-bis-(p-methoxyphenyl) coumarone; α-stilbene derivative, as p-(2,2-diphenylacetylene)-N, N-diphenyl aniline; Enamine derivates; Carbazole derivates, as the N-ethyl carbazole; Poly-N-vinyl carbazole and derivant thereof; With the electron transport material, naphtoquinone compounds for example, as chloranil and bromo anthraquinone; Four cyano quinone bismethane compound; The Fluorenone compound, as 2,4,7-trinitro-fluorenone and 2,4,5,7-tetranitro-9-Fluorenone; The xanthone compound; There is the polymkeric substance derived from the group of arbitrary above-claimed cpd in thiophene compound and main chain or side chain.These charge-transporting materials can be used alone or two or more being used in combination with it.

The example that forms the adhesive resin of charge transport layer comprises: insulative resin, for example, polycarbonate resins such as bisphenol A-type or bisphenol Z type, acrylic resin, methacrylic resin, polyarylate resin, vibrin, Corvic, polystyrene resin, the acrylonitritrile-styrene resin resin, the acrylonitrile-butadiene copolymer resin, vinylite, vinyl-formal resin, polysulfone resin, the Styrene-Butadiene resin, vinylidene chloride-acrylonitrile compolymer resin, vinyl chloride-vinyl acetate-maleic resin, silicones, phenol formaldehyde resin, polyacrylamide resin, polyamide and neoprene, with the organic photoconductive polymkeric substance, for example Polyvinyl carbazole, polyvinyl anthracene and polyvinyl pyrene.These adhesive resins can be used alone or two or more being used in combination with it.

The mixture ratio preference of charge-transporting material and adhesive resin is as be 10:1～1:5.

The charge transport layer formation that employing contains mentioned component in solvent forms charge transport layer with coating fluid.

In charge transport layer formation, for example, with the example of the method for discrete particles in coating fluid (fluorinated resin particle), comprising: the medium decollator, such as bowl mill, vibromill, masher, sand mill and horizontal sand mill, with without the medium decollator, such as stirrer, ultrasonic decollator, roller mill and high pressure homogenisers.Described high pressure homogenisers can be to collide to realize by liquid under high pressure-liquid collision or liquid-wall the collision type disperseed, or by under high pressure through fine channel, realizing the penetrating type disperseed.

Comprise dip-coating, the coating of upper pushing-type, the excellent coating that winds the line, spraying, scraper plate coating, scraper for coating and the coating of curtain formula for the example that charge transport layer formation is applied to the method for charge generation layer with coating fluid.

The thickness of charge transport layer is preferably 5 μ m～50 μ m, more preferably 10 μ m～40 μ m.

Protective seam

Protective seam is made with the cured film of the composition of the charge-transporting material with chain polymerization functional group by comprising the compound meaned with following formula (M1).

The compound that formula (M1) means further describes as follows.

integer

0,1,2 or 3 independently of one another.

In formula (M1), by X ¹⁰¹And X ¹⁰²The example of the halogen atom meaned comprises fluorine atom, chlorine atom and bromine atoms.

In formula (M1), by X ¹⁰¹, X ¹⁰²And X ¹⁰³The example of the alkyl meaned comprises having substituent or do not have substituent straight chain, side chain or a cyclic alkyl.Described alkyl preferably has 1～10 carbon atom.

The object lesson of alkyl comprises methyl, ethyl, isopropyl, butyl, the tert-butyl group, isopentyl, amyl group, hexyl, cyclohexyl, octyl group, ethylhexyl, different nonyl, decyl, dodecyl and myristyl.

In formula (M1), by X ¹⁰¹, X ¹⁰²And X ¹⁰³The example of the alkoxy meaned comprises having substituent or do not have substituent straight chain, side chain or a cyclic alkoxy.Described alkoxy preferably has 1～15 carbon atom, more preferably has 1～10 carbon atom.

The object lesson of alkoxy comprises methoxyl, ethoxy, isopropoxy, butoxy, isoamoxy, amoxy, own oxygen base, cyclohexyloxy, octyloxy, ethyl hexyl oxy, different ninth of the ten Heavenly Stems oxygen base, last of the ten Heavenly stems oxygen base, dodecyloxy and tetradecyloxyaniline.

In formula (M1), by X ¹⁰¹, X ¹⁰²And X ¹⁰³The example of the phenoxy group meaned comprises having substituent or do not have a substituent phenoxy group.

In formula (M1), by X ¹⁰¹, X ¹⁰²And X ¹⁰³The example of the aryl meaned comprises having substituent or do not have substituent phenyl, have substituent or do not have substituent many cyclophanes perfume base (aromatic radical be connected with phenyl ring) and have substituent or do not have a substituent condensation aromatic radical.Described aryl preferably has 6～30 carbon atoms, more preferably 6～20 carbon atoms.

The example of described many cyclophanes perfume base comprises xenyl and terphenyl.

Described condensation aromatic radical comprises indenyl, naphthyl, Azulene base, fluorenyl, phenanthryl, anthryl, acenaphthenyl and biphenylene.

In formula (M1), by above by X arbitrarily ¹⁰¹And X ¹⁰²The substituent example that the group meaned forms comprises following structure (M1-A)～(M1-B).

In structure (M1-A)～(M1-B), X ¹⁰⁴, X ¹⁰⁵And X ¹⁰⁶Mean independently of one another hydrogen atom, halogen atom, there is the alkyl of 1～15 carbon atom, the alkoxy with 1～15 carbon atom, cyano group, phenoxy group, have 6～30 carbon atoms aryl ,-Y ¹⁰¹-X ¹⁰³(Y wherein ¹⁰¹Mean azo group or siloxy; X ¹⁰³Mean the aryl that there is the alkyl of 1～15 carbon atom, the alkoxy with 1～15 carbon atom, cyano group, phenoxy group or there are 6～30 carbon atoms).X ¹⁰⁴, X ¹⁰⁵And X ¹⁰⁶Details and X ¹⁰¹Identical.

In formula (M1), by R ¹⁰¹And R ¹⁰³The example of the alkoxy meaned comprises having substituent or do not have substituent straight chain, side chain or a cyclic alkoxy.Described alkoxy preferably has 1～15 carbon atom, more preferably has 1～10 carbon atom.

The object lesson of alkoxy comprises methoxyl, ethoxy, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy.

In formula (M1), when m11 and m13 mean integer 1 separately, by R ¹⁰¹And R ¹⁰³The contraposition that the hydroxyl meaned or alkoxy are preferably placed at each phenyl in formula (M1).

In formula (M1), by R ¹⁰²And R ¹⁰⁴The example of the alkyl meaned comprises having substituent or do not have substituent straight chain, side chain or a cyclic alkyl.Described alkyl preferably has 1～15 carbon atom, more preferably has 1～10 carbon atom.

The object lesson of alkyl comprises methyl, ethyl, isopropyl, butyl, the tert-butyl group, isopentyl, amyl group, hexyl, cyclohexyl, octyl group, ethylhexyl, different nonyl and decyl.

In formula (M1), when any above-mentioned group has substituting group, described substituent example comprises hydrogen atom, alkyl, alkoxy, phenoxy group, aryl, aralkyl, substituted-amino and halogen atom.

Preferably have 1～10 carbon atom as substituent alkyl, its example comprises methyl, ethyl, propyl group and isopropyl.Preferably have 1～10 carbon atom as substituent alkoxy, its example comprises methoxyl, ethoxy, propoxyl group and isopropoxy.Preferably have 6～20 carbon atoms as substituent aryl, its example comprises phenyl and tolyl.Aralkyl preferably has 7～20 carbon atoms, and its example comprises benzyl and phenethyl.The substituent example of substituted-amino comprises alkyl, aryl and aralkyl, and its object lesson is same as described above.

Especially from preventing the angle of the image retention (ghost image) caused due to residual formerly image, the compound meaned by formula (M1) is preferably any of the compound that meaned by formula (M2)～(M3).

Other examples of the compound meaned by formula (M1) comprise wherein X ¹⁰¹Mean hydrogen atom, X ¹⁰²Mean to have the alkyl of 1～15 carbon atom, R ¹⁰¹And R ¹⁰³Mean independently of one another hydroxyl or have the alkoxy of 1～15 carbon atom, m11 and m13 mean integer 1 independently of one another, and m12 and m14 mean 0 compound.

Wherein, the compound preferably meaned by formula (M2).

In formula (M2), X ²⁰¹Mean hydrogen atom, halogen atom, the alkyl with 1～15 carbon atom, the alkoxy with 1～15 carbon atom, cyano group, phenoxy group, have 6～30 carbon atoms aryl or-Y ²⁰¹-X ²⁰²(Y wherein ²⁰¹Mean azo group or siloxy; X ²⁰²Mean the aryl that there is the alkyl of 1～15 carbon atom, the alkoxy with 1～15 carbon atom, cyano group, phenoxy group or there are 6～30 carbon atoms).

X ²⁰¹Concrete condition and the X in formula (M1) ¹⁰¹Identical.

In formula (M2), R ²⁰¹, R ²⁰³And R ²⁰⁵Mean independently of one another hydroxyl; M21, m23 and m25 mean integer 0 or 1 independently of one another.

R ²⁰¹, R ²⁰³And R ²⁰⁵Concrete condition, and the concrete condition of m21, m23 and m25 respectively with formula (M1) in R ¹⁰¹Identical with m11.

In (M2), R ²⁰², R ²⁰⁴And R ²⁰⁶Mean to have independently of one another the alkyl of 1～15 carbon atom; M22, m24 and m26 mean

integer

0,1,2 or 3 independently of one another.

R ²⁰², R ²⁰⁴And R ²⁰⁶Concrete condition, and the concrete condition of m22, m24 and m26 respectively with formula (M1) in R ¹⁰²Identical with m12.

Particularly preferably be, in formula (M2), X ²⁰¹Mean hydrogen atom or-Y ²⁰¹-X ²⁰²(Y wherein ²⁰¹Mean azo group, X ²⁰²Mean to have the aryl of 6～30 carbon atoms); R ²⁰¹, R ²⁰³And R ²⁰⁵Mean independently of one another hydroxyl; M21, m23 and m25 mean integer 0 or 1 independently of one another; M22, m24 and m26 mean 0.

In formula (M3), X ³⁰¹And X ³⁰²Mean independently of one another hydrogen atom, halogen atom, there is the alkyl of 1～15 carbon atom, the alkoxy with 1～15 carbon atom, cyano group, phenoxy group, have 6～30 carbon atoms aryl or-Y ³⁰¹-X ³⁰³(Y wherein ³⁰¹Mean azo group or siloxy; X ³⁰³Mean the aryl that there is the alkyl of 1～15 carbon atom, the alkoxy with 1～15 carbon atom, cyano group, phenoxy group or there are 6～30 carbon atoms).

X ³⁰¹And X ³⁰²Concrete condition and the X in formula (M1) ¹⁰¹Identical.

In formula (M3), R ³⁰¹, R ³⁰³, R ³⁰⁵And R ³⁰⁷Mean independently of one another hydroxyl; M31, m33, m35 and m37 mean integer 0 or 1 independently of one another.

R ³⁰¹, R ³⁰³, R ³⁰⁵And R ³⁰⁷Concrete condition, and the concrete condition of m31, m33, m35 and m37 respectively with formula (M1) in R ¹⁰¹Identical with m11.

In (M3), R ³⁰², R ³⁰⁴, R ³⁰⁶And R ³⁰⁸Mean to have independently of one another the alkyl of 1～15 carbon atom; M32, m34, m36 and m38 mean

integer

0,1,2 or 3 independently of one another.

R ³⁰², R ³⁰⁴, R ³⁰⁶And R ³⁰⁸Concrete condition, and the concrete condition of m32, m34, m36 and m38 respectively with formula (M1) in R ¹⁰²Identical with m12.

Be particularly preferably, in formula (M3), X ³⁰¹Mean cyano group or phenoxy group.

The object lesson of the compound meaned by formula (M1) comprises following compound.Yet illustrative embodiments of the present invention is not limited to this.

From preventing the angle of the image retention (ghost image) caused due to residual formerly image, the compound meaned by formula (M1) preferably has the weight-average molecular weight below 5000, and more preferably 100～2000, more more preferably 150～1000.

With respect to the composition that is used to form protective seam, the content of the compound meaned by formula (M1) is preferably 0.01 % by weight～20 % by weight, 0.05 % by weight～10 % by weight more preferably, then 0.1 % by weight～5 % by weight more preferably.

Charge-transporting material with chain polymerization functional group further describes as follows.

Charge-transporting material with chain polymerization functional group is the compound that has charge transport skeleton and chain polymerization functional group in its molecule.

Described charge transport skeleton can be the skeleton derived from nitrogenous cavity conveying compound (such as triarylamine compound, benzidine compound or hydrazone compound), wherein this structure and nitrogen-atoms conjugation.

The example of described chain polymerization functional group comprises acryloyl group, methacryl and styryl.Be particularly preferably methacryl.

Object lesson with charge-transporting material of chain polymerization functional group is preferably the compound with following formula (I).

F in formula (I) means to have the n valency organic group of cavity conveying.The example of organic group comprises the organic group derived from the arylamine derivant, by remove the organic group that hydrogen atom obtains from the arylamine derivant.In the arylamine derivant, preferably derived from the n valency organic group of arylamine derivants such as triphenylamine derivant or tetraphenyl benzidine derivative.

So the n in formula (I) means the integer more than 1.Yet, from improving cross-linking density and obtaining thus the more angle of strong cross-linking film (cured film), n is preferably more than 2, more preferably more than 4.From the stability of coating fluid and the angle of electrical specification, the higher limit of n is preferably 20, and more preferably 10.

In the time of within n is set in above-mentioned preferable range, especially, when using scraper cleaner, the rotary torque of Electrophtography photosensor reduces; Therefore, the damage of scraper and the wearing and tearing of Electrophtography photosensor are suppressed.Its mechanism is not clear.Yet, it is envisaged that, when the number of reactive functional groups increases, obtain having the cured film of high crosslink density, and therefore suppressed the molecular motion of Electrophtography photosensor most surface, thereby make with the scraper component surface in the interaction of molecule die down.

In addition, in formula (I), R means hydrogen atom or alkyl.As alkyl, preferably there is the straight or branched alkyl of 1～5 carbon atom.

Wherein, R is preferably methyl.That is,, in the compound meaned by formula (I), the substituent end in bracket is preferably methacryl.Although its reason is also unclear, it is as follows that the inventor thinks.

Usually, there is the acryloyl group of high response in being commonly used in curing reaction.Yet, it is believed that when the acryloyl group with high response is used as the substituting group of the large volume charge-transporting material as the compound of formula (I) expression, non-homogeneous curing reaction easily occurs, and this will cause microcosmic (macroscopic view) island type structure.Such a island type structure is not special existing problems in the field outside electronic applications.Yet, when described island type structure is used for Electrophtography photosensor, will cause such as the inhomogeneous or shortcomings such as fold or Density inhomogeneity in the most surface layer.Therefore, R is preferably methyl.

It is believed that, when a plurality of functional groups, with a charge transport skeleton (F in formula (I)), while being connected, the formation of such island type structure is especially remarkable.

In addition, the L in formula (I) means divalent organic group.As divalent organic group, preferably contain the organic group of the alkylidene with 2 above carbon atoms.In addition, from the angle of electrical specification and physical strength, j is preferably 1.Why preferably the reason of such structure is also unnecessary clear.Yet it is as follows that the inventor thinks.

; it is believed that; therein as formula (I) represented compound; the free radical polymerization substituent carries out in the situation of polymerization; when the free radical produced in polymerization has while being easy to move to the structure of charge transport skeleton (F in formula (I)); the free radical produced makes the charge transport function deteriorated, and this causes the deteriorated of electrical specification.In addition, about physical strength, it is believed that, when large volume charge transport skeleton and polymerism site mutually near and while being rigidity, the polymerism site is difficult to mutually move closer to, this will cause reacting the remarkable reduction of possibility.According to these reasons, think that L preferably contains the alkylidene with two above carbon atoms, and j is preferably 1.

Herein, when L is the organic group that contains the alkylidene with two above carbon atoms, described organic group can only consist of the alkylidene with two above carbon atoms, or can be alkylidene with two above carbon atoms and the combination of divalent groups such as alkenylene, alkynylene, ether, thioether, ester or arlydene (such as phenylene).From the angle of physical strength, the carbon number purpose higher limit of alkylidene is preferably 20, and more preferably 10.

The compound that formula (I) means is preferably by the compound meaned with following formula (II).

The compound that formula (II) means is especially very excellent aspect the stability to charge mobility and oxidation.

In formula (II), Ar ¹～Ar ⁴Mean independently of one another to have substituent or do not there is substituent aryl, Ar ⁵Mean to have substituent or do not there is substituent aryl or have substituent or do not there is substituent arlydene, D means-(L) _j-O-CO-C (R)=CH ₂, j mean 0 or 1, five c mean independently of one another 0 or 1, k mean 0 or 1, and the ading up to more than 1 of D, L, R and j have the definition identical with j with L, R in formula (I) separately.In addition, R is preferably hydrogen atom or has the straight or branched alkyl of 1～5 carbon atom.

The sum of D is corresponding to the n in formula (I) in formula (II), and, from improving cross-linking density and can obtaining the above-mentioned angle with cross linking membrane (cured film) of higher mechanical strength, is preferably more than 2, more preferably more than 4.

As mentioned above, R is preferably methyl.

In formula (II), Ar ¹Or Ar ⁴Mean independently of one another to have substituent or do not there is substituent aryl.Ar ¹～Ar ⁴Can be identical or differ from one another.

Herein, about the substituting group in thering is substituent aryl, can enumerate except D:-(L) _j-O-CO-C (R)=CH ₂Substituent example in addition comprises the alkyl with 1～4 carbon atom, the alkoxy with 1～4 carbon atom, replace and the phenyl of the alkoxy with 1～4 carbon atom is arranged, do not have substituent phenyl, have aralkyl and the halogen atom of 7～10 carbon atoms.

Ar ¹～Ar ⁴Be preferably separately any in structural formula shown below (1)～(7).The structural formula of the following stated (1)～(7) with can with each Ar ¹～Ar ⁴" (D) c " be connected shows together." (D) c " equivalent in meaning in " (D) c " herein and formula (II), preferred example is also identical with " (D) c " in formula (II).

In structural formula (1), R ⁰¹Mean to select free hydrogen atom, have 1～4 carbon atom alkyl, replace by the alkyl with 1～4 carbon atom or there is the phenyl of the alkoxy of 1～4 carbon atom, do not there is substituent phenyl and there is a group in the group that the aralkyl of 7～10 carbon atoms forms.

In structural formula (2) and (3), R ⁰²～R ⁰⁴Mean independently of one another to select free hydrogen atom, have 1～4 carbon atom alkyl, have 1～4 carbon atom alkoxy, replace by the phenyl of the alkoxy with 1～4 carbon atom, do not there is substituent phenyl, there is a group in the aralkyl of 7～10 carbon atoms and group that halogen atom forms.In addition, m means 1～3 integer.

In structural formula (7), Ar means to have substituent or does not have a substituent arlydene.

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

In structural formula (8) and (9), R ⁰⁵And R ⁰⁶Mean independently of one another to select free hydrogen atom, have 1～4 carbon atom alkyl, have 1～4 carbon atom alkoxy, replace by the phenyl of the alkoxy with 1～4 carbon atom, do not there is substituent phenyl, there is a group in the aralkyl of 7～10 carbon atoms and group that halogen atom forms.In addition, q means 1～3 integer separately.

In structural formula (7), Z' means the organic linking group of divalence, and preferably any in structural formula shown below (10)～(17) is represented.In addition, p means 0 or 1.

In structural formula (10)～(17), R ⁰⁷And R ⁰⁸Mean independently of one another to select free hydrogen atom, have 1～4 carbon atom alkyl, have 1～4 carbon atom alkoxy, replace by the phenyl of the alkoxy with 1～4 carbon atom, do not there is substituent phenyl, there is a group in the aralkyl of 7～10 carbon atoms and group that halogen atom forms, W means divalent group, r and s mean 1～10 integer independently of one another, and t means 1～3 integer separately.

In addition, the W in structural formula (16)～(17) is preferably any divalent group of any expression in structural formula shown below (18)～(26).Yet, in formula (25), u means 0～3 integer.

In formula (II), when k is 0, Ar ⁵Have substituent or do not there is substituent aryl, and the example of described aryl and Ar ¹～Ar ⁴In the example of aryl identical.When k is 1, Ar ⁵Have substituent or do not there is substituent arlydene, and, as arlydene, can enumerate by from Ar ¹～Ar ⁴Description in remove a resulting arlydene of hydrogen atom of pre-position in the aryl that exemplifies.

The object lesson of the compound represented by formula (I) hereinafter, will be shown.The compound represented by formula (I) not is confined to this fully.

At first, the object lesson (compound i-1～i-14) when having listed n in formula (I) and being 1, but not limited thereto.

Following compound is that wherein n is the object lesson (compound ii-1～ii-26) of the compound that means of 2 formula (I).Yet described compound is not limited to these examples.

Following compound is that wherein n is the object lesson (compound iii-1～iii-11) of the compound that means of 3 formula (I).Yet described compound is not limited to these examples.

Following compound is that wherein n is 4 (compound iv-1～iv-18), and n is 5 (compound v-1), and n is the object lesson of the compound that means of the formula (I) of 6 (compound vi-1～vi-2).

The example of the synthetic route of compound iv-4 and iv-17 shows below.

Other represented compounds of formula (I) for example can be synthesized according to the synthetic route identical with iv-17 with compound iv-4.

As mentioned above, in this illustrative embodiments, by formula (I), the n value of represented compound is preferably more than 2, more preferably more than 4.

By formula (I), represented compound can be the combination that the n value is compound more than 4 and the n value compound that is 1～3.Described combination enables to control curing film strength and does not cause the deteriorated of charge delivery capability.

When the compound meaned when formula (I) is the combination that is compound more than 4 and the n value compound that is 1～3 of n value, total content with respect to the compound meaned by formula (I), more than the content that the n value is the compound more than 4 is preferably 5 % by weight, more preferably more than 20 % by weight.

Below listed the object lesson of the charge-transporting material with chain polymerization functional group except the represented compound of formula (I).But, described material is not limited to these examples.

With respect in order to form the composition of protective seam, more than the total content with charge-transporting material of chain polymerization is preferably 40 % by weight, more preferably more than 50 % by weight, more more preferably more than 60 % by weight.

When meeting above-mentioned scope, obtain good electrical properties, and make the cured film with adequate thickness.

In this illustrative embodiments, the charge-transporting material with chain polymerization functional group can be used in combination with the known charge-transporting material that does not have reactive group.The described known charge-transporting material that does not have reactive group does not have any reactive group that does not play electric charge conveying effect, therefore has advantages of the constituent concentration that improves charge-transporting material and further improves electrical properties.

As known charge-transporting material, can use those materials that are enumerated as the charge-transporting material that forms above-mentioned charge transport layer 3.

Other compositions that are used to form the composition of protective seam are described below.

The composition that is used to form protective seam can contain the following table surface-active agent, thereby has guaranteed film forming ability.

For example, described surfactant contains at least one structure in the choosing group that freely following structure forms in its molecule: the structure (A) formed by the polymerization of the propylene Monomer of acyls with fluorine atom; (B) there is the structure of carbon-carbon double bond and fluorine atom; (C) alkylene oxide structure; (D) there is the structure of carbon carbon triple bond and hydroxyl.

Described surfactant can contain at least one structure that is selected from (A)～(D) in its molecule, and can contain the combination of the two or more structure that is selected from (A)～(D) in its molecule.

Structure (A)～(D) further is described following with the surfactant with described structure.

(A) structure formed by the polymerization of the propylene Monomer of acyls with fluorine atom

The structure (A) formed by the polymerization of the propylene Monomer of acyls with fluorine atom is not particularly limited, but be preferably the structure that the polymerization by the propylene Monomer of acyls with fluoro-alkyl forms, the structure more preferably formed by the polymerization of the propylene Monomer of acyls with perfluoroalkyl.

Object lesson with surfactant of structure (A) comprises POLYFLOW KL-600 (being manufactured by chemistry society of common prosperity society), EFTOP EF-351, EF-352, EF-801, EF-802, EF-601 (by JEMCO, Inc. manufactures).

(B) there is the structure of carbon-carbon double bond and fluorine atom

Structure (B) with carbon-carbon double bond and fluorine atom is not particularly limited, but is preferably by the structure so that in following formula (B1) or formula (B2), at least one means.

Surfactant with structure (B) is preferably to have by formula (B1) or the compound of the group that at least one means (B2) in the side chain of acryloyl base polymer, or serves as reasons with the compound of any expression in following formula (B3)～(B5).

When the surfactant with structure (B) is to have by formula (B1) in the side chain of acryloyl base polymer or (B2) during the compound of the group that at least one means; other composition highly compatibles of described acryloyl group structure and described composition, this contributes to form uniform outmost surface layer.

Alternatively, when the surfactant with structure (B) is the compound of any expression in following formula (B3)～(B5), the contraction while having prevented coating, thus can suppress paint film defect.

In formula (B3)～(B5), v and w mean the integer more than 1 independently of one another, and R ' means hydrogen atom or any monovalent organic radical group, and Rf means independently of one another by (B1) or the group that (B2) means.

In formula (B3)～(B5), the example of any monovalent organic radical group meaned by R ' comprises the alkyl with 1～30 carbon atom and has the hydroxyalkyl of 1～30 carbon atom.

The example of commercially available prod with surfactant of structure (B) is enumerated as follows.

In formula (B3)～(B5), the example of the compound of any expression comprises FTERGENT100, 100C, 110, 140A, 150, 150CH, A-K, 501, 250, 251, 222F, FTX-218, 300, 310, 400SW, 212M, 245M, 290M, FTX-207S, FTX-211S, FTX-220S, FTX-230S, FTX-209F, FTX-213F, FTX-222F, FTX-233F, FTX-245F, FTX-208G, FTX-218G, FTX-230G, FTX-240G, FTX-204D, FTX-280D, FTX-212D, FTX-216D, FTX-218D, FTX-220D and FTX-222D (by Neos Company Limited, being manufactured).

In the side chain of acryloyl base polymer, have by formula (B1) or (B2) example of the compound of the structure that at least one means comprise KB-L82, KB-L85, KB-L97, KB-L109, KB-L110, KB-F2L, KB-F2M, KB-F2S, KB-F3M and KB-FaM (being manufactured by Neos Company Limited).

(C) alkylene oxide structure

Alkylene oxide structure (C) can be oxyalkylene or polyoxyalkylene.The object lesson of oxyalkylene comprises ethylene oxide and propylene oxide.In polyoxyalkylene, the repeat number of oxyalkylene can be 2～10000.

Example with surfactant of alkylene oxide structure (C) comprises polyglycol, polyether antifoam agent and polyether modified silicon oil.

Polyglycol preferably has the mean molecular weight below 2000.2000), Macrogol 600 (mean molecular weight: 600), PEG400 (mean molecular weight: 400) and Macrogol 200 (mean molecular weight: 200) example with polyglycol of the mean molecular weight below 2000 comprises Macrogol 2000 (mean molecular weight:.

Other preferred example comprise polyether antifoam agent, such as PE-M, PE-L (by manufacturing with the pure pharmaceutical worker's industry of light society), No. 1, defoamer and No. 5, defoamer (being manufactured by Hua Wangshe).

The example that has the surfactant of alkylene oxide structure (C) and fluorine atom in its molecule is included in those surfactants that have oxyalkylene or polyoxyalkylene in the side chain of the polymkeric substance with fluorine atom, and end replaces oxyalkylene or the polyoxyalkylene that the group that contains fluorine atom is arranged.

The object lesson that has the surfactant of alkylene oxide structure (C) and fluorine atom in its molecule comprises MEGAFAC F-443, F-444, F-445, F-446 (being manufactured by Dainippon Ink. & Chemicals Inc), FTERGENT250,251,222F (being manufactured by Neos Company Limited), POLY FOX PF636, PF6320, PF6520 and PF656 (You Bei village chemistry society manufactures).

The object lesson that has the surfactant of alkylene oxide structure (C) and siloxane structure in its molecule comprises KF351 (A), KF352 (A), KF353 (A), KF354 (A), KF355 (A), KF615 (A), KF618, KF945 (A), KF6004 (being manufactured by chemistry society of SHIN-ETSU HANTOTAI), TSF4440, TSF4445, TSF4450, TSF4446, TSF4452, TSF4453, TSF4460 is (by GE Toshiba Silicones Co., Ltd. manufacture), BYK-300, 302, 306, 307, 310, 315, 320, 322, 323, 325, 330, 331, 333, 337, 341, 344, 345, 346, 347, 348, 370, 375, 377, 378, UV3500, UV3510 and UV3570 (by BYK-ChemieJapan, being manufactured).

(D) there is the structure of carbon carbon triple bond and hydroxyl

Structure (D) with carbon carbon triple bond and hydroxyl is not particularly limited.Example with surfactant of this structure comprises following compound.

Surfactant with the structure (D) that contains carbon carbon triple bond and hydroxyl can be to have the compound of carbon carbon triple bond and hydroxyl in its molecule, and its object lesson comprises 2-propine-1-alcohol, 1-butine-3-alcohol, the 2-butyne-1-ol, the 3-butyne-1-ol, 1-pentyne-3-alcohol, valerylene-1-alcohol, the 3-pentyne-1-alcohol, the 4-pentyne-1-alcohol, 4-pentyne-2-alcohol, 1-hexin-3-alcohol, 2-hexin-1-alcohol, 3-hexin-1-alcohol, 5-hexin-1-alcohol, 5-hexin-3-alcohol, 1-heptyne-3-alcohol, 2-heptyne-1-alcohol, 3-heptyne-1-alcohol, 4-heptyne-2-alcohol, 5-heptyne-3-alcohol, 1-octyne-3-alcohol, 1-octyne-3-alcohol, 3-octyne-1-alcohol, 3-n-heptylacetylene-1-alcohol, 2-decine-1-alcohol, 3-decine-1-alcohol, 10-hendecyne-1-alcohol, 3-methyl isophthalic acid-butine-3-alcohol, 3-Methyl-1-pentene-4-alkynes-3-alcohol, methylpentynol, 5-methyl isophthalic acid-hexin-3-alcohol, 3-ethyl-1-pentyne-3-alcohol, 3-ethyl-1-heptyne-3-alcohol, 4-ethyl-1-octyne-3-alcohol, 3,4-dimethyl-1-pentyne-3-alcohol, 3,5-dimethyl-1-hexin-3-alcohol, 3,6-dimethyl-1-heptyne-3-alcohol, 2,2,8,8-tetramethyl-3,6-diine in the ninth of the ten Heavenly Stems-5-alcohol, 4,6-, 19 carbon diines-1-alcohol, 10,12-, 25 carbon diines-1-alcohol, 2-butine-Isosorbide-5-Nitrae-glycol, 3-hexin-2, the 5-glycol, 2,4-hexadiine-1, the 6-glycol, 2,5-dimethyl-3-hexin-2, the 5-glycol, 3,6-dimethyl-4-octyne-3, the 6-glycol, 2,4,7,9-tetramethyl-5-decine-4, the 7-glycol, (+)-1,6-bis-(2-chlorphenyl)-1,6-diphenyl-2,4-hexadiine-1,6-glycol, (-)-1,6-bis-(2-chlorphenyl)-1,6-diphenyl-2,4-hexadiine-1,6-glycol, 2-butine-Isosorbide-5-Nitrae-glycol two (2-hydroxyethyl), Isosorbide-5-Nitrae-diacetoxy-2-butine, 4-diethylamino-2-butyne-1-ol, 1,1-diphenyl-2-propine-1-alcohol, 1-ethinyl-1-cyclohexanol, 9-ethinyl-9-fluorenol, 2,4-hexadiindiol-1,6-bis-(4-phenylazo benzene sulfonate), 2-hydroxyl-3-tetrolic acid, 2-hydroxyl-3-ethyl butyn, 2-methyl 4-phenyl-3-butyne-2-alcohol, the methyl propargyl ether, 5-phenyl-4-pentyne-1-alcohol, 1-phenyl-1-propine-3-alcohol, 1-phenyl-2-propine-1-alcohol, 4-trimethyl silyl-3-butyne-2-alcohol and 3-trimethyl silyl-2-propine-1-alcohol.

Other examples comprise wherein partly or entirely hydroxyl and the above-claimed cpd combined such as oxyalkylenes such as ethylene oxides (for example, trade name: SURFYNOL400 series, by the manufacture of chemistry society of SHIN-ETSU HANTOTAI).

Surfactant with the structure (D) that contains carbon carbon triple bond and hydroxyl is preferably by with following formula (D1) or the compound that (D2) means.

In formula (D1) with (D2), R ^a, R ^b, R ^cAnd R ^dMean independently of one another any monovalent organic radical group, x, y and z mean the integer more than 1 independently of one another.

By formula (D1) or in the compound (D2) meaned, preferred R ^a, R ^b, R ^cAnd R ^dAlkyl, more preferably R ^aOr R ^bIn at least one, or R ^cOr R ^dIn at least one is branched alkyl, more more preferably z is 1～10, and x and y are 1～500.

By formula (D1) or the example of the commercially available prod of the compound (D2) meaned comprise SURFYNOL400 series (being manufactured by chemistry society of SHIN-ETSU HANTOTAI).

Having any surfactant in structure (A)～(D) can use separately, or two or more being used in combination with it.When being used in combination two or more surfactants, can add with the amount that does not affect described surfactant effect other surfactants with the structure that is different from structure (A)～(D).

The example of other surfactants comprises the following surfactant with fluorine atom or siloxane structure.

Can comprise perfluoro alkyl sulfonic acid (for example, perfluor fourth sulfonic acid and perfluorooctane sulfonate), perfluoro carboxylic acid (for example perfluoro butyl carboxylic acid and perfluoro capryl carboxylic acid) and the phosphate that contains perfluoroalkyl with the preferred example with surfactant with fluorine atom that in structure (A)～(D), any surfactant combination is used.Described perfluoro alkyl sulfonic acid and perfluoro carboxylic acid can be its salt or its acid amides modified derivative.

The example of the commercially available prod of perfluoro alkyl sulfonic acid comprises MEGAFAC F-114 (being manufactured by Dainippon Ink. & Chemicals Inc), EFTOP EF-101, EF102, EF-103, EF-104, EF-105, EF-112, EF-121, EF-122A, EF-122B, EF-122C, EF-123A (being manufactured by JEMCO Inc.), FTERGENT100,100C, 110,140A, 150,150CH, A-K and 501 (being manufactured by Neos Company Limited).

The example of the commercially available prod of perfluoro carboxylic acid comprises MEGAFAC F-410 (being manufactured by Dainippon Ink. & Chemicals Inc), EFTOP EF-201 and EF-204 (being manufactured by JEMCO Inc.).

The example of the commercially available prod of the phosphate that contains perfluoroalkyl comprises MEGAFAC F-493, F-494 (being manufactured by Dainippon Ink. & Chemicals Inc), EFTOP EF-123A, EF-123B, EF-125M, EF-132 (by JEMCO, Inc. manufactures).

Can be not limited to above-mentioned example with the example with surfactant with fluorine atom that in structure (A)～(D), any surfactant combination is used, other preferred example comprise contain fluorine atom betaine compound (for example, FTERGENT400SW, by Neos Company Limited, manufactured), with the surfactant with zwitter-ion group (for example, FTERGENT SW, manufactured by NeosCompany Limited).

Can comprise common silicone oils with the example with surfactant with siloxane structure that in structure (A)～(D), any surfactant combination is used, such as dimethyl siloxane, methyl phenyl siloxane, diphenyl siloxane and derivant thereof.

With respect to the total solids content of protective seam (outmost surface layer) 5, surface-active contents is preferably 0.01 % by weight～1 % by weight, more preferably 0.02 % by weight～0.5 % by weight.If surface-active contents is less than 0.01 % by weight, prevent that the effect of paint film defect may be not enough.On the other hand, if surface-active contents surpasses 1 % by weight, because surfactant and separating of cure component (compound and other monomers and oligomer that are meaned by formula (I)) may cause the cured film undercapacity.

In whole surfactant, more than the content with any surfactant in structure (A)～(D) is preferably 1 % by weight, more preferably more than 10 % by weight.

Purpose for physical strength, flexibility, planarization and the spatter property of the viscosity of control group compound, film, can join the free radical polymerization monomer or the oligomer that do not have charge-transporting in the composition that is used to form protective seam.

The example of simple function free radical polymerization monomer comprises isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, dodecylacrylate, the acrylic acid stearyl, isobornyl acrylate, cyclohexyl acrylate, acrylic acid 2-methoxy ethyl ester, methoxyl triethylene glycol acrylate, acrylic acid 2-ethoxyethyl group ester, the acrylic acid tetrahydro furfuryl ester, benzyl acrylate, the ethyl carbitol acrylate, acrylic acid phenoxy group ethyl ester, acrylic acid 2-hydroxyethyl ester, acrylic acid 2-hydroxy-propyl ester, acrylic acid 4-hydroxybutyl ester, methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate-styrene polymer, the phenoxy group polyethylene glycol acrylate, the phenoxy group polyethylene glycol methacrylate-styrene polymer, hydroxyethyl o-phenyl phenol acrylate and o-phenyl phenol glycidyl ether acrylate.

The example of difunctionality free radical polymerization monomer comprises 1,4-butanediol diacrylate, 1,6-hexanediyl ester, 1,9-nonanediol diacrylate, 2-normal-butyl-2-ethyl-1,3-PD diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, dioxane omega-diol diacrylate, polytetramethylene glycol acrylate, ethoxylated bisphenol a diacrylate, ethoxyquin bisphenol a dimethacrylate, tricyclodecane methanol diacrylate and tricyclodecane methanol dimethylacrylate.

The example of the free radical polymerization monomer that trifunctional is above comprises trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol acrylate, trimethylolpropane EO addition triacrylate, glycerine PO addition triacrylate, tricresyl phosphate acrylyl oxy-ethyl ester, tetramethylol methane tetraacrylate and ethoxylation isocyanuric acid triacrylate.

The example of free radical polymerization oligomers comprises epoxy acrylate oligomer, urethane acrylate oligomer and polyester acrylic ester oligomer.

With respect to the total solids content in composition, do not there is the free radical polymerization monomer of charge-transporting or the content of oligomer and can be preferably with 0 % by weight～50 % by weight, 0 % by weight～40 % by weight more preferably, then 0 % by weight～30 % by weight more preferably.

The composition that is used to form protective seam preferably contains thermal free radical initiator.

The cured film (cross linking membrane) that forms protective seam (outmost surface layer) can be cured and obtain by the method for utilizing heat, light or electron beam etc. by the composition that will contain said components.In order to obtain the cured film had such as the equilibrium property of electrical properties and physical strength etc., described film is preferably by heat and is cured.For solidifying of conventional acryloyl class coating, preferably can realize the curing electron beam of on-catalytic and can realize quick-setting photopolymerization.Yet, in Electrophtography photosensor, the photographic layer that forms the outmost surface layer contains photosensitive material.Therefore, in order to be down to minimum to the damage of described photosensitive material, and improve the surface nature of the cured film will formed, preferably carry out the heat curing of gentle reaction.

Therefore, can be in the situation that catalyst-free carry out heat curing, but preferably by thermal free radical initiator, carry out catalysis.

Described thermal free radical initiator is not particularly limited, but is preferably those thermal free radical initiators that use 10 hours half life temperatures with 40 ℃～110 ℃, thereby can be suppressed in the protective seam forming process damage to the photographic layer photosensitive material.

The example of the commercially available prod of thermal free radical initiator comprises following product.The temperature provided in parenthesis refers to 10 hours half life temperatures.

Azo initiator, such as V-30 (104 ℃), V-40 (88 ℃), V-59 (67 ℃), V-601 (66 ℃), V-65 (51 ℃), V-70 (30 ℃), VF-096 (96 ℃), Vam-110 (111 ℃), Vam-111 (111 ℃) (manufacture of the pure pharmaceutical worker's industry of each freedom and light society), OT _AZO-15 (61 ℃), OT _AZO-30, AIBM (65 ℃), AMBN (67 ℃), ADVN (52 ℃) or ACVA (68 ℃) (each chemical society of freely large mound manufactures), PERTETRA A, PERHEXA HC, PERHEXA C, PERHEXA V, PERHEXA22, PERHEXA MC, PERBUTYL H, PERCUMYL H, PERCUMYL P, PERMENTA H, PEROCTA H, PERBUTYL C, PERBUTYL D, PERHEXYL D, PEROYL IB, PEROYL355, 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, PERHEXA250, PEROCTA O, PERHEXYL O, PERBUTYL O, PERBUTYL L, PERBUTYL355, PERHEXYL I, PERBUTYL I, PERBUTYL E, PERHEXA 25Z, PERBUTYL A, PERHEXYL Z, PERBUTYL ZT, PERBUTYL Z (each free NOF Corporation manufactures), KAYAketal AM-C55, TRIGONOX36-C75, LAUROX, PERKADOX L-W75, PERKADOX CH-50L, TRIGONOX TMBH, KAYACUMENE H, KAYAbutyl H-70, PERKADOX BC-FF, KAYAHEXA AD, PERKADOX14, KAYABUTYL C, KAYABUTYL D, KAYAHEXA YD-E85, PERKADOX12-XL25, PERKADOX12-EB20, TRIGONOX 22-N70, TRIGONOX22-70E, TRIGONOX D-T50, TRIGONOX423-C70, KAYAESTER CND-C70, KAYAESTER CND-W50, TRIGONOX23-C70, TRIGONOX23-W50N, TRIGONOX257-C70, KAYAESTER P-70, KAYAESTER TMPO-70, TRIGONOX121, KAYAESTER O, KAYAESTER HTP-65W, KAYAESTER AN, TRIGONOX42, TRIGONOX F-C50, KAYABUTYL B, KAYACARBON EH-C70, KAYACARBON EH-W60, KAYACARBON I-20, KAYACARBON BIC-75, TRIGONOX117, KAYALENE6-70 (each free Kayaku Akzo Corporation manufactures), LUPEROX LP (64 ℃), LUPEROX610 (37 ℃), LUPEROX188 (38 ℃), LUPEROX844 (44 ℃), LUPEROX259 (46 ℃), LUPEROX10 (48 ℃), LUPEROX701 (53 ℃), LUPEROX11 (58 ℃), LUPEROX26 (77 ℃), LUPEROX80 (82 ℃), LUPEROX7 (102 ℃), LUPEROX270 (102 ℃), LUPEROX P (104 ℃), LUPEROX546 (46 ℃), LUPEROX554 (55 ℃), LUPEROX575 (75 ℃), LUPEROX TANPO (96 ℃), LUPEROX555 (100 ℃), LUPEROX570 (96 ℃), LUPEROX TAP (100 ℃), LUPEROX TBIC (99 ℃), LUPEROX TBEC (100 ℃), LUPEROX JW (100 ℃), LUPEROX TAIC (96 ℃), LUPEROX TAEC (99 ℃), LUPEROX DC (117 ℃), LUPEROX101 (120 ℃), LUPEROX F (116 ℃), LUPEROX DI (129 ℃), LUPEROX130 (131 ℃), LUPEROX220 (107 ℃), LUPEROX230 (109 ℃), LUPEROX233 (114 ℃) and LUPEROX531 (93 ℃) (each free Arkema Yoshitomi, Ltd. manufactures).

With respect to the reactive compounds in composition, the content of described thermal free radical initiator is preferably 0.001 % by weight～10 % by weight, 0.01 % by weight～5 % by weight more preferably, then 0.1 % by weight～3 % by weight more preferably.

In being used to form the composition of protective seam; purpose for the oxidation that suppresses excessive absorption by the gas of discharge generation and effectively suppress thus to be caused by produced gas; can add other thermoset resins, such as phenol resin, melamine resin or benzoguanamine resin.

In addition, in being used to form the composition of protective seam, can further add coupling agent, hard coating agent or fluorochemicals to adjust film forming, flexibility, lubricity or the cohesive of film.The object lesson of described adjuvant comprises various silane coupling agents and commercially available siloxane hard coating agent.

The example of silane coupling agent comprises vinyl trichlorosilane, vinyltrimethoxy silane, vinyltriethoxysilane, γ-glycidoxypropyl methyldiethoxysilane, γ-glycidoxypropyltrimewasxysilane, γ aminopropyltriethoxy silane, the gamma-amino propyl trimethoxy silicane, gamma-amino propyl group methyl dimethoxysilane, N-β-(amino-ethyl)-γ aminopropyltriethoxy silane, tetramethoxy-silicane, methyltrimethoxy silane and dimethyldimethoxysil,ne.

The example of commercially available hard coating agent comprises KP-85, X-40-9740 and X-8239 (trade name, all by Shin-Etsu Silicone Co., Ltd. manufacture) and AY42-440, AY42-441 and AY49-208 (trade name, all by Dow Corning Toray Co., Ltd. manufactures).

In addition, in order to introduce hydrophobicity, can add fluorochemicals, such as (ten three fluoro-1,1,2,2-tetrahydrochysene octyl group) triethoxysilane, (3,3,3-trifluoro propyl) trimethoxy silane, 3-(seven fluorine isopropoxies) propyl-triethoxysilicane, 1H, 1H, 2H, 2H-perfluoroalkyl triethoxysilane, 1H, 1H, 2H, 2H-perfluor decyl triethoxysilane or 1H, 1H, 2H, 2H-perfluoro capryl triethoxysilane.

Silane coupling agent can be used with any amount.Yet the weight of fluorochemicals is preferably set to below 0.25 times of amount of not fluorine-containing compound.The excessive shortcoming that will cause the film forming aspect of cross linking membrane.

In addition; in the composition in order to form protective seam, can add thermoplastic resin to improve discharge gas tolerance, physical strength and mar resistance, and further reduce moment of torsion; control wear extent, extend storage period and be controlled at respectively particle dispersion and the viscosity in protective seam.

The example of thermoplastic resin comprises: polyvinyl acetal resin, as polyvinyl butyral resin, vinyl-formal resin or the polyvinyl acetal resin of the part acetalation that wherein butyral is modified through dimethoxym ethane or acetyl acetal (acetoacetal) part (for example, S-LEC B, K (trade name, by the ponding chemistry, society manufactures)), polyamide, celluosic resin and polyvinyl phenol resin.Angle preferably polyethylene acetal resin and polyvinyl phenol resin from electrical specification.The weight-average molecular weight of described resin is preferably 2000～100, and 000, more preferably 5,000～50,000.When the weight-average molecular weight of described resin is less than at 2,000 o'clock, the additive effect of resin tends to deficiency.On the other hand, when the weight-average molecular weight of described resin surpasses at 100,000 o'clock, dissolubility reduces to tend to cause limiting addition and causes the film forming defect in coating.The addition of resin is preferably 1 % by weight～40 % by weight, 1 % by weight～30 % by weight more preferably, then 5 % by weight～20 % by weight more preferably.When the addition of resin is less than 1 % by weight, the additive effect of resin tends to deficiency.On the other hand, when its addition surpasses 40 % by weight, hot and humid degree (for example, 28 ℃, 85%RH) in the environment, tend to occur image blurring.

In being used to form the composition of protective seam, preferably add antioxidant deteriorated because of the oxidizing gas such as ozone that charhing unit produces to suppress protective seam.If the physical strength of photosensitive surface increases and make thus the life of photoreceptor, photoreceptor becomes the time in the past longer with the oxidizing gas contact gear ratio.As a result, need than stronger in the past oxidative resistance.

Antioxidant is preferably hindered phenol antioxidant or hindered amine antioxidant, and also can use known antioxidant, such as organic sulfur antioxidant, phosphite antioxidant, dithiocar-bamate antioxidant, thiocarbamide antioxidant or benzimidazole antioxidant.The addition of antioxidant is preferably below 20 % by weight, more preferably below 10 % by weight.

The example of hindered phenol antioxidant comprises 2, the 6-di-tert-butyl-4-methy phenol, 2, the 5-di-tert-butyl hydroquinone, N, N'-hexa-methylene two (3, 5-di-t-butyl-4-hydroxyl) hydrocinnamamide, 3, 5-di-t-butyl-4-hydroxyl-benzylphosphonic acid diethyl ester, 2, 4-bis-[(octylsulfo) methyl]-orthoresol, 2, 6-di-t-butyl-4-ethyl-phenol, 2, 2'-methylene two (4-methyl-6-tert-butylphenol), 2, 2'-methylene two (4-ethyl-6-tert-butyl phenol), 4, 4'-butylidene two (3 methy 6 tert butyl phenol), 2, 5-bis-amyl hydroquinone, the 2-tert-butyl group-6-(3-butyl-2-hydroxy-5-methyl-benzyl)-4-aminomethyl phenyl acrylate and 4, 4'-butylidene two (3 methy 6 tert butyl phenol).

In addition, in being used to form the composition of protective seam, can add various particles to reduce the physical strength of residual electromotive force or raising protective seam.

The example of described particle comprises silicon-containing particles.Described silicon-containing particles is to contain silicon those particles as component, particularly, can enumerate silica gel and siloxane particles.The silica gel that is used as silicon-containing particles is selected from and contains acidity or alkaline water dispersion liquid and organic solvent (such as alcohol, ketone or the ester) dispersion liquid that mean grain size is 1nm～100nm the silica gel that is preferably 10nm～30nm.Can use commercially available silica gel.Silica gel solid body burden in protective seam is not particularly limited.Yet from the angle of film forming, electrical specification and physical strength, with respect to the total solids content in protective seam, the silica gel solid body burden is 0.1 % by weight～50 % by weight, and is preferably 0.1 % by weight～30 % by weight.

The silica dioxide granule that is selected from silicon resin particle, silicone rubber particles and processes through siloxane surface as the siloxane particles of silicon-containing particles, and usually use commercially available siloxane particles.Siloxane particles forms spherical, and its mean grain size is preferably 1nm～500nm, and 10nm～100mn more preferably.Described siloxane particles is chemically inert fine granular, and the excellent dispersion in resin realizes that the necessary content of enough characteristics is lower, and therefore in the situation that do not disturb cross-linking reaction to improve the surface nature of Electrophtography photosensor.That is to say, in siloxane particles is incorporated into to the rigidity cross-linked structure and do not cause under the state of fluctuating, lubricity and the hydrophobicity on Electrophtography photosensor surface are improved, and have kept thus excellent wearing quality and resistant thing tack in the long period.

With respect to the total solids content in protective seam, the siloxane particles content in protective seam is preferably 0.1 % by weight～30 % by weight, more preferably 0.5 % by weight～10 % by weight.

The example of other particles comprises: the fluorine class particle of tetrafluoroethene, trifluoro-ethylene, hexafluoropropylene, fluorothene or vinylidene fluoride; As " Preprints of the8th Polymer Material Forum, the p.89 " particle that the described resin obtained by fluororesin and hydroxyl monomer copolymerizable is made; With the semiconduction metal oxide, such as ZnO-Al ₂O ₃, SnO ₂-Sb ₂O ₃, In ₂O ₃-SnO ₂, ZnO ₂-TiO ₂, ZnO-TiO ₂, MgO-Al ₂O ₃, FeO-TiO ₂, TiO ₂, SnO ₂, In ₂O ₃, ZnO or MgO.In addition, can add oil for identical purpose, as silicone oil.The example of silicone oil comprises: silicone oil, such as dimethyl polysiloxane, diphenyl polysiloxane or phenyl methyl siloxane; Reactive silicone oil, modify polysiloxane, methacryl modification polysiloxane, sulfydryl modification polysiloxane or phenol such as amido modified polysiloxane, epoxy group modified polysiloxane, carboxyl modified polysiloxane, methyl alcohol and modify polysiloxane; Ring-type dimethyl cyclosiloxane, such as hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane or ten diformazan basic ring six siloxane; The ring-type methyl phenyl ring siloxane, such as 1,3,5-trimethyl-1,3,5-triphenyl cyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenyl cyclotetrasiloxane or 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentaphene basic ring five siloxane; The ring-type phenyl ring siloxane, such as the hexaphenyl cyclotrisiloxane; Fluorine-containing cyclosiloxane, such as (3,3,3-trifluoro propyl) methyl cyclotrisiloxane; The cyclosiloxane of hydrogeneous silicyl, such as methyl hydrogen siloxane potpourri, pentamethyl D5 or phenyl hydrogen cyclosiloxane; With the cyclosiloxane containing vinyl, such as five vinyl pentamethyl D5s.

In being used to form the composition of protective seam, can add metal, metal oxide or carbon black etc.The example of metal comprises aluminium, zinc, copper, chromium, nickel, silver and stainless steel, and surface deposition has the plastic grain of these metals arbitrarily.The example of metal oxide comprises zinc paste, titanium dioxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, antimony or tantalum doping tin oxide and antimony doped zirconia.These materials can be used alone or with at least two kinds be used in combination wherein.When wherein at least two kinds while being used in combination, can adopt any in simple mixtures, its solid solution and motlten metal oxide.From the angle of the transparency of protective seam, the mean grain size of conductive particle is preferably below 0.3 μ m, is particularly preferably below 0.1 μ m.

Preferably be prepared as protective seam formation coating fluid in order to the composition that forms protective seam.Protective seam forms and can not contain solvent with coating fluid, or can contain solvent as required, and alcohols for example, such as methyl alcohol, ethanol, propyl alcohol, butanols, cyclopentanol or cyclohexanol; Ketone, such as acetone or methyl ethyl ketone; Or ethers, such as tetrahydrofuran, Anaesthetie Ether or dioxane.

These solvents can be used alone or use with the potpourri of at least two kinds wherein, and preferably have the boiling point below 100 ℃.As solvent, preferably use at least one solvent with hydroxyl (for example, alcohols).

The protective seam that will contain to form the composition of protective seam according to conventional coating process forms and is applied on charge transport layer with coating fluid, and described coating process is as scraper plate rubbing method, the excellent rubbing method that winds the line, spraying process, dip coating, slot scraping rubbing method (bead coating method), airblade coating method or curtain formula rubbing method.Then, if necessary, thereby heating obtains solidfied material by curing of coatings at the temperature of 100 ℃～170 ℃.As a result, obtain the protective seam (outmost surface layer) made by solidfied material.

Form by the oxygen concentration in coating fluid curing and be preferably below 1% at protective seam, more preferably below 1000ppm, more more preferably below 500ppm.

Except being applied to photoreceptor, protective seam forms with coating fluid and for example also can be used in the fluorescence photochromic coating, or in the antistatic film on glass surface or frosting.When using described coating fluid, formed lower floor has been shown to excellent adhering film, and suppressed thus to reuse for a long time the performance degradation caused.

As Electrophtography photosensor, the example of function divergence type has more than been described.The content of the charge generating material in single-layer type photographic layer 6 (charge generation/charge transport layer) is 10 % by weight～85 % by weight, or about 85 % by weight of 10 % by weight～approximately, and is preferably 20 % by weight～50 % by weight.The content of charge-transporting material is preferably 5 % by weight～50 % by weight.The method that forms single-layer type photographic layer 6 (charge generation/charge transport layers) is carried out according to the same way as in the method that forms charge generation layer 2 and charge transport layer 3.The film thickness of single-layer type photographic layer (charge generation/charge transport layer) 6 preferably sets and is being essentially 5 μ m～50 μ m, or about 50 μ m of 5 μ m～approximately, and 10 μ m～40 μ m more preferably.

In above-mentioned illustrative embodiments, having described the outmost surface layer of wherein being made by the solidfied material of particular composition is the form of protective seam.Yet, not forming therein in the situation of layer structure of protective seam, the charge transport layer that is positioned at the outmost surface place of described layer structure is the outmost surface layer.

Image processing system/handle box

Fig. 4 is the schematic configuration diagram of the related image processing system 100 of demonstration illustrative embodiments of the present invention.

Image processing system 100 shown in Fig. 4 comprises: the handle box 300 that is equipped with Electrophtography photosensor 7; Exposure sources (electrostatic latent image formation unit) 9; Transfer apparatus (transfer printing unit) 40; With intermediate transfer medium 50.In image processing system 100, exposure sources 9 is arranged at the position that can Electrophtography photosensor 7 be exposed by the opening on handle box 300, transfer apparatus 40 is arranged at the position that faces Electrophtography photosensor 7 across intermediate transfer medium 40, and intermediate transfer medium 50 is set to contact with Electrophtography photosensor 7 parts.

Handle box 300 in Fig. 4 integrally holds Electrophtography photosensor 7, charging equipment (charhing unit) 8, developing apparatus (developing cell) 11 and cleaning equipment 13 in housing.Cleaning equipment 13 comprises cleaning doctor (cleaning member), and described cleaning doctor 131 is set to contact with the surface of Electrophtography photosensor 7.

Show such example in Fig. 4, wherein as cleaning equipment 13, provide in order to the fibrous member 132 (roller) of lubricant 14 to be provided on photoreceptor 7 surfaces, and used fibrous member 133 (surface brush) clean to assist.Yet these can be used as required.

As charging equipment 8, used contact-type charging device, it adopts for example electric conductivity or semiconduction charging roller, charging brush, charging film, charging rubber scraper or charging valve.Can use too known charging devices such as noncontact roll-type charging device, the gate type corona tube corona charging device that utilizes corona discharge or corona tube corona charging device.

Although do not illustrate in the drawings, also can by the temperature in order to improve Electrophtography photosensor 7 with the photoreceptor heater block that reduces relative temperature be arranged on Electrophtography photosensor around to improve picture steadiness.

As exposure sources 9, can enumerate and use so that the optical devices that semiconductor laser beam, LCD light or liquid crystal shutter optical expose with desirable imaging mode on the surface of photoreceptor 7.The optical source wavelength of employing within photoreceptor spectrum sensitive scope.As for semiconductor laser wavelength, mainly adopt near the near infrared of oscillation wavelength 780nm.Yet, be not limited to described wavelength, also can use the laser of the oscillation wavelength with 600nm left and right, or be the laser of the oscillation wavelength with 400nm～450nm left and right of blue laser.In addition, when forming coloured image, the surface-emission laser light source that can export multiple beam is also effective.

As developing apparatus 11, can use conventional developing apparatus, wherein for example adopt magnetic or non-magnetic mono-component developer or two-component developing agent to be developed with contact or discontiguous mode.Can select developing apparatus according to purpose, as long as there is above-mentioned functions.For example, can enumerate known developing apparatus, wherein brush by use or roller is attached to single component or two-component developing agent on photoreceptor 7.In the middle of these, preferably use developer is remained on to its lip-deep developer roll.

Hereinafter, the toner for developing apparatus 11 has been described.

The monocomponent toner that described developer can be comprised of toner, or the two-component developing agent that comprises toner and carrier.

Toner for example by toner particle and the external additive used in case of necessity form, described toner particle contains adhesive resin, colorant and such as other optional adjuvants such as detackifiers.

(the equal shape coefficient of number, this shape coefficient is expressed as (ML to the average shape factor of toner particle ²/ A) * (π/4) * 100, wherein ML means the largest particles length, and A means the projected area of particle) be preferably 100～150, more preferably 105～145, more more preferably 110～140.The volume average particle size of toner is preferably 3 μ m～12 μ m, 3.5 μ m～10 μ m more preferably, then 4 μ m～9 μ m more preferably.

Toner is not subject to the special restriction of its manufacture method.Can use the toner of manufacturing according to following methods, for example mixing comminuting method, wherein add adhesive resin, colorant, detackifier and the charge control agent of use, mixing, also sorting of pulverizing subsequently in case of necessity; The particle wherein described mixing comminuting method obtained changes the method for shape by physical shock or heat energy; The emulsion polymerization agglutination, wherein will be in order to obtain the polymerizable monomer emulsion polymerization of adhesive resin, then by the dispersion liquid of gained, colorant and detackifier and the dispersion phase mixing of spendable charge control agent in case of necessity, aggegation subsequently, heating and melting obtain toner; Suspension polymerization, wherein will in order to the polymerizable monomer, colorant and the release agent that obtain adhesive resin and in case of necessity the solution of spendable charge control agent be suspended in aqueous solvent to carry out polymerization; Perhaps dissolve suspension method, wherein by adhesive resin, colorant and detackifier and in case of necessity the solution of spendable charge control agent be suspended in aqueous solvent and carry out granulation.

In addition, also can adopt known manufacture method, such as the toner that wherein will adopt said method to obtain, as core, and the particle that will flocculate is further attached to it, with the method by heating and melting formation core-shell structure.As the method for manufacturing toner, from the angle that shape is controlled and particle diameter distributes and controls, the suspension polymerization, emulsion polymerization agglutination and the dissolving suspension method that preferably all adopt aqueous solvent to be manufactured, and emulsion polymerization agglutination particularly preferably.

For example adopt Henschel mixer or V-type stirrer that toner particle is mixed to the manufacture toner mutually with external additive.When with wet method, manufacturing toner particle, external additive can add with wet method.

When toner is used as two-component developing agent, the blending ratio of toner and carrier is set in known ratio.There is no particular restriction for carrier, but its preferred example comprises its surface-coated, the magnetic-particle of resin arranged.

As transfer apparatus 40, can use known charging device equally, such as using for example contact transfer printing charging device of band, roller, film or rubber scraper; Or utilize gate type corona tube corona charging device or the corona tube corona charging device of corona discharge.

As intermediate transfer medium 50, can use the band (intermediate transfer belt) of being made by semiconductive polyimide, polyamidoimide, polycarbonate, poly-fragrant fat, polyester or rubber etc.As the form of intermediate transfer medium 50, except band, can also use drum.

Except above-mentioned each equipment, described image processing system 100 for example can also have to photoreceptor 7 carry out light except electric light except electrical equipment.

Fig. 5 is the schematic cross-section of the image processing system 120 that shows that another illustrative embodiments of the present invention relates to.

At the image processing system 120 shown in Fig. 5, are the tandem full-color image forming apparatus that comprise four handle boxes 300.

Described image processing system 120 has four handle boxes 300 that are arranged side by side separately on intermediate transfer medium 50, and has the structure of an Electrophtography photosensor for a kind of color.Except image processing system 120 forms series system, image processing system 120 has the structure identical with image processing system 100.

Image processing system related in this illustrative embodiments is not limited to said structure, also can use the image processing system of other known manner.

In above-mentioned illustrative embodiments, the outmost surface layer of Electrophtography photosensor is made by the cured film of following composition, and described composition contains formula (M1) compound meaned and the charge-transporting material with chain polymerization functional group.Yet described cured film is not limited to above-mentioned a kind of.Described cured film can for example be applied to organic electroluminescent (EL) device, storage arrangement or Wavelength converter.

As mentioned above, when described cured film contains the compound shown in formula (M1), kation, negative ion or the free radical for example, produced by initiating agent and stimulation (heat, electron beam or light) optionally attack chain polymerization functional group with the begin chain polymerization, thereby avoided the attack to the part of the charge transport in charge-transporting material (charge transport skeleton).Thus, can think that cured film is in the situation that do not damage charge-transporting and form.Therefore, described film shows good film forming when forming multilayer, and can not cause often seeing in conventional film because the thermogenetic pattern of joule changes.In other words, except such as solvent resistance and thermotolerance, also given described cured film good charge-transporting.

As a result, described cured film can be used for such use.

Embodiment

Further describe illustrative embodiments of the present invention referring to embodiment, but the present invention is not limited to these embodiment.

Embodiment 1

The manufacture of Electrophtography photosensor

The preparation of undercoat

At first, by the zinc paste of 100 weight portions (mean grain size: 70nm, specific surface area: 15m ²/ g, by TEIKA Co., Ltd. manufactures) with 500 parts by weight of toluene, mix mutually and stir, 1.3 weight portion silane coupling agents (trade name: KBM503 is manufactured by chemistry society of SHIN-ETSU HANTOTAI), stir 2 hours subsequently wherein., remove toluene, subsequently in 120 ℃ of bakings 3 hours, thereby obtain through silane coupling agent surface-treated zinc paste thereafter.

Then, when stirring, the surface treated zinc paste of 110 weight portion is mixed mutually with 500 weight portion tetrahydrofurans.Add by 0.6 weight portion alizarin being dissolved in to the solution obtained in 50 weight portion tetrahydrofurans in described potpourri, stir 5 hours in 50 ℃ subsequently.Subsequently, filtration under diminished pressure is added with the zinc paste of alizarin, subsequently in 60 ℃ of drying under reduced pressure, thereby obtains being added with the zinc paste of alizarin.

After this, by passing through the zinc paste that is added with alizarin of 60 weight portions, 13.5 weight portion rigidizer (blocked isocyanates of 38 weight portions, trade name: SUMIDULE3175, by Sumitomo-Bayer Urethane Co., Ltd. manufacture) and 15 weight portion butyral resins (trade name: S-LEC BM-1, by ponding chemistry society, manufactured) be blended in the solution obtained in 85 weight portion methyl ethyl ketones and mix mutually with the methyl ethyl ketone of 25 weight portions, use subsequently the sand mill of the beaded glass that adopts diameter 1mm φ to disperse 2 hours, thereby obtain dispersion liquid.

Add two lauric acid dioctyl tins and the 40 weight portion silicon resin particle (trade names: TOSPEARL145 of 0.005 weight portion as catalyzer in the gained dispersion liquid, by GE-Toshiba Silicone Co., Ltd. manufacture), thus undercoat formation coating fluid obtained.By dipping, described coating fluid is applied on aluminum substrate, subsequently in 170 ℃ of dryings with solidify 40 minutes, thereby obtains the undercoat that thickness is 20 μ m.

The preparation of charge generation layer

At first, use adopts the sand mill of the beaded glass of diameter 1mm φ will contain the phthalocyanine of the hydroxyl as charge generating material gallium, 10 weight portion vinyl chloride/vinyl acetate copolymer resin (trade names: VMCH of 15 weight portions, by Nippon Unicar Co., Ltd. manufacture) and the potpourri dispersion of 200 weight portion n-butyl acetates 4 hours, in the x-ray diffraction pattern obtained with CuK α characteristic X ray, at least at the Bragg angle, (2 θ ± 0.2 °) is 7.3 °, 16.0 °, 24.9 ° and 28.0 ° and locates to have diffraction peak wherein said hydroxyl phthalocyanine gallium.Add 175 weight portion n-butyl acetates and 180 weight portion methyl ethyl ketones in the gained dispersion liquid, stir subsequently, thereby obtain charge generation layer formation coating fluid.By dipping, described charge generation layer is formed and is applied on undercoat with coating fluid, subsequently in room temperature (25 ℃) drying, thus the charge generation layer of formation film thickness 0.2 μ m.

The preparation of charge transport layer

At first, by 45 weight portion N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl) [1,1'] xenyl-4,4'-diamines (hereinafter referred to " TPD ") and 55 weight portion bisphenol Z polycarbonate resins (hereinafter referred to " PCZ500 ", viscosity average molecular weigh: 50000) be dissolved in 800 weight portion chlorobenzenes, thereby obtain charge transport layer formation coating fluid.Described coating fluid is applied on charge generation layer, subsequently in 130 ℃ of heating 45min, thus the charge transport layer of formation thickness 20 μ m.

The preparation of protective seam

The monomer that the compound (compound ii-22) that 120 weight portions are meaned by formula (I) and 40 weight portions do not have charge-transporting (trade name: A-DCP, You Xinzhong village chemical industry society manufactures) is dissolved in 100 weight portion tetrahydrofurans (THF).Subsequently; by 3 weight portion initiating agent (trade names: VE-73; by manufacturing with the pure pharmaceutical worker's industry of light society) and 5 weight portions by compound (the compound M-1 of formula (M1) expression; trade name: triphenyl methane; changing into society by Tokyo manufactures) be dissolved in described solution, thereby forming, the layer that is protected uses coating fluid.Described coating fluid is applied on charge transport layer, then heating 40 minutes in 145 ℃ of atmosphere that are about 100ppm in oxygen concentration, thus form the protective seam of thickness 8 μ m.

Obtain in this way Electrophtography photosensor.Described photoreceptor is called photoreceptor 1.

Assessment

The Electrophtography photosensor of so manufacturing is installed to 700Digital Color Press (being manufactured by Fuji Xerox Co., Ltd) upper, and in 10 ℃, the environment of 15%RH printing 10% half tone image on 10000 pages of paper continuously.

After 10000 pages of printings, carry out image evaluation test (1) in equivalent environment.In image evaluation test (1) afterwards, image processing system is kept 24 hours in 28 ℃, 80%RH, then continue printing.Image quality to the first page image in equivalent environment carries out image evaluation test (2).

In image evaluation test (1) and (2), the afterimage phenomena (hereinafter referred to " ghost image ") of having assessed the even property of density unevenness, striped, image deterioration of the following stated and having caused due to residual formerly image.

Use P paper (A4 size, laterally paper feed, manufactured by Fuji Xerox Co., Ltd) in imaging test.

Assessment result is listed in table 3 and 4.

The assessment of the even property of density unevenness

Adopt 5% shadow tone sample to carry out visual assessment to the even property of density unevenness.

A: excellence.

B: observe the even property of part density unevenness.

C: observe from the image quality angle and think the even property of problematic density unevenness.

The striped assessment

Adopt 10% shadow tone sample to carry out visual assessment to striped.

A: excellence.

B: part striped.

C: observe from the image quality angle and think problematic striped.

The image deterioration assessment

Together with above-mentioned test, also as followsly carried out the image deterioration assessment.

Adopt 10% shadow tone sample to carry out visual assessment to image deterioration.

A: excellence.

B: do not find the image deterioration problem in the continuous printing test, but pinpoint the problems after placing 24 hours.

C: even also pinpoint the problems in the continuous printing test.

The ghost image assessment

By after the pattern table with G and black region as shown in Figure 6A of printing, visualization in black region symbol G present degree, assess ghost image.

A: excellent or very slight, as shown in Figure 6A.

B: slightly remarkable, as shown in Figure 6B.

C: clear confirmation, as shown in Figure 6 C.

Surface observation

Following observation and assessment are carried out in Electrophtography photosensor surface after each time in image evaluation test (1) and (2) observed.

A: excellence, that is, even both do not found under 20 times of amplifications that scratch did not have to find to adhere to yet yet.

B: under 20 times of amplifications, find slight scratch or adhere to.

C: be observed visually scratch or adhere to.

Embodiment 2-11, comparative example 1

The manufacture of Electrophtography photosensor

According to same way as in embodiment 1, carry out to the step formed till charge transport layer.Composition in protective seam becomes as shown in table 1 and 2, and the layer that is protected thus forms uses coating fluid.Described coating fluid is applied on charge transport layer, and heating 40 minutes in 145 ℃ of atmosphere that are about 100ppm in oxygen concentration, forms thus the protective seam of thickness 8 μ m.

Obtain Electrophtography photosensor by said method.These photoreceptors are called photoreceptor 2～11, and relatively use photoreceptor 1.

Assessment

Same way as according to embodiment 1 is assessed the photoreceptor so obtained.Result is presented in table 3 and 4.

Embodiment 12

The manufacture of Electrophtography photosensor

According to same way as in embodiment 1, carry out to the step formed till charge transport layer.Composition in protective seam becomes as shown in table 2, and the layer that is protected thus forms uses coating fluid.Described coating fluid is applied on charge transport layer, and uses that to carry out illumination in the atmosphere that metal halide lamp (being manufactured by Ushio Inc.) is about 100ppm in oxygen concentration be 700mW/cm ²The UV at (365nm place) irradiates 60 seconds.Coating, in 145 ℃ of heating 40 minutes, is formed to the protective seam that thickness is 8 μ m thus.

Obtain Electrophtography photosensor by said method.Described photoreceptor is called photoreceptor 12.

Assessment

Embodiment 13-15

The manufacture of Electrophtography photosensor

According to same way as in embodiment 1, carry out to the step formed till charge generation layer.Composition in charge transport layer becomes as shown in table 2.The listed compound meaned by formula (I), the monomer that does not have charge-transporting, initiating agent in table 2 and the compound that meaned by formula (M1) are dissolved in the tetrahydrofuran (THF) of 180 weight portions, obtain thus charge transport layer and form and use coating fluid.Described coating fluid is applied on charge generation layer, and heating 40 minutes in 145 ℃ of atmosphere that are about 100ppm in oxygen concentration, forms thus the charge transport layer of thickness 17 μ m.

Obtain Electrophtography photosensor by said method.These photoreceptors are called photoreceptor 13～15.

Assessment

Same way as according to embodiment 1 is assessed the photoreceptor so obtained.Result is presented in table 4.

Table 1

Table 2

Table 3

Table 4

The above results shows, with comparative example 1, compares, and aspect the even property of density unevenness, striped, image deterioration and surface observation, embodiment 1～15 realizes comprehensively better result.

Abbreviation in table 1～4 is as follows:

M-1: the compound meaned by formula (M1) (trade name: triphenyl methane changes into society by Tokyo and manufactures)

M-6: the compound meaned by formula (M1) (trade name: BisP-IOTD, chemistry society manufactures by Honshu)

M-7: the compound meaned by formula (M1) (trade name: BisP-BA, chemistry society manufactures by Honshu)

M-8: the compound meaned by formula (M1) (trade name: BisP-PHBA, chemistry society manufactures by Honshu)

TPD:N, N '-diphenyl-N, N '-bis-(3-aminomethyl phenyl)-[1,1 '] xenyl-4,4 '-diamines

A-DCP: the monomer (manufacture of You Xinzhong village chemical industry society) that does not there is charge-transporting

A-DPH: the monomer (manufacture of You Xinzhong village chemical industry society) that does not there is charge-transporting

Z-400: the monomer (the bisphenol Z polycarbonate is manufactured by Mitsubishi Chemical society) that does not there is charge-transporting

VE-73: initiating agent (hot radical produces agent, by manufacturing with the pure pharmaceutical worker's industry of light society)

VE-75: initiating agent (hot radical produces agent, by manufacturing with the pure pharmaceutical worker's industry of light society)

V-601: initiating agent (hot radical produces agent, by manufacturing with the pure pharmaceutical worker's industry of light society)

V-60: initiating agent (hot radical produces agent, by manufacturing with the pure pharmaceutical worker's industry of light society)

V-70: initiating agent (hot radical produces agent, by manufacturing with the pure pharmaceutical worker's industry of light society)

OT _azo15: initiating agent (hot radical produces agent, and You Da mound chemistry society manufactures)

LUPEROX26: initiating agent (hot radical produces agent, and by Arkema Yoshitomi, Ltd. manufactures)

Irganox819: initiating agent (optical free radical produces agent, is manufactured by Ciba Specialty Chemicals)

Embodiment 16

The manufacture of organic electroluminescent device

The ito glass substrate that preparation consists of the glass substrate that is provided with the ITO film on it, described ITO film be take the strips that width is 2mm and is carried out etching, thereby forms ITO electrode (anode).By the ultrasonic cleaning in isopropyl alcohol (electronics use, chemistry society manufactures by the Northeast) of described ito glass substrate, then with the rotary coating machine, carry out drying.

Then, by the CuPc that passes through sublimation purification in a side vacuum moulding machine of the ITO of formation like this electrode to ito glass substrate, thereby form the film that thickness is 0.015 μ m.

Subsequently, the compound (compound ii-22) that 1.2 weight portions are meaned by formula (I), the monomer that 0.2 weight portion does not have charge-transporting (trade name: A-DCP, You Xinzhong village chemical industry society manufactures) are dissolved in 100 weight portion tetrahydrofurans (THF).In addition, compound (compound M-1 by 0.03 weight portion initiating agent VE-73 (by manufacturing with the pure pharmaceutical worker's industry of light society) and 0.05 weight portion by formula (M1) expression, trade name: triphenyl methane changes into society by Tokyo and manufactures) be dissolved in described solution, obtain thus coating fluid.Described coating fluid is coated on the phthalocyanine copper film, in the atmosphere that is about 100ppm in oxygen concentration in 145 ℃ of heating 40 minutes, thereby form the film that thickness is 0.05 μ m.In this way, form and there is double-deck hole transporting layer on the ITO electrode.

Thereafter, as luminescent material, by compound (A1q3) vapour deposition that is expressed from the next on hole transporting layer, thereby form the luminescent layer of thickness 0.060 μ m.

Again by the Mg-Ag alloy through vapour deposition and codeposition on luminescent layer, thereby form the Mg-Ag electrode (negative electrode) of the strips that wide 2mm and thickness are 0.13 μ m, obtain thus organic electroluminescent device.Described ITO electrode and Mg-Ag electrode so that the mutually orthogonal mode of its bearing of trend form.The organic electroluminescent device so obtained has 0.04cm ²Useful area.

The assessment of device character

The component properties of the organic electroluminescent device that following test so obtains.In vacuum (0.125Pa) thus in DC voltage is applied to as the ITO electrode of anode and luminous between the Mg-Ag electrode of negative electrode, and assessed maximum brightness and glow color.These results are presented in table 5.

In addition, measured as follows the luminescent lifetime of described organic electroluminescent device in drying nitrogen.Current value is set as realizing 50cd/m ²Original intensity, brightness be reduced to its initial value 50% the time hourage be decided to be device lifetime.Drive current density is presented in table 5 together with device lifetime.

Comparative example

According to the same way as in embodiment 16, CuPc is carried out to vacuum moulding machine and form the film that thickness is 0.015 μ m, then will carry out vapour deposition by the benzidine compound R meaned with following formula, thereby form the film of thickness 0.050 μ m.In this way, form and there is double-deck hole transporting layer on the ITO electrode.Subsequently, according to the same way as in embodiment 16, form luminescent layer and electrode on described hole transporting layer.

The organic electroluminescent device so obtained has 0.04cm ²Useful area.

Described organic electroluminescent device is detected according to the same way as in embodiment 16.

Table 5

The above results shows, with comparative example 2, compares, and aspect maximum brightness, drive current density and device lifetime, embodiment 16 realizes better result.

The aforementioned description of illustrative embodiments of the present invention is provided for the purpose of illustration and description.Not be intended to limit or limit the invention to disclosed clear and definite form.Obviously, many changes and variation are apparent to those skilled in the art.Select and describe illustrative embodiments to explain best principle of the present invention and practical application thereof, thereby making others skilled in the art can understand various embodiment of the present invention, and the various changes that are applicable to contemplated application-specific.Scope of the present invention is determined by following claim and equivalent thereof.

Claims

1. an Electrophtography photosensor, described Electrophtography photosensor at least comprises conductive base and is arranged on the photographic layer on described conductive base, wherein, the outmost surface layer of described Electrophtography photosensor is made by the cured film of following composition, and described composition comprises by the compound with shown in following formula (M1) and the charge-transporting material with chain polymerization functional group:

Wherein, in formula (M1), X ¹⁰¹And X ¹⁰²Mean independently of one another hydrogen atom, halogen atom, have the alkyl of 1～15 carbon atom or have substituent or do not have substituent phenyl, wherein substituting group is the alkyl with 1～10 carbon atom; R ¹⁰¹And R ¹⁰³Mean independently of one another hydroxyl; M11 and m13 mean integer 0 or 1 independently of one another; M12 and m14 mean integer 0 independently of one another,

Wherein, the outmost surface layer of described Electrophtography photosensor is protective seam.

2. Electrophtography photosensor as claimed in claim 1, wherein, described charge-transporting material is at least one by the compound meaned with following formula (II):

In formula (II), Ar ¹～Ar ⁴Mean independently of one another to have substituent or do not there is substituent aryl, Ar ⁵Mean to have substituent or do not there is substituent aryl or have substituent or do not there is substituent arlydene, D means-(L) _j-O-CO-C (R)=CH ₂, j mean 0 or 1, five c mean independently of one another 0 or 1, k mean 0 or 1, and the ading up to more than 1 of D, R is hydrogen atom or the straight or branched alkyl with 1～5 carbon atom; L means divalent organic group; Wherein except D:-(L) _j-O-CO-C (R)=CH ₂Substituting group in addition is selected from the alkyl with 1～4 carbon atom, the alkoxy with 1～4 carbon atom, replace and the phenyl of the alkoxy with 1～4 carbon atom is arranged, do not have substituent phenyl, have aralkyl and the halogen atom of 7～10 carbon atoms.

3. Electrophtography photosensor as claimed in claim 1, wherein, described photographic layer is the individual layer photographic layer, or comprises the stack-up type photographic layer of charge generation layer and charge transport layer.

4. Electrophtography photosensor as claimed in claim 3, wherein, described charge transport layer is the outmost surface layer of the described Electrophtography photosensor made by the cured film of following composition, and described composition comprises by the described compound shown in formula (M1) and has the described charge-transporting material of chain polymerization functional group.

5. Electrophtography photosensor as claimed in claim 1, described Electrophtography photosensor also comprises the undercoat be arranged on described conductive base.

6. a handle box, described handle box comprises at least one unit in the group that in claim 1～5, the described Electrophtography photosensor of any one and the freely following unit of choosing form: for the charhing unit to described Electrophtography photosensor charging; For using toner will be formed on the developing cell of the latent electrostatic image developing on described Electrophtography photosensor; Remove unit with the toner that the toner for remaining in described Electrophtography photosensor surface is removed.

7. an image processing system, described image processing system comprises: the described Electrophtography photosensor of any one in claim 1～5; For the charhing unit to described Electrophtography photosensor charging; Form unit for the electrostatic latent image that forms electrostatic latent image on the described Electrophtography photosensor through charging; Thereby for using toner will be formed on the developing cell of the latent electrostatic image developing formation toner image on described Electrophtography photosensor; With for described toner image being transferred to the transfer printing unit of transfer printing body.