CN102163015A

CN102163015A - Electrophotographic photoreceptor, process cartridge, image forming apparatus, cured film, and organic electroluminescent device

Info

Publication number: CN102163015A
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: 2011-08-24
Anticipated expiration: 2030-09-15
Also published as: CN102163015B

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 by following process and form thing: by the surface charging of charhing unit to Electrophtography photosensor; Thereby by being exposed to light through the surface of described Electrophtography photosensor of charging so that the discharge of described surface selectivity forms electrostatic latent image on described surface with imaging mode; Thereby by developing cell toner is attached to and makes image development on the described sub-image to form toner image; And described toner image is transferred on the transfer printing body by transfer printing unit.

In recent years, the Electrophtography photosensor that is made of organic photoconductive material (Organophotoreceptor) became main flow.

The various materials of the outmost surface layer of Electrophtography photosensor have been proposed to be used for.For example, No. the 3287678th, Jap.P. proposes those materials of being made of the conductive powder that is dispersed in the phenolics.Those materials that the proposition of Japanese kokai publication hei 12-019749 communique is made of hybrid inorganic-organic materials.Those materials that the proposition of TOHKEMY 2005-234546 communique is made of the chain polymerization material.Those materials that the proposition of TOHKEMY 2000-66424 communique is made of acrylic material.

TOHKEMY 2004-240079 communique proposes by carrying out those materials that overshoot induces crosslinked radiation-initiated crosslinking agent and charge transport material to constitute.

The Electrophtography photosensor that the proposition of TOHKEMY 2008-058779 communique is made of hindered phenol, hindered amine and alkyl phenyl ketone antioxidant.

The Electrophtography photosensor that the proposition of TOHKEMY 2008-233893 communique is made of hindered phenol, hindered amine, alkyl phenyl ketone, benzophenone antioxidant and metal complex quencher.

The Electrophtography photosensor that the proposition of TOHKEMY 2006-234943 communique is made of the active oxygen quencher.

The Electrophtography photosensor that the proposition of TOHKEMY 2005-345782 communique is made of hindered phenol or amine etc.

The Electrophtography photosensor that the proposition of TOHKEMY 2002-040686 communique is made of halogen compounds.

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

Summary of the invention

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

In formula (M1), X ¹⁰¹And X ¹⁰²Represent hydrogen atom, halogen atom independently of one another, have 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 ¹⁰¹Expression azo group or siloxy; X ¹⁰³Expression has the alkyl of 1～15 carbon atom, the alkoxy with 1～15 carbon atom, cyano group, phenoxy group or has the aryl of 6～30 carbon atoms), or the substituting group that forms by these moiety combinations; R ¹⁰¹And R ¹⁰³Represent hydroxyl independently of one another or have the alkoxy of 1～15 carbon atom; M11 and m13 represent integer 0 or 1 independently of one another; R ¹⁰²And R ¹⁰⁴Expression independently of one another has the alkyl of 1～15 carbon atom; M12 and m14 represent

integer

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

Description of drawings

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 synoptic diagram that shows the image processing system of illustrative embodiments of the present invention;

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

Fig. 6 A～6C is the synoptic 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 as the described Electrophtography photosensor of first aspect, and wherein, described charge-transporting material is at least a by with the compound of following formula (I) expression.

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

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

A fourth aspect of the present invention be as first to the third aspect the described Electrophtography photosensor of either side, 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 as the described Electrophtography photosensor of 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 the 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 that is arranged on the 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 a handle box, described handle box comprises the described Electrophtography photosensor of either side in first aspect to the six aspects and is selected from least one unit in the group of being made up of following unit: be used for the charhing unit to described Electrophtography photosensor charging; Be used to use toner will be formed on the developing cell of the latent electrostatic image developing on the described Electrophtography photosensor; Remove the unit with the toner that is used for the toner that remains in described Electrophtography photosensor surface is removed.

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

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

integer

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

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

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

First to the 6th aspect of the present invention provides Electrophtography photosensor, described Electrophtography photosensor with do not comprise by comparing the image retention (ghost image) that less appearance causes owing to residual image formerly as those Electrophtography photosensors of outmost surface layer material with the compound of following formula (M1) expression and the combination of charge-transporting material with chain polymerization functional group.

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

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 with the combination of the compound of following formula (M1) expression and the charge-transporting material with chain polymerization functional group, has such as durability and good charge-transportings such as solvent resistance and thermotolerances.

Electrophtography photosensor

The Electrophtography photosensor of this illustrative embodiments comprises conductive base and the photographic layer that is arranged on the described conductive base at least.The outmost surface layer of described Electrophtography photosensor is made by the cured film of following composition, and described composition comprises by compound shown in the 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 the deterioration that may cause electrical properties, the image retention (ghost image) that causes owing to residual image formerly 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 charge-transporting material with chain polymerization functional group and the compound of being represented by above-mentioned formula (M1), thereby prevents the image retention (ghost image) that causes owing to residual image formerly.Its reason is also unclear, but as follows by inference.

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

On the other hand, in the presence of the compound of representing by formula (M1), kation, negative ion or the free radical that produces by initiating agent and stimulation (for example 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 the described charge-transporting material (charge transport skeleton), this helps formation to have intac charge-transporting probably 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 selectivity attack, can prevent attack thus the part of the charge transport in the charge-transporting material (charge transport skeleton) to chain polymerization functional group.

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 owing to residual image formerly.As a result, the outmost surface layer that is made of the cured film of described composition shows high mechanical properties, and reuses the electrical properties that causes and the deterioration of image property is suppressed for a long time.

In addition, the result comprises the handle box of Electrophtography photosensor of this illustrative embodiments and image processing system makes the minimum appearance of image because the image retention (ghost image) that residual image formerly causes.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, is preferably used as protective seam or charge transport layer especially.

For example, when described outmost surface layer 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.

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 the Electrophtography photosensor that relates in the exemplary embodiment with reference to the accompanying drawings 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 naturally Fig. 2 and Fig. 3 in another illustrative embodiments.

The Electrophtography photosensor 7A that shows 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 the conductive base 4, forms charge generation layer 2, charge transport layer 3 and protective seam 5 more thereon successively.In Electrophtography photosensor 7A, photographic layer is made of charge generation layer 2 and charge transport layer 3.

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

The Electrophtography photosensor 7B that shows among Fig. 2 has following structure, and wherein undercoat 1 is formed on the conductive base 4, forms charge transport layer 3, charge generation layer 2 and protective seam 5 more thereon successively.In Electrophtography photosensor 7B, photographic layer is made of charge transport layer 3 and charge generation layer 2.

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

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

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

With the Electrophtography photosensor 7A that shows among 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, such as (for example having film on it, such as metals such as aluminium, nickel, chromium, stainless steels, 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 coating of electric conductivity imparting agent or dipping with through the plastic foil of 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 for example less than 10 ⁷The specific insulation of Ω cm.

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

Undercoat

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

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

The example of the adhesive resin that contains 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 that preferably in the upper strata, uses.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 does not have specified metal compound and binder resin, this ratio can be through selecting to realize the desired Electrophtography photosensor character that obtains.

Undercoat can contain 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, the surface that is arranged on the undercoat on the conductive base can be polished by for example buff polishing, sandblast, wet type honing or grinding etc.

For example, undercoat can contain adhesive resin and conductive particle at least.Described conductive particle preferably has for example 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 be exercised with its two or more being combined into and be used.

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 the 10 weight %～80 weight % with respect to binder resin, and 40 weight %～80 weight % more preferably.

Employing contains mentioned component in solvent undercoat formation forms undercoat with coating fluid.

The example of the method for discrete particles comprises the medium decollator in undercoat forms with coating fluid, such as bowl mill, vibromill, masher, sand mill and horizontal sand mill, with no medium decollator, such as stirrer, ultrasonic decollator, roller mill and high pressure homogenisers.Described high pressure homogenisers can be to collide by liquid under high pressure-liquid collision or liquid-wall to realize the collision type that disperses, or realizes the penetrating type that disperses by under high pressure passing fine channel.

Be used for undercoat formation is comprised that with the example that coating fluid is applied to the method for conductive base dip-coating, upward pushing-type coating, the excellent coating that winds the line, spraying, scraper plate coating, scraper coating and curtain formula are coated with.

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

Although do not indicate, between undercoat and photographic layer, can form the middle layer.The example of the adhesive resin that contains in the 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 use separately, perhaps use with its two or more potpourri or condensed polymer.Wherein, preferably contain the organometallics of zirconium or silicon, also suppressed the potential change that environment or repeated use cause thus because they have the low-residual electromotive force.

Employing contains mentioned component in solvent middle layer formation forms the middle layer with coating fluid.

Be used to be coated with the example that the middle layer forms with the method for coating fluid and comprise common method, such as dip-coating, go up pushing-type coating, the excellent coating that winds the line, spraying, scraper plate coating, scraper coating and act formula and be coated with.

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

Charge generation layer

Charge generation layer is made up 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 phthalocyanine tin and TiOPc.Object lesson comprises for CuK α characteristic x ray having 7.4 ° at least, 16.6 °, 25.5 ° and the chlorine phthalocyanine gallium crystal of 28.3 ° Bragg angle (2 θ ± 0.2 °) strong diffraction peak of locating, at least have 7.7 ° for CuK α characteristic x ray, 9.3 °, 16.9 °, 17.5 °, 22.4 ° and the metal-free phthalocyanine crystal of 28.8 ° Bragg angle (2 θ ± 0.2 °) strong diffraction peak of locating, at least have 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 28.3 ° Bragg angle (2 θ ± 0.2 °) strong diffraction peak of locating, have 9.6 ° at least for CuK α characteristic x-ray, 24.1 ° and the TiOPc crystal of 27.2 ° Bragg angle (2 θ ± 0.2 °) strong diffraction peak of locating.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 use separately or with its two or more being used in combination.

The example of forming the adhesive resin of charge generation layer comprises: such as polycarbonate resins such as bisphenol A-type or bisphenol Z types, 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 use separately or with its two or more being used in combination.

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

Employing contains mentioned component in solvent charge generation layer formation forms charge generation layer with coating fluid.

The example of the method for discrete particles (for example charge generating material) comprising in charge generation layer forms with coating fluid: the medium decollator, such as bowl mill, vibromill, masher, sand mill and horizontal sand mill, with no medium decollator, such as stirrer, ultrasonic decollator, roller mill and high pressure homogenisers.Described high pressure homogenisers can be to collide by liquid under high pressure-liquid collision or liquid-wall to realize the collision type that disperses, or realizes the penetrating type that disperses by under high pressure passing fine channel.

Be used for charge generation layer formation is comprised that with the example that coating fluid is applied to the method on the undercoat dip-coating, upward pushing-type coating, the excellent coating that winds the line, spraying, scraper plate coating, scraper coating and curtain formula are coated with.

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

The example of described charge-transporting material comprises: the cavity conveying material, and Li such as oxadiazole derivant, as 2,5-two (right-the diethylamino phenyl)-1,3,4-oxadiazole; Pyrazoline derivative, as 1,3,5-triphenyl-pyrazoline and 1-[pyridine radicals-(2)]-3-(right-the diethylamino styryl)-5-(right-the diethylamino styryl) pyrazoline; Aromatic series uncle amino-compound, as triphenylamine, N, N '-two (3, the 4-3,5-dimethylphenyl) xenyls-4-amine and three (right-aminomethyl phenyl) amino-4-amine and dibenzyl aniline; Aromatic series two uncle's amino-compounds, as N, N '-two (3-aminomethyl phenyl)-N, N '-diphenylbenzidine; 1,2, the 4-pyrrolotriazine derivatives, as 3-(4 '-dimethylaminophenyl)-5,6-two (4 '-methoxyphenyl)-1,2, the 4-triazine; Hydazone derivative is as 4-diethyl amino benzaldehyde-1,1-diphenyl hydrazone; Quinazoline derivant is as 2-phenyl-4-styryl-quinazoline; Benzofuran derivatives, as 6-hydroxyl-2,3-two (right-methoxyphenyl) coumarone; α-stilbene derivative is as right-(2, the 2-diphenylacetylene)-N, N-diphenyl aniline; Enamine derivates; Carbazole derivates is as the N-ethyl carbazole; Poly-N-vinyl carbazole and derivant thereof; With the electron transport material, naphtoquinone compounds for example is 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; Has polymkeric substance in thiophene compound and main chain or the side chain derived from the group of arbitrary above-claimed cpd.These charge-transporting materials can use separately or with its two or more being used in combination.

The example of forming the adhesive resin of charge transport layer comprises: insulative resin, for example, such as polycarbonate resins such as bisphenol A-type or bisphenol Z types, 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 use separately or with its two or more being used in combination.

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

Employing contains mentioned component in solvent charge transport layer formation forms charge transport layer with coating fluid.

The example of the method for discrete particles (for example fluorinated resin particle) comprising in charge transport layer forms with coating fluid: the medium decollator, such as bowl mill, vibromill, masher, sand mill and horizontal sand mill, with no medium decollator, such as stirrer, ultrasonic decollator, roller mill and high pressure homogenisers.Described high pressure homogenisers can be to collide by liquid under high pressure-liquid collision or liquid-wall to realize the collision type that disperses, or realizes the penetrating type that disperses by under high pressure passing fine channel.

Be used for charge transport layer formation is comprised that with the example that coating fluid is applied to the method for charge generation layer dip-coating, upward pushing-type coating, the excellent coating that winds the line, spraying, scraper plate coating, scraper coating and curtain formula are coated with.

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 the compound that comprises with following formula (M1) expression.

The compound of formula (M1) expression 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 of expression comprises fluorine atom, chlorine atom and bromine atoms.

In formula (M1), by X ¹⁰¹, X ¹⁰²And X ¹⁰³The example of alkyl of expression comprises having substituent or do not have substituent straight chain, side chain or 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 alkoxy of expression comprises having substituent or do not have substituent straight chain, side chain or 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 phenoxy group of expression comprises having substituent or do not have substituent phenoxy group.

In formula (M1), by X ¹⁰¹, X ¹⁰²And X ¹⁰³The example of aryl of expression comprises having substituent or do not have substituent phenyl, have substituent or do not have substituent many cyclophanes perfume base (aromatic radical that links to each other with phenyl ring) and have substituent or do not have 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 of expression constitutes comprises following structure (M1-A)～(M1-B).

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

In formula (M1), by R ¹⁰¹And R ¹⁰³The example of alkoxy of expression comprises having substituent or do not have substituent straight chain, side chain or 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 represent integer 1 separately, by R ¹⁰¹And R ¹⁰³The contraposition that the hydroxyl of expression or alkoxy are preferably placed at each phenyl in the formula (M1).

In formula (M1), by R ¹⁰²And R ¹⁰⁴The example of alkyl of expression comprises having substituent or do not have substituent straight chain, side chain or 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 had substituting group, described substituent example comprised 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 because the angle of the image retention (ghost image) that causes of residual image formerly, be preferably by any of the compound of formula (M2)～(M3) expression by the compound of formula (M1) expression.

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

Wherein, the compound of preferably representing by formula (M2).

In formula (M2), X ²⁰¹The expression 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 ²⁰¹Expression azo group or siloxy; X ²⁰²Expression has the alkyl of 1～15 carbon atom, the alkoxy with 1～15 carbon atom, cyano group, phenoxy group or has the aryl of 6～30 carbon atoms).

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

In formula (M2), R ²⁰¹, R ²⁰³And R ²⁰⁵Represent hydroxyl independently of one another; M21, m23 and m25 represent 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 ²⁰⁶Expression independently of one another has the alkyl of 1～15 carbon atom; M22, m24 and m26 represent

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 ²⁰¹The expression hydrogen atom or-Y ²⁰¹-X ²⁰²(Y wherein ²⁰¹The expression azo group, X ²⁰²Expression has the aryl of 6～30 carbon atoms); R ²⁰¹, R ²⁰³And R ²⁰⁵Represent hydroxyl independently of one another; M21, m23 and m25 represent integer 0 or 1 independently of one another; M22, m24 and m26 represent 0.

In formula (M3), X ³⁰¹And X ³⁰²Represent hydrogen atom, halogen atom independently of one another, have 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 ³⁰¹Expression azo group or siloxy; X ³⁰³Expression has the alkyl of 1～15 carbon atom, the alkoxy with 1～15 carbon atom, cyano group, phenoxy group or has the aryl of 6～30 carbon atoms).

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

In formula (M3), R ³⁰¹, R ³⁰³, R ³⁰⁵And R ³⁰⁷Represent hydroxyl independently of one another; M31, m33, m35 and m37 represent 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 ³⁰⁸Expression independently of one another has the alkyl of 1～15 carbon atom; M32, m34, m36 and m38 represent

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 preferably especially, in formula (M3), X ³⁰¹Expression cyano group or phenoxy group.

Object lesson by the compound of formula (M1) expression comprises following compound.Yet illustrative embodiments of the present invention is not limited thereto.

Because the angle of the image retention (ghost image) that causes of residual image formerly, preferably has weight-average molecular weight below 5000 from preventing, more preferably 100～2000, more more preferably 150～1000 by the compound of formula (M1) expression.

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

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 preferably methacryl especially.

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

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

So the n in the formula (I) represents the integer more than 1.Yet from improving the angle that cross-linking density also obtains stronger cross linking membrane (cured film) thus, 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 the scraper clearer, 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 most surperficial molecular motion of Electrophtography photosensor, thereby the interaction of the molecule in feasible and the scraper component surface dies down.

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

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

Usually, has 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 takes place easily, and this will cause microcosmic (macroscopic view) island type structure.In the such a field of island type structure outside electronic applications is not special existing problems.Yet, when described island type structure is used for Electrophtography photosensor, will cause such as shortcomings such as the inhomogeneous or fold in superficial layer or density unevenness are even.Therefore, R is preferably methyl.

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

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

Promptly, it is believed that, therein as the represented compound of formula (I), the free radical polymerization substituent carries out under the situation of polymerization, when the free radical that produces in polymerization has when being easy to move to the structure of charge transport skeleton (F in the formula (I)), the free radical that is produced makes charge transport function deterioration, and this causes the deterioration of electrical specification.In addition,, it is believed that about physical strength, when large volume charge transport skeleton and polymerism site mutually near and when being rigidity, the polymerism site is difficult to move closer to mutually, 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 when containing the organic group of the alkylidene with two above carbon atoms, described organic group can only be made of the alkylidene with two above carbon atoms, perhaps can be for alkylidene with two above carbon atoms with such as the combination of alkenylene, alkynylene, ether, thioether, ester or arlydene divalent groups such as (for example phenylenes).From the angle of physical strength, the carbon number purpose higher limit of alkylidene is preferably 20, and more preferably 10.

The compound of formula (I) expression is preferably by the compound with following formula (II) expression.

The compound of formula (II) expression is especially very excellent aspect charge mobility and oxidation stable.

In formula (II), Ar ¹～Ar ⁴Expression independently of one another has substituent or does not have substituent aryl, Ar ⁵Expression has substituent or does not have substituent aryl or have substituent or do not have substituent arlydene, and D represents-(L) _j-O-CO-C (R)=CH ₂, j represents that 0 or 1, five c represents 0 or 1 independently of one another, k represents 0 or 1, and the ading up to more than 1 of D, L, R and j have separately with formula (II) in L, the R definition identical with j.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 the formula (I) in the formula (II), and from improving cross-linking density and can obtaining 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 ⁴Expression independently of one another has substituent or does not have substituent aryl.Ar ¹～Ar ⁴Can be identical or differ from one another.

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

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

In structural formula (1), R ⁰¹Expression be selected from by hydrogen atom, have 1～4 carbon atom alkyl, be substituted with alkyl or have the phenyl of the alkoxy of 1～4 carbon atom, do not have substituent phenyl and have a group in the group that the aralkyl of 7～10 carbon atoms forms with 1～4 carbon atom.

In structural formula (2) and (3), R ⁰²～R ⁰⁴Expression independently of one another be selected from by hydrogen atom, have 1～4 carbon atom alkyl, have 1～4 carbon atom alkoxy, be substituted with the phenyl of alkoxy, do not have substituent phenyl, have a group in the aralkyl of 7～10 carbon atoms and the group that halogen atom is formed with 1～4 carbon atom.In addition, m represents 1～3 integer.

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

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

In structural formula (8) and (9), R ⁰⁵And R ⁰⁶Expression independently of one another be selected from by hydrogen atom, have 1～4 carbon atom alkyl, have 1～4 carbon atom alkoxy, be substituted with the phenyl of alkoxy, do not have substituent phenyl, have a group in the aralkyl of 7～10 carbon atoms and the group that halogen atom is formed with 1～4 carbon atom.In addition, q represents 1～3 integer separately.

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

In structural formula (10)～(17), R ⁰⁷And R ⁰⁸Expression independently of one another be selected from by hydrogen atom, have 1～4 carbon atom alkyl, have 1～4 carbon atom alkoxy, be substituted with the phenyl of alkoxy, do not have substituent phenyl, have a group in the aralkyl of 7～10 carbon atoms and the group that halogen atom is formed with 1～4 carbon atom, W represents divalent group, r and s represent 1～10 integer independently of one another, and t represents 1～3 integer separately.

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

In formula (II), when k is 0, Ar ⁵Be to have substituent or do not have substituent aryl, and the example of described aryl and Ar ¹～Ar ⁴In the example of aryl identical.When k is 1, Ar ⁵Be to have substituent or do not have 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 exemplified.

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

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

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

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

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

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

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

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

By the represented compound of formula (I) can be that the n value is that compound more than 4 and n value are 1～3 combination of compounds.Described combination enables to control the deterioration of solidifying film strength and not causing charge delivery capability.

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

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

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

When satisfying above-mentioned scope, obtain good electrical properties, and make 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 constituent concentration that improves charge-transporting material and the advantage of further improving electrical properties.

As known charge-transporting material, can use those materials that are enumerated as the charge-transporting material that constitutes 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 a structure that is selected from the group of being made up of following structure in its molecule: (A) structure that is formed by the polymerization of the acryloyl class monomer with fluorine atom; (B) has the structure of carbon-carbon double bond and fluorine atom; (C) alkylene oxide structure; (D) has the structure of carbon carbon triple bond and hydroxyl.

Described surfactant can contain at least a 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 that forms by the polymerization of acryloyl class monomer with fluorine atom

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

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

(B) has 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 with the structure represented of one at least in following formula (B1) or the formula (B2).

Surfactant with structure (B) is preferably to have by formula (B1) in the side chain of acryloyl base polymer or the compound of the group represented of one at least (B2), perhaps serves as reasons with the compound of any expression in the 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) at least during the compound of the group represented of one; other composition highly compatibles of described acryloyl group structure and described composition, this helps to form uniform outmost surface layer.

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

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

In formula (B3)～(B5), the example of being rolled into a ball by any monovalent organic radical of R ' expression comprises alkyl with 1～30 carbon atom and the hydroxyalkyl with 1～30 carbon atom.

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

Example by the compound of any expression in the formula (B3)～(B5) comprises FTERGENT 100,100C, 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 (making) by Neos Company Limited.

In the side chain of acryloyl base polymer, have by formula (B1) or (B2) at least the example of the compound of the structure represented of one comprise KB-L82, KB-L85, KB-L97, KB-L109, KB-L110, KB-F2L, KB-F2M, KB-F2S, KB-F3M and KB-FaM (making) 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 making with the pure pharmaceutical worker's industry of light society), No. 1, defoamer and No. 5, defoamer (being made 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 terminal oxyalkylene or the polyoxyalkylene that is substituted with the group that contains fluorine atom.

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 made by Dainippon Ink. ﹠ Chemicals Inc), FTERGENT 250,251,222F (being made by Neos Company Limited), POLYFOX PF636, PF6320, PF6520 and PF656 (being made by northern village chemistry society).

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 (making) by chemistry society of SHIN-ETSU HANTOTAI, TSF4440, TSF4445, TSF4450, TSF4446, TSF4452, TSF4453, TSF4460 (by GE Toshiba Silicones Co., Ltd. makes), 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 (making) by BYK-ChemieJapan.

(D) has 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 the compound that has carbon carbon triple bond and hydroxyl in its molecule, its object lesson comprises 2-propine-1-alcohol, 1-butine-3-alcohol, 2-butine-1-alcohol, 3-butine-1-alcohol, 1-pentyne-3-alcohol, valerylene-1-alcohol, 3-pentyne-1-alcohol, 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 diine-1-alcohol, 10,12-25 carbon diine-1-alcohol, 2-butine-1, the 4-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-two (2-chlorphenyl)-1,6-diphenyl-2,4-hexadiine-1, the 6-glycol, (-)-1,6-two (2-chlorphenyl)-1,6-diphenyl-2,4-hexadiine-1, the 6-glycol, 2-butine-1,4-glycol two (2-hydroxyethyl), 1,4-diacetoxy-2-butine, 4-diethylamino-2-butine-1-alcohol, 1,1-diphenyl-2-propine-1-alcohol, 1-ethinyl-1-cyclohexanol, 9-ethinyl-9-fluorenol, 2,4-hexadiindiol-1,6-two (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 that combines such as oxyalkylenes such as ethylene oxides (for example, trade name: SURFYNOL 400 series are made by chemistry society of SHIN-ETSU HANTOTAI).

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

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

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

By formula (D1) or (D2) example of commercially available prod of the compound of expression comprise SURFYNOL 400 series (making) by chemistry society of SHIN-ETSU HANTOTAI.

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

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

The phosphate that the preferred example of the surfactant with fluorine atom that can use with the combinations-of surfactants that has in the structure (A)～(D) any comprises 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 contains perfluoroalkyl.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 made 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 made by JEMCO Inc.), FTERGENT 100,100C, 110,140A, 150,150CH, A-K and 501 (being made by Neos Company Limited).

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

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

Can be not limited to above-mentioned example with example with surfactant that any combinations-of surfactants is used in the structure (A)～(D) with fluorine atom, other preferred example comprise contain fluorine atom betaine compound (for example, FTERGENT 400SW, make by Neos Company Limited), with the surfactant with zwitter-ion group (for example, FTERGENT SW is made by Neos Company Limited).

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

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

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

Purpose for physical strength, flexibility, planarization and the spatter property of the viscosity of control combination thing, film can join free radical polymerization monomer or the oligomer that does 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, the methoxy poly (ethylene 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, ammediol 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 the composition, do not have the free radical polymerization monomer of charge-transporting or the content of oligomer and can be preferably, 0 weight %～40 weight % more preferably, 0 weight %～30 weight % more preferably again with 0 weight %～50 weight %.

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 by the method for utilizing heat, light or electron beam etc. by the composition that will contain said components and obtain.In order to obtain to have the cured film such as the equilibrium property of electrical properties and physical strength etc., described film is preferably by heat and is cured.For the curing of conventional acryloyl class coating, preferably can realize the electron beam that on-catalytic solidifies 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 reduce to minimum and to improve the surface nature of the cured film that will form, preferably carry out the heat curing of gentle reaction to the damage of described photosensitive material.

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

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 that provides in parenthesis refers to 10 hours half life temperatures.

Azo initiator is 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 ℃) (the pure pharmaceutical worker's industry of each freedom and light society makes); OT _AZO-15 (61 ℃), OT _AZO-30, AIBM (65 ℃), AMBN (67 ℃), ADVN (52 ℃) or ACVA (68 ℃) (each chemical society of free big mound makes); PERTETRA A, PERHEXA HC, PERHEXA C, PERHEXA V, PERHEXA 22, PERHEXA MC, PERBUTYL H, PERCUMYL H, PERCUMYL P, PERMENTAH, PEROCTA H, PERBUTYL C, PERBUTYL D, PERHEXYL D, PEROYLIB, PEROYL 355, PEROYL L, PEROYL SA, NYPER BW, NYPERBMT-K40/M, PEROYL IPP, PEROYL NPP, PEROYL TCP, PEROYL OPP, PEROYL SBP, PERCUMYL ND, PEROCTA ND, PERHEXYL ND, PERBUTYL ND, PERBUTYL NHP, PERHEXYL PV, PERBUTYL PV, PERHEXA 250, PEROCTA O, PERHEXYL O, PERBUTYL O, PERBUTYLL, PERBUTYL 355, PERHEXYL I, PERBUTYL I, PERBUTYL E, PERHEXA25Z, PERBUTYL A, PERHEXYL Z, PERBUTYL ZT, PERBUTYL Z (each free NOF Corporation makes); KAYAketal AM-C55, TRIGONOX 36-C75, LAUROX, PERKADOX L-W75, PERKADOX CH-50L, TRIGONOX TMBH, KAYACUMENE H, KAYAbutyl H-70, PERKADOX BC-FF, KAYAHEXA AD, PERKADOX 14, KAYABUTYL C, KAYABUTYL D, KAYAHEXAYD-E85, PERKADOX 12-XL25, PERKADOX 12-EB20, TRIGONOX22-N70, TRIGONOX 22-70E, TRIGONOX D-T50, TRIGONOX 423-C70, KAYAESTER CND-C70, KAYAESTER CND-W50, TRIGONOX 23-C70, TRIGONOX 23-W50N, TRIGONOX 257-C70, KAYAESTER P-70, KAYAESTER TMPO-70, TRIGONOX 121, KAYAESTER O, KAYAESTERHTP-65W, KAYAESTER AN, TRIGONOX 42, TRIGONOX F-C50, KAYABUTYL B, KAYACARBON EH-C70, KAYACARBON EH-W60, KAYACARBON I-20, KAYACARBON BIC-75, TRIGONOX 117, KAYALENE 6-70 (each free Kayaku Akzo Corporation makes); LUPEROX LP (64 ℃), LUPEROX 610 (37 ℃), LUPEROX 188 (38 ℃), LUPEROX 844 (44 ℃), LUPEROX 259 (46 ℃), LUPEROX 10 (48 ℃), LUPEROX 701 (53 ℃), LUPEROX 11 (58 ℃), LUPEROX 26 (77 ℃), LUPEROX 80 (82 ℃), LUPEROX 7 (102 ℃), LUPEROX 270 (102 ℃), LUPEROX P (104 ℃), LUPEROX 546 (46 ℃), LUPEROX 554 (55 ℃), LUPEROX 575 (75 ℃), LUPEROX TANPO (96 ℃), LUPEROX 555 (100 ℃), LUPEROX 570 (96 ℃), LUPEROX TAP (100 ℃), LUPEROX TBIC (99 ℃), LUPEROX TBEC (100 ℃), LUPEROX JW (100 ℃), LUPEROX TAIC (96 ℃), LUPEROX TAEC (99 ℃), LUPEROX DC (117 ℃), LUPEROX 101 (120 ℃), LUPEROX F (116 ℃), LUPEROX DI (129 ℃), LUPEROX 130 (131 ℃), LUPEROX 220 (107 ℃), LUPEROX 230 (109 ℃), LUPEROX 233 (114 ℃) and LUPEROX 531 (93 ℃) (each free Arkema Yoshitomi, Ltd. makes).

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

In being used to form the composition of protective seam; for suppressing excessive absorption by the gas of discharge generation and suppress the purpose of the oxidation that causes by the gas that is produced thus effectively; 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-An Jibingjisanyiyangjiguiwan, the gamma-amino propyl trimethoxy silicane, gamma-amino propyl group methyl dimethoxysilane, N-β-(amino-ethyl)-γ-An Jibingjisanyiyangjiguiwan, 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. make) and AY42-440, AY42-441 and AY49-208 (trade name, all by Dow Corning Toray Co., Ltd. makes).

In addition, in order to introduce hydrophobicity, can add fluorochemicals, such as (13 fluoro-1,1,2,2-tetrahydrochysene octyl group) triethoxysilane, (3,3, the 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 use 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 in order to the composition that forms protective seam, can add thermoplastic resin improving discharge gas tolerance, physical strength and mar resistance, and further reduce moment of torsion; the control wear extent prolongs storage period and is controlled at particle dispersion and viscosity in the protective seam respectively.

The example of thermoplastic resin comprises: polyvinyl acetal resin, as polyvinyl butyral resin, vinyl-formal resin or wherein the butyral part acetalation of modifying through dimethoxym ethane or acetyl acetal (acetoacetal) part polyvinyl acetal resin (for example, S-LEC B, K (trade name, society makes by the ponding chemistry)), 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 less than 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 reduce with tend to cause limiting addition and cause being coated with in the film forming defective.The addition of resin is preferably 1 weight %～40 weight %, 1 weight %～30 weight % more preferably, 5 weight %～20 weight % more preferably again.When the addition of resin was less than 1 weight %, the additive effect of resin tended to deficiency.On the other hand, when its addition surpasses 40 weight %, hot and humid degree (for example, 28 ℃, 85%RH) tend in the environment occur image blurring.

In being used to form the composition of protective seam, preferably add antioxidant to suppress the oxidizing gas deteriorations such as ozone that protective seam produces because of charhing unit.If the physical strength of photosensitive surface increases and make the life-span of photoreceptor prolong thus, then photoreceptor becomes and the former longer time of oxidizing gas contact gear ratio.As a result, then 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 the 20 weight %, more preferably below the 10 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-two [(octylsulfo) methyl]-orthoresol, 2,6-di-t-butyl-4-ethyl-phenol, 2,2 '-methylene two (4-methyl-6-tert butyl phenol), 2,2 '-methylene two (4-ethyl-6-tert-butyl phenol), 4,4 '-butylidene two (3 methy 6 tert butyl phenol), 2,5-two 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 and contains silicon grain.The described silicon grain that contains is to contain silicon those particles as component, particularly, can enumerate silica gel and siloxane particles.Be selected from as the silica gel that contains silicon grain and contain 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 and the silica gel that is preferably 10nm～30nm.Can use commercially available silica gel.Silica gel solids content 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 the protective seam, the silica gel solids content is 0.1 weight %～50 weight %, and is preferably 0.1 weight %～30 weight %.

Be used as the silica dioxide granule that the siloxane particles that contains silicon grain is selected from silicon resin particle, silicone rubber particles and handles through siloxane surface, and use commercially available siloxane particles usually.Siloxane particles forms sphere, 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 has therefore improved the surface nature of Electrophtography photosensor under the situation of not disturbing cross-linking reaction.That is to say, in that being incorporated in the rigidity cross-linked structure, siloxane particles do not cause under the state of fluctuating, the lubricity and the hydrophobicity on Electrophtography photosensor surface are improved, and have kept excellent abrasive and resistant thing tack thus in the long period.

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

The example of other particles comprises: the fluorine class particle of tetrafluoroethene, trifluoro-ethylene, hexafluoropropylene, fluorothene or vinylidene fluoride; As " Preprints of the 8th Polymer Material Forum, the p.89 " particle that the described resin that is 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 is modified polysiloxane, methacryl modification polysiloxane, sulfydryl modification polysiloxane or phenol such as amido modified polysiloxane, epoxy group modified polysiloxane, carboxyl modified polysiloxane, methyl alcohol and is modified polysiloxane; Ring-type dimethyl cyclosiloxane is such as hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane or ten diformazan basic rings, 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 is such as the hexaphenyl cyclotrisiloxane; Fluorine-containing cyclosiloxane is such as (3,3, the 3-trifluoro propyl) methyl cyclotrisiloxane; The cyclosiloxane of hydrogeneous silicyl is such as methyl hydrogen siloxane potpourri, pentamethyl D5 or phenyl hydrogen cyclosiloxane; With the cyclosiloxane that contains 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 use separately or with at least two kinds be used in combination wherein.When wherein at least two kinds when being used in combination, can adopt in simple mixtures, its solid solution and the motlten metal oxide any.From the angle of the transparency of protective seam, the mean grain size of conductive particle is preferably below the 0.3 μ m, is preferably especially below the 0.1 μ m.

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

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

To contain protective seam in order to the composition that forms protective seam according to conventional coating process forms and is applied on the charge transport layer described coating process such 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 with coating fluid.Then, if desired, thereby heating obtains solidfied material with coating curing under 100 ℃～170 ℃ temperature.As a result, obtain the protective seam (outmost surface layer) made by solidfied material.

Be preferably below 1% with the oxygen concentration in the curing of coating fluid in protective seam formation, more preferably below the 1000ppm, more more preferably below the 500ppm.

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

As Electrophtography photosensor, the example of function divergence type has been described more than.The content of the charge generating material in single-layer type photographic layer 6 (charge generation/charge transport layer) is 10 weight %～85 weight %, perhaps about 10 weight %～about 85 weight %, and be preferably 20 weight %～50 weight %.The content of charge-transporting material is preferably 5 weight %～50 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 5 μ m～about 50 μ m, 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 under 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 Figure 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 can be by the position of the opening on the handle box 300 with Electrophtography photosensor 7 exposures, 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 among 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.

In Fig. 4, shown such example,, 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) with auxiliary cleaning wherein as cleaning equipment 13.Yet these can use as required.

As charging equipment 8, used the contact 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 such as 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 devices.

Although do not illustrate in the drawings, also can with in order to the temperature that improves 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.Employing is in the optical source wavelength within the 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 laser with the oscillation wavelength about 600nm, perhaps be the laser with the oscillation wavelength about 400nm～450nm of blue laser.In addition, when forming coloured image, the surface-emission laser light source that can export multiple beam also is 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 develop with contact or discontiguous mode.Can select developing apparatus according to purpose, as long as have above-mentioned functions.For example, can enumerate known developing apparatus, wherein by using brush or roller that single component or two-component developing agent are attached on the photoreceptor 7.In the middle of these, the preferred use remains on its lip-deep developer roll with developer.

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

The monocomponent toner that described developer can be made up of toner perhaps comprises the two-component developing agent of toner and carrier.

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

(the number average shape coefficient, this shape coefficient is expressed as (ML to the average shape factor of toner particle ²/ A) * (π/4) * 100, wherein ML represents the largest particles length, and A represents 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, 4 μ m～9 μ m more preferably again.

Toner is not subjected to the special restriction of its manufacture method.Can use the toner of making according to following method, for example mixing comminuting method, the charge control agent that wherein adds adhesive resin, colorant, detackifier and use in case of necessity, mixing subsequently, also sorting of pulverizing; Wherein the particle that described mixing comminuting method is 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, with dispersion liquid, colorant and the detackifier of gained and the dispersion liquid phase mixing of spendable charge control agent in case of necessity, aggegation subsequently, heating and fusion obtain toner then; 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 the aqueous solvent to carry out polymerization; Perhaps dissolve suspension method, wherein with adhesive resin, colorant and detackifier and in case of necessity the solution of spendable charge control agent be suspended in and carry out granulation in the aqueous solvent.

In addition, also can adopt known manufacture method, as core, and the particle that will flocculate is further attached to it such as the toner that wherein will adopt said method to obtain, with after the method for heating and fusion formation core-shell structure.As the method for making toner, from the angle of shape control and size distribution control, the suspension polymerization, emulsion polymerization agglutination and the dissolving suspension method that preferably all adopt aqueous solvent to make, and special preferred emulsion polymerization agglutination.

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

When toner was used as two-component developing agent, the blending ratio of toner and carrier was 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 the 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 of making by semiconductive polyimide, polyamidoimide, polycarbonate, poly-fragrant fat, polyester or rubber etc. (intermediate transfer belt).As the form of intermediate transfer medium 50, except that band, can also use drum.

Except that above-mentioned each equipment, described image processing system 100 for example can also have and photoreceptor 7 to be carried out the light that light removes electricity removes 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 shown in Fig. 5 120 is that the tandem full-colour image that comprises four handle boxes 300 forms device.

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 that an Electrophtography photosensor is used for a kind of color.Except image processing system 120 forms the series system, image processing system 120 has and image processing system 100 identical construction.

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

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

Embodiment

Followingly further describe illustrative embodiments of the present invention, but the present invention is not limited to these embodiment with reference to embodiment.

Embodiment 1

The manufacturing of Electrophtography photosensor

The preparation of undercoat

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

Then, when stirring, the surface treated zinc paste of 110 weight portions is mixed mutually with 500 weight portion tetrahydrofurans.In described potpourri, add by 0.6 weight portion alizarin is dissolved in the solution that obtains in the 50 weight portion tetrahydrofurans, stirred 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, the zinc paste that is added with alizarin, the 13.5 weight portion rigidizer (blocked isocyanates of passing through with 38 weight portions with 60 weight portions, trade name: SUMIDULE 3175, by Sumitomo-Bayer Urethane Co., Ltd. make) and 15 weight portion butyral resins (trade name: S-LEC BM-1, make by ponding chemistry society) be blended in the solution that obtains in the 85 weight portion methyl ethyl ketones and the methyl ethyl ketone of 25 weight portions mixes mutually, use the sand mill of the beaded glass that adopts diameter 1mm φ to disperse subsequently 2 hours, thereby obtain dispersion liquid.

In the gained dispersion liquid, add two lauric acid dioctyl tins and 40 weight portion silicon resin particle (trade name: the TOSPEARLs 145 of 0.005 weight portion as catalyzer, by GE-Toshiba Silicone Co., Ltd. make), thus undercoat formation coating fluid obtained.By dipping described coating fluid is applied on the aluminum substrate,, thereby obtains the undercoat that thickness is 20 μ m subsequently in 170 ℃ of dryings and curing 40 minutes.

The preparation of charge generation layer

At first, use adopts the sand mill of the beaded glass of diameter 1mm φ will contain the hydroxyl phthalocyanine gallium as charge generating material, 10 weight portion vinyl chloride/vinyl acetate copolymer resin (trade names: VMCH of 15 weight portions, by Nippon Unicar Co., Ltd. make) and the potpourri dispersion of 200 weight portion n-butyl acetates 4 hours, (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 at least at the Bragg angle in the x-ray diffraction pattern that obtains with CuK α characteristic X ray.In the gained dispersion liquid, add 175 weight portion n-butyl acetates and 180 weight portion methyl ethyl ketones, stir subsequently, thereby obtain charge generation layer formation coating fluid.By dipping described charge generation layer formation is applied on the 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, with 45 weight portion N, N '-diphenyl-N, N '-two (3-aminomethyl phenyl) [1,1 '] xenyl-4,4 '-diamines (hereinafter being called " TPD ") and 55 weight portion bisphenol Z polycarbonate resins (hereinafter are called " PCZ500 ", viscosity average molecular weigh: 50000) be dissolved in 800 weight portion chlorobenzenes, form and use coating fluid thereby obtain charge transport layer.Described coating fluid is applied on the 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

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

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

Assessment

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

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

In image evaluation test (1) and (2), assessed the even property of density unevenness, striped, image deterioration and because the afterimage phenomena (hereinafter being called " ghost image ") that residual image formerly causes of the following stated.

In imaging test, use P paper (A4 size, laterally paper feed is made by Fuji Xerox Co., Ltd).

Assessment result is listed in table 3 and 4.

The assessment of the even property of density unevenness

Adopt 5% shadow tone sample that the even property of density unevenness is carried out visual assessment.

A: excellence.

B: observe the even property of part density unevenness.

C: observe from the image quality angle and think that problematic density unevenness spares property.

The striped assessment

Adopt 10% shadow tone sample that striped is carried out visual assessment.

A: excellence.

B: part striped.

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

The image deterioration assessment

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

Adopt 10% shadow tone sample that image deterioration is carried out visual assessment.

A: excellence.

B: do not finding the image deterioration problem in the printing test continuously, but after placing 24 hours, pinpointing the problems.

C: even also pinpointing the problems in the printing test continuously.

The ghost image assessment

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

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

B: remarkable slightly, shown in Fig. 6 B.

C: clear affirmation, shown in Fig. 6 C.

Surface observation

Electrophtography photosensor surface is afterwards observed in each time in image evaluation test (1) and (2) carried out following observation and assessment.

A: excellence, that is, do not find to adhere to even under 20 times of amplifications, both found scratch 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 manufacturing of Electrophtography photosensor

Carry out according to same way as among the embodiment 1 to the step that forms till the charge transport layer.Composition in the 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 the charge transport layer, and is heating in the atmosphere of about 100ppm 40 minutes in oxygen concentration, form the protective seam of thickness 8 μ m thus in 145 ℃.

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 that so obtains.The result is presented in table 3 and 4.

Embodiment 12

The manufacturing of Electrophtography photosensor

Carry out according to same way as among the embodiment 1 to the step that forms till the charge transport layer.Composition in the 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 the charge transport layer, and uses metal halide lamp (by Ushio Inc. manufacturing) to be 700mW/cm for carrying out illumination in the atmosphere of about 100ppm in oxygen concentration ²The UV irradiation at (365nm place) 60 seconds.Coating in 145 ℃ of heating 40 minutes, is formed 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 manufacturing of Electrophtography photosensor

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

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 that so obtains.The result is presented in the table 4.

The above results shows, compares with comparative example 1, 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: by the compound (trade name: triphenyl methane changes into society by Tokyo and makes) of formula (M1) expression

M-6: by the compound (trade name: BisP-IOTD, society makes by Honshu chemistry) of formula (M1) expression

M-7: by the compound (trade name: BisP-BA, society makes by Honshu chemistry) of formula (M1) expression

M-8: by the compound (trade name: BisP-PHBA, society makes by Honshu chemistry) of formula (M1) expression

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

A-DCP: the monomer (making) that does not have charge-transporting by Xin Zhong village chemical industry society

A-DPH: the monomer (making) that does not have charge-transporting by Xin Zhong village chemical industry society

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

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

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

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

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

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

OT _Azo15: initiating agent (hot radical produces agent, and You Da mound chemistry society makes)

LUPEROX 26: initiating agent (hot radical produces agent, and by Arkema Yoshitomi, Ltd. makes)

Irganox 819: initiating agent (optical free radical produces agent, is made by Ciba Specialty Chemicals)

Embodiment 16

The manufacturing of organic electroluminescent device

The ito glass substrate that preparation is made of its glass substrate that is provided with the ITO film, described ITO film are that the strips of 2mm is carried out etching with the width, thereby form ITO electrode (anode).With the ultrasonic cleaning in isopropyl alcohol (electronics usefulness, society makes by Northeast chemistry) of described ito glass substrate, carry out drying with the rotary coating machine then.

Then, with 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, be the film of 0.015 μ m thereby form thickness.

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

Thereafter, as luminescent material, with compound (Alq3) vapour deposition that is expressed from the next on hole transporting layer, thereby form the luminescent layer of thickness 0.060 μ m.

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

Compd A lq3

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 luminous between the ITO electrode of anode and the Mg-Ag electrode as negative electrode, and assessed maximum brightness and glow color.These results are presented in the table 5.

In addition, the following luminescent lifetime of in drying nitrogen, measuring described organic electroluminescent device.Current value is set at realizes 50cd/m ²Original intensity, 50% o'clock the hourage that is reduced to its initial value in brightness is decided to be device lifetime.Drive current density is with being presented in the table 5 device lifetime.

Comparative example

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

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

Described organic electroluminescent device detects according to the same way as among the embodiment 16.

Benzidine compound R

Table 5

The above results shows, compares with comparative example 2, 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.Be not to be intended to limit or to limit the invention to disclosed clear and definite form.Obviously, many changes and variation are conspicuous to those skilled in the art.Select and describe illustrative embodiments explaining principle of the present invention and practical application thereof best, thereby make 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. Electrophtography photosensor, described Electrophtography photosensor comprises conductive base and the photographic layer that is arranged on the described conductive base at least, wherein, the outmost surface layer of described Electrophtography photosensor is made by the cured film of following composition, and described composition comprises by with the compound shown in the following formula (M1) with have the charge-transporting material of chain polymerization functional group:

Wherein, in formula (M1), X ¹⁰¹And X ¹⁰²Represent hydrogen atom, halogen atom independently of one another, have 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, or the substituting group that forms by these moiety combinations; R ¹⁰¹And R ¹⁰³Represent hydroxyl independently of one another or have the alkoxy of 1～15 carbon atom; M11 and m13 represent integer 0 or 1 independently of one another; R ¹⁰²And R ¹⁰⁴Expression independently of one another has the alkyl of 1～15 carbon atom; M12 and m14 represent integer 0,1,2 or 3 independently of one another; At described-Y ¹⁰¹-X ¹⁰³In, Y ¹⁰¹Expression azo group or siloxy, X ¹⁰³Expression has the alkyl of 1～15 carbon atom, the alkoxy with 1～15 carbon atom, cyano group, phenoxy group or has the aryl of 6～30 carbon atoms.

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

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

3. Electrophtography photosensor as claimed in claim 1, wherein, the outmost surface layer of described Electrophtography photosensor is a protective seam.

4. 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.

5. Electrophtography photosensor as claimed in claim 4, 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 the formula (M1) and has the described charge-transporting material of chain polymerization functional group.

6. Electrophtography photosensor as claimed in claim 1, described Electrophtography photosensor also comprises the undercoat that is arranged on the described conductive base.

7. handle box, described handle box comprise each described Electrophtography photosensor in the claim 1～6 and are selected from least one unit in the group of being made up of following unit: be used for charhing unit that described Electrophtography photosensor is charged; Be used to use toner will be formed on the developing cell of the latent electrostatic image developing on the described Electrophtography photosensor; Remove the unit with the toner that is used for the toner that remains in described Electrophtography photosensor surface is removed.

8. image processing system, described image processing system comprises: each described Electrophtography photosensor in the claim 1～6; Be used for charhing unit to described Electrophtography photosensor charging; Be used for forming the unit at the electrostatic latent image that on the described Electrophtography photosensor of charging, forms electrostatic latent image; Thereby be used to use toner will be formed on the developing cell of the latent electrostatic image developing formation toner image on the described Electrophtography photosensor; With the transfer printing unit that is used for described toner image is transferred to transfer printing body.

9. the cured film of a composition, described composition comprise by with the compound shown in the following formula (M1) with have the charge-transporting material of chain polymerization functional group:

10. cured film as claimed in claim 9, wherein, described charge-transporting material is at least a by with the compound of following formula (I) expression:

11. an organic electroluminescent device, described organic electroluminescent device comprises anode, hole transporting layer, luminescent layer and negative electrode, and wherein, described hole transporting layer comprises claim 9 or 10 described cured film at least.