CN100549842C

CN100549842C - The manufacture method of Electrophtography photosensor, Electrophtography photosensor, handle box and electro-photography apparatus

Info

Publication number: CN100549842C
Application number: CNB2005800097951A
Authority: CN
Inventors: 雨宫升司; 中田浩一; 池末龙哉; 满居隆浩; 岛田明; 植松弘规; 石井周二; 丸山晶夫
Original assignee: Canon Inc
Current assignee: Canon Inc
Priority date: 2004-03-26
Filing date: 2005-03-25
Publication date: 2009-10-14
Anticipated expiration: 2025-03-25
Also published as: CN100492182C; CN1938648A; CN1950756A; CN1957301A; CN100549841C

Abstract

The objective of the invention is to for suppress by the superficial layer on the surface of Electrophtography photosensor and and the device of its butt between the trembling of the big cleaning balde that causes of friction force, roll or the marginal portion damaged and occurred when having made the recess of shallow concave shape of regulation shape on the superficial layer surface, the lost of life phenomenon of the endurance life that is caused by damage is improved, and especially is the significant especially the problems referred to above that become when the initial stage stably improves the intensity of using the improved surface layer for the high-durability of realizing Electrophtography photosensor and will have an improvement of high resiliency deformation rate till many printings curable resin etc. is used for the Electrophtography photosensor of superficial layer.Above-mentioned purpose can solve by using following Electrophtography photosensor, this Electrophtography photosensor possesses supporter and organic photosensitive layer, it is characterized in that, be formed with the recess of shallow concave shape on the surface of the superficial layer of this Electrophtography photosensor, and then also be formed with recess with this superficial layer surface identical patterns by the superficial layer of this Organophotoreceptor with interface that following one deck (surperficial lower floor) of its next-door neighbour forms.

Description

The manufacture method of Electrophtography photosensor, Electrophtography photosensor, handle box and electro-photography apparatus

Technical field

The handle box and the electro-photography apparatus that the present invention relates to the manufacture method of Electrophtography photosensor, Electrophtography photosensor and have Electrophtography photosensor.

Background technology

As Electrophtography photosensor, from having cheap and advantage such as high productivity, be provided with on cylindric supporter and use the photographic layer formed Electrophtography photosensor of organic material as photoconductivity material (charge generation material, charge transport materials), promptly so-called electrophotographic photoreceptor is used widely.As the electrophotographic photoreceptor, from having advantages such as ISO and high-durability, main flow is the Electrophtography photosensor with so-called cascade type photographic layer, and described cascade type photographic layer is the photographic layer that charge generating layer that will contain charge generation materials such as photoconductivity dyestuff or photoconductivity pigment and the charge transport layer that contains charge transport materials such as photoconductivity polymkeric substance or photoconductivity low molecular compound are laminated.

The surface of Electrophtography photosensor charged by directly applying (once charged), exposure (image exposure), utilize the development of toner, to the transfer printing of transfer materials such as paper, the electric external force and/or the mechanical external forces such as removing of transfer printing remaining toner, require that for Electrophtography photosensor these external force are had permanance.Specifically, require, promptly require to have mar resistance or mar proof etc. having permanance by the damage on the surface that these external force caused or the wearing and tearing of generation.

As the mar resistance on the surface of improving the electrophotographic photoreceptor and the technology of mar proof, for example, in Japanese patent laid-open 02-127652 communique, disclose and to have used curable resin (to be positioned at the layer of the outmost surface of Electrophtography photosensor as superficial layer as the cured layer of binder resin, in other words, be positioned at layer away from the position of supporter.) Electrophtography photosensor.

In addition, in Japanese patent laid-open 05-216249 communique and Japanese patent laid-open 07-072640 communique, disclose and a kind ofly will be cured charge transfer cured layer that polymerization forms Electrophtography photosensor by monomer that utilizes heat energy or luminous energy to make to have carbon-to-carbon double bond and charge transfer monomer with carbon-to-carbon double bond as superficial layer.

In addition, open the 2000-066424 communique and the Jap.P. spy opens in the 2000-066425 communique the Jap.P. spy, disclose a kind of hole transport ability compound that in a part, has chain polymerization functional group that will make by the energy that utilizes electron ray and be cured charge transfer cured layer that polymerization forms Electrophtography photosensor as superficial layer.

As mentioned above, in recent years, as the mar resistance on the surface of improving the electrophotographic photoreceptor and the technology of mar proof, the superficial layer of day by day having established Electrophtography photosensor adopts cured layer, with the technology of the physical strength that improves superficial layer.

And as mentioned above, Electrophtography photosensor is generally used for comprising that the electrophotographic image of charged operation-exposure process-developing procedure-transfer printing process-cleaning process forms in the technology.

Form in the technology at electrophotographic image, by removing the toner that remains on the Electrophtography photosensor, promptly removing the cleaning process that the transfer printing remaining toner cleans this Electrophtography photosensor surface is the very important operation that obtains distinct image after transfer printing process.

As clean method, advantages such as, easy design low from cost, main flow is a method as described below: by making cleaning balde and Electrophtography photosensor butt, eliminate the gap between this cleaning balde and this Electrophtography photosensor, prevent that toner from pushing through this gap, thus the method that the transfer printing remaining toner is struck off.

Especially, when forming coloured image, by reproducing desirable color with the toner of multiple colors such as magenta, cyan, yellow, black is superimposed, so the use amount of toner is far more than the situation that forms monochrome image, therefore, it is only using the clean method of cleaning balde.

But, the clean method of use cleaning balde, because the friction force of cleaning balde and Electrophtography photosensor is very big, existence causes trembling, rolling of cleaning balde or the shortcoming that the marginal portion is damaged easily.In addition, the trembling of so-called cleaning balde is meant that the frictional resistance owing to the surface of cleaning balde and Electrophtography photosensor becomes the phenomenon that causes cleaning balde that vibration takes place greatly, and rolling of so-called cleaning balde is meant the phenomenon of cleaning balde to the moving direction counter-rotating of Electrophtography photosensor.

The physical strength of the superficial layer of Electrophtography photosensor is high more, be that the surface of Electrophtography photosensor is difficult to friction more, it is remarkable more that the problem of these cleaning baldes will become.

In addition, the superficial layer of electrophotographic photoreceptor normally forms by dip coating, but owing to the surface of the superficial layer that forms by dip coating, be that the surface of Electrophtography photosensor becomes very level and smooth, thereby the surface contact area of cleaning balde and Electrophtography photosensor becomes big, cleaning balde and becomes greatly with the frictional resistance on the surface of Electrophtography photosensor, and it is remarkable that the problems referred to above become.

As suppressing trembling, roll or one of the damaged method of marginal portion of cleaning balde, known have a method of the surface of Electrophtography photosensor suitably being carried out surface roughening.

As technology with the surface roughening of Electrophtography photosensor, for example, open in the clear 53-092133 communique the Jap.P. spy, disclose a kind of for easily from the surface isolation transfer materials of Electrophtography photosensor, with the surfaceness restriction technology within the limits prescribed of Electrophtography photosensor.Open in the clear 53-092133 communique the Jap.P. spy, disclose a kind of drying condition that passes through to control when forming superficial layer, the rough surface of Electrophtography photosensor is changed into the method for orange peel shape.

In addition, open in the clear 52-026226 communique, disclose and a kind ofly contained particle in the superficial layer, thereby made the technology of the surface roughening of Electrophtography photosensor by making the Jap.P. spy.

In addition, open in the clear 57-094772 communique the Jap.P. spy, disclose a kind of by using metal wire brush that the surface of superficial layer is ground, thereby make the technology of the surface roughening of Electrophtography photosensor.

In addition, in Japanese patent laid-open 01-099060 communique, disclose a kind of in order to solve at the counter-rotating (rolling) of using the cleaning balde that is occurred when using in specific cleaning unit and toner and the electro-photography apparatus more than specific process velocity or the deletion problem of marginal portion, with the technology of the surface roughening of electrophotographic photoreceptor.

In addition, in Japanese patent laid-open 02-139566 communique, disclose a kind of by using membranaceous abrasive substance that the surface of superficial layer is ground, thereby make the technology of the surface roughening of Electrophtography photosensor.

But, in above-mentioned prior art, can not fully solve trembling and rolling problem of above-mentioned cleaning balde.

In addition, as other technology with the surface roughening of Electrophtography photosensor, in Japanese patent laid-open 02-150805 communique, disclose a kind ofly, the outer peripheral face of Electrophtography photosensor has been carried out the technology of surface roughening by blasting treatment for the counter-rotating (rolling) that prevents cleaning balde or damaged (breach) of marginal portion.

Summary of the invention

Present inventors for solve the trembling of above-mentioned cleaning balde, roll, the deletion problem of marginal portion, attempted the method put down in writing by Japanese patent laid-open 02-150850 communique surface roughening with Electrophtography photosensor, its result has obtained surperficial Electrophtography photosensor with recess of a plurality of shallow concave shape, but carry out image when output in the electro-photography apparatus in that such Electrophtography photosensor is installed to, but have following new problem.

That is the reduction speed on the surface when, Electrophtography photosensor being used for electro-photography apparatus and the speed of growth of damage normally the degree by suffered electric external force of Electrophtography photosensor in the electro-photography apparatus or mechanical external force, superficial layer with employed material in the coating fluid and be coated with this superficial layer and make after with coating fluid its condition dry or when solidifying wait default.The thickness of the coated film of the moisture state when therefore, the life-span of Electrophtography photosensor, normally the speed of growth, coating surface layer of the reduction speed by default surface and damage was with coating fluid waits to preset.

But, have in the situation of Electrophtography photosensor of recess of shallow concave shape on the surface, if it is used in long-time repeatedly, will image deflects earlier take place than the anticipation life-span of this Electrophtography photosensor, thereby earlier become and to be difficult to use (below be also referred to as " lost of life that damage causes ") life-span than anticipation.

The object of the present invention is to provide a kind ofly to have the Electrophtography photosensor that above-mentioned " lost of life that damage causes " phenomenon of being taken place in the Electrophtography photosensor of recess of shallow concave shape is inhibited on the surface, and the handle box and the electro-photography apparatus that the manufacture method of this Electrophtography photosensor are provided and possess this Electrophtography photosensor.

Present inventors carry out the result of active research, found out ought be only on the surface of Electrophtography photosensor, promptly only form the recess of shallow concave shape and when making the local attenuation of thickness (the part attenuation of this recess) of this superficial layer on the surface of the superficial layer of Electrophtography photosensor, above-mentioned " lost of life that damage causes " becomes significant problem, and found to have in the Electrophtography photosensor of recess of a plurality of shallow concave shape on the surface, by superficial layer and and following one deck of superficial layer next-door neighbour between the interface also have a plurality of and the corresponding recess of recess this shallow concave shape (towards the depression of supporter one side), can suppress above-mentioned " lost of life that damage causes ", thereby finish the present invention.

That is, the present invention is:

(1) a kind of Electrophtography photosensor, it has supporter and the organic photosensitive layer that is arranged on this supporter, it is characterized in that: the recess that is formed with a plurality of shallow concave shape on the surface of the superficial layer of this Electrophtography photosensor, in the recess of this shallow concave shape, longest diameter the scope of 1～50 μ m and the degree of depth more than 0.1 μ m and volume at 1 μ m ³The number of the recess of above shallow concave shape is 5～50 on the surface of the superficial layer of this square Electrophtography photosensor of per 100 μ m, and this superficial layer and and following one deck of this superficial layer next-door neighbour between the interface be formed with the corresponding recess of recess of the shallow concave shape on a plurality of and the surface that is formed on this superficial layer;

(2) according to (1) described Electrophtography photosensor, wherein, the matching rate of the recess that the recess of the shallow concave shape that forms on the surface of described superficial layer and the interface between following one deck of described superficial layer and described and superficial layer next-door neighbour form is 50～100%;

(3) according to (2) described Electrophtography photosensor, wherein, the matching rate of the recess that the recess of the shallow concave shape that forms on the surface of described superficial layer and the interface between following one deck of described superficial layer and described and superficial layer next-door neighbour form is 70～100%;

(4) according to any described Electrophtography photosensor in (1)～(3), wherein, the elastic deformation rate on the surface of described superficial layer is more than 46%;

(5) according to (4) described Electrophtography photosensor, wherein, the elastic deformation rate on the surface of described superficial layer is more than 50%;

(6) according to any described Electrophtography photosensor in (1)～(5), wherein, the elastic deformation rate on the surface of described superficial layer is below 63%; (7) according to any described Electrophtography photosensor in (1)～(6), wherein, the universal hardness on the surface of described superficial layer (Universal Hardness) value (HU) is 150～230N/mm ²Below;

(8) according to any described Electrophtography photosensor in (1)～(7), wherein, the elastic deformation rate of described and superficial layer next-door neighbour's following one layer surface is 45% below, universal hardness value (HU) is 230N/mm ²Below;

(9) according to any described Electrophtography photosensor in (1)～(8), wherein, the thickness of described superficial layer is below the 10 μ m;

(10) according to (9) described Electrophtography photosensor, wherein, the thickness of described superficial layer is below the 6 μ m;

(11) according to any described Electrophtography photosensor in (1)～(10), wherein, described superficial layer is a cured layer;

(12) according to any described Electrophtography photosensor in (1)～(11), wherein, described superficial layer is to contain the cured layer that is selected from least a kind curable resin in the group that acryl resin, phenolics, epoxy resin, silicone resin and urethane resin form;

(13) according to any described Electrophtography photosensor in (1)～(12), wherein, described superficial layer contains by making with the hole transport ability compound that has 2 above chain polymerization functional groups in a part and is cured the solidfied material that polymerization obtains;

(14) according to (13) described Electrophtography photosensor, wherein, described solidfied material is to make with the hole transport ability compound that has 2 above chain polymerization functional groups in a part by heating or irradiation radioactive ray to be cured the solidfied material that polymerization obtains;

(15) according to (14) described Electrophtography photosensor, wherein, described radioactive ray are electron ray;

(16) according to any described Electrophtography photosensor in (1)～(15), wherein, described superficial layer is the layer that forms by coating;

(17) according to any described Electrophtography photosensor in (1)～(16), wherein, described superficial layer is the layer that forms by dip-coating;

(18) according to any described Electrophtography photosensor in (1)～(17), wherein, described photographic layer is from the described stacked charge generation layer of supporter one side and charge transport layer and the cascade type photographic layer that forms, described superficial layer is this charge transport layer, and described following one deck with the superficial layer next-door neighbour is this charge generation layer;

(19) according to any described Electrophtography photosensor in (1)～(18), wherein, described photographic layer is the cascade type photographic layer that forms from the stacked charge generation layer of described supporter one side, first charge transport layer and second charge transport layer, described superficial layer is this second charge transport layer, and described following one deck with the superficial layer next-door neighbour is first charge transport layer;

(20) according to any described Electrophtography photosensor in (1)～(19), wherein, described Electrophtography photosensor also has the protective seam that is arranged on the described photographic layer, described photographic layer is from the described stacked charge generation layer of support body one side and charge transport layer and the cascade type photographic layer that forms, described superficial layer is this protective seam, and described following one deck with the superficial layer next-door neighbour is this charge transport layer;

(21) a kind of manufacture method of Electrophtography photosensor, it is the manufacture method of any described Electrophtography photosensor in (1)～(20), it is characterized in that, comprises following operation:

Superficial layer forms operation: form described superficial layer above the next-door neighbour of described and following one deck that superficial layer is close to;

Recess forms operation: handle by the surface that is formed the formed described superficial layer of operation by this superficial layer being carried out dry type blasting treatment or wet type honing, thereby form the recess of a plurality of shallow concave shape on the surface of described superficial layer, and the interface between following one deck of described superficial layer and described and superficial layer next-door neighbour forms and the corresponding recess of recess this shallow concave shape a plurality of;

(22) a kind of handle box, it is characterized in that, be with any described Electrophtography photosensor in (1)～(20) or the Electrophtography photosensor by (21) described manufacture method manufacturing and be selected from least a kind of handle box that the unit one supports in charged elements, developing cell and the cleaning unit, and this handle box can freely load and unload with respect to the electro-photography apparatus main body;

(23) a kind of electro-photography apparatus, it is characterized in that, possess (1)～(20) in any described Electrophtography photosensor or Electrophtography photosensor and charged elements, exposing unit, developing cell, transfer printing unit and the cleaning unit made by (21) described manufacture method.

According to the present invention, can provide a kind of and have above-mentioned " lost of life that the damage causes " Electrophtography photosensor that is inhibited and manufacture method of this Electrophtography photosensor that is taken place in the Electrophtography photosensor of recess of shallow concave shape and handle box and the electro-photography apparatus that possesses this Electrophtography photosensor on the surface.

Description of drawings

Fig. 1 is the mensuration schematic flow sheet of microsclerometry device Fischer scope H100V (manufacturing of H.Fischer company).

Fig. 2 is the synoptic diagram of sand blasting unit.

Fig. 3 is an example of the cross-section photograph of Electrophtography photosensor of the present invention.

Fig. 4 A is an example of the layer structure of Electrophtography photosensor of the present invention.

Fig. 4 B is another example of the layer structure of Electrophtography photosensor of the present invention.

Fig. 4 C is another example of the layer structure of Electrophtography photosensor of the present invention.

Fig. 4 D is another example of the layer structure of Electrophtography photosensor of the present invention.

Fig. 4 E is other example of the layer structure of Electrophtography photosensor of the present invention.

Fig. 4 F is another example of the layer structure of Electrophtography photosensor of the present invention.

Fig. 4 G is another example of the layer structure of Electrophtography photosensor of the present invention.

Fig. 4 H is another example of the layer structure of Electrophtography photosensor of the present invention.

Fig. 4 I is another example of the layer structure of Electrophtography photosensor of the present invention.

Fig. 5 is the synoptic diagram of electro-photography apparatus of the present invention.

Fig. 6 is the synoptic diagram with electro-photography apparatus of handle box of the present invention.

Fig. 7 is other surface roughening schematic representation of apparatus.

Embodiment

If by using Electrophtography photosensor to cause surperficial damage growth and this damage that produces to reach the following one deck (hereinafter referred to as " surperficial lower floor ") that is close to superficial layer repeatedly, then the use of this Electrophtography photosensor can become difficult usually.

When only on the surface of Electrophtography photosensor, when promptly only forming the recess of shallow concave shape on the surface of the superficial layer of Electrophtography photosensor, compare with the most non-recess that occupies the surface, the thickness of superficial layer is thinner in this recess, thereby reach surperficial lower floor with the damage of non-recess and compare, the damage of this recess reaches surperficial lower floor earlier.The reason that present inventors think that Here it is above-mentioned " lost of life that damage causes ".

Electrophtography photosensor of the present invention, not only form the recess of shallow concave shape on the surface of superficial layer, and the interface between superficial layer and surperficial lower floor, also be formed with recess with the corresponding position of the recess of this shallow concave shape, thereby the part of the local attenuation of the thickness that does not have or exist hardly superficial layer, therefore, compare with the Electrophtography photosensor that only forms the recess of shallow concave shape on the surface of superficial layer, in the Electrophtography photosensor of the present invention, the damage that the recess on the surface produces has reduced than the probability that the damage that produces at non-recess earlier arrives surperficial lower floor.

" recess of shallow concave shape " of the present invention is meant the trickle recess that forms on the surface of the superficial layer of Electrophtography photosensor.Recess preferably exists as far as possible isolatedly, and has the interval of suitable size, the degree of depth, suitable recess, and the existing way that preferred especially recess can not connect into striated, recess has directivity ground to form.

Electrophtography photosensor of the present invention, it is for shape such as for example cylindric, the band shape can be in electro-photography apparatus used repeatedly and have turning axle, repeats electrophotographic processes such as charged, exposure, development, transfer printing, cleaning while rotating.Cleaning balde is provided with respect to the rotating shaft parallel ground of Electrophtography photosensor usually, and with the surperficial butt of the superficial layer of Electrophtography photosensor.Therefore, so-called circumferencial direction is meant the direction vertical with respect to turning axle, the i.e. direction that contacts repeatedly with each treating apparatus by the rotation of Electrophtography photosensor.

In the present invention, 10 mean roughness (Rzjis), concavo-convex equispaced (RSm), maximum peak height (Rp), maximum valley depth (Rv) are that the method for putting down in writing according to JIS-B0601-2001 is measured.In addition, these mensuration are to use surface roughness measurement device (trade name Surfcoder SE3500 type, little slope research institute makes) to carry out.

The surfaceness of the superficial layer of Electrophtography photosensor is all preferred 0.3 μ m of Rzjis～2.5 μ m, more preferably scope of 0.4 μ m～2.0 μ m under two kinds of situations measuring on circumferencial direction and the turning axle direction.If surfaceness is too small, then can not obtain the effect of improving of the present invention that surface roughening brings, if surfaceness is excessive, then on resulting image, occur, and toner pushes through from cleaning balde in a large number owing to the frosted sense that surface roughening produced.

Surface configuration of the presently claimed invention be can be expressed as so-called scrobicula (dimple) shape recess, have a plurality of as far as possible near the shape of circular and isolated recess.The recess of this shallow concave shape does not preferably have directivity with respect to all directions on the surface of Electrophtography photosensor.

In the surface of Electrophtography photosensor concavo-convex, when paddy partly connects into striated, the problem of the image deflects of the caused striated of surface configuration particularly under hot and humid long-term down situation about using, takes place in this striated part in low resistance material aggregations such as charged product easily.

Therefore, the ratio of axial Rzjis (B) value the when value of the Rzjis of circumferencial direction (A) and Electrophtography photosensor rotation is near 1, and is just preferred more.

Preferred concavo-convex equispaced RSm is 5 μ m～120 μ m when circumferencial direction and turning axle direction detection, the ratio of RSm of circumferencial direction (C) and the axial RSm of rotation (D) must be RSm (D)/RSm (C)=0.5～1.5.

In addition, more preferably RSm is 10～100 μ m, RSm (D)/RSm (C)=0.8～1.2 when circumferencial direction and turning axle direction detection.

Can not connect but the whole surface configuration of surface roughening randomly at circumferencial direction by identical shape, can make Electrophtography photosensor can not concentrate identical shape in certain part of cleaning balde when rotated, scatteredload, damaged etc. with the marginal portion rolled that can improve phenomenon that toner pushes through, improve scraper plate.

In addition, carry out butt, therefore have only concavo-convex interval because the surface of Electrophtography photosensor and cleaning balde band velocity contrast, when RSm is too small, the effect that does not have surface roughening, if when excessive, the bad tendency that increases of cleaning balde that then exists toner to push through etc.

In addition, surface configuration of the present invention is contemplated to be and compares the shape with more recesses with protuberance.If the convex form on Electrophtography photosensor is many, the height of protuberance is big, then the shock resistance of cleaning balde is increased, particularly when long-time durable the use, produce the damaged problem in marginal portion of cleaning balde.

Therefore, in the present invention, in order optionally to form the shape that reduces protuberance, increases recess, preferred maximum peak height (Rp) is below the 0.6 μ m, more preferably below the 0.4 μ m.In addition, the ratio of maximum valley depth Rv and maximum peak height Rp more than the preferred Rv/Rp=1.2, more preferably more than 1.5, at this moment has better effect.

Describe at further studying these results in great detail with recess of shallow concave shape.In the mensuration of the recess of shallow concave shape, use surface shape measuring system (SurfaceExplorer SX-520DR type instrument, the manufacturing of (strain) water chestnutization システ system company) to estimate.

During test, at first will rouse sample and be placed on the worktable, and adjust degree of tilt and make its level, read the three-dimensional shape data on the surface of Electrophtography photosensor with waveform pattern.At this moment, object lens use 50 times multiplying power observing within sweep of the eye at 100 μ m * 100 μ m.Then, use the contour line data of the particle analysis program presentation surface in the data analysis software.

Hole analytical parameters when asking the recess of calculating shallow concave shape, area etc. is made as the longest diameter upper limit: 50 μ m, longest diameter lower limit: 1 μ m, degree of depth lower limit: 0.1 μ m is above, the volume lower limit: 1 μ m ³More than observe, be regarded as the number of part of the recess of shallow concave shape on the computed image.The recess number of the shallow concave shape of the square area of per 100 μ m is the number of recess of the shallow concave shape that can see in the visual field of instrumentation analysis diagram picture and the number that obtains.

The area ratio of the recess of shallow concave shape is obtained as follows, under the visual field same as described above, identical analysis condition, the total area is made as 10000 μ m that is: ²Thereby, and obtain the area of the recess part of shallow concave shape by the calculated value summation of particle being resolved software, obtain (the recess total area/total area of shallow concave shape) * 100 (%), be the area ratio of the recess of shallow concave shape.

The average aspect ratio of the recess of shallow concave shape (aspect ratio) is by under the visual field same as described above, identical analysis condition, and the data of the recess of the shallow concave shape that collection can be discerned obtain that the mean value of this length-diameter ratio determines.

It is 5～50 that the number of the recess of the suitable shallow concave shape of Electrophtography photosensor of the present invention is preferably per 100 μ m square, more preferably 5～40.The area ratio of the recess of preferred shallow concave shape is 3%～60%, more preferably 3～50%.If the number of the recess of these shallow concave shape and area ratio surpass the upper limit or be lower than lower limit, all can not obtain the effect of surface roughening.

In addition, the average aspect ratio of the recess of preferred shallow concave shape is 0.5～0.95.

That the surface configuration that conforms to the regulation of these numerical value demonstrates is of the presently claimed invention, have concavo-convex near the recess of the isolated shallow concave shape of circular shape.Have the appropriate rough surface shape and the surface of direction-free surface roughening by having such shape, becoming, thereby based on the reason of above-mentioned record, such surface configuration can obtain the effect of improving of the present invention effectively.

The invention is characterized in: when superficial layer is applied with the recess of stating optimized specific shallow concave shape, the pattern of the recess of the shallow concave shape on the surface of superficial layer and between superficial layer and surperficial lower floor the pattern of the recess of the shallow concave shape at formed interface roughly the same.

About the recess pattern of the shallow concave shape on the surface of superficial layer of the present invention and between superficial layer and surperficial lower floor the shallow concave shape at formed interface the recess pattern meet ratio, this meets the numerical value of ratio as quantificational expression to use matching rate.

Matching rate ask the calculation method as described below.

At first, in the face of Electrophtography photosensor, cut out the square several places sample in the 5mm left and right sides arbitrarily.Therein, use SEM to observe the cross section of 1 sample, from wherein selecting the recess part of several shallow concave shape arbitrarily, surperficial lower floor, the superficial layer of taking this part are present in the interior cross-section photograph of same field of view, for the recess part of each shallow concave shape, use cross-section photograph to carry out following test.

Provide the example of the cross-section photograph of Electrophtography photosensor of the present invention among Fig. 3.

The Rv11max (maximum valley depth) of the recess of the shallow concave shape by cross-section photograph surface measurements laminar surface and at Rv12max (maximum valley depth) corresponding to the recess of the formed shallow concave shape in interface of the superficial layer of the part of this depression and surperficial lower floor.And, similarly measure the diameter L11 and the L12 of the recess of above-mentioned two shallow concave shape from cross-section photograph.Use these values, try to achieve matching rate by following formula.

100×(Rv12/Rv11+L12/L11)/2＝F1％

(: the matching rate of sample No.1)

To a plurality of positions in the sample that is cut out, and then a plurality of positions of the sample that cuts out are all carried out this operation in the face of Electrophtography photosensor, get and amount to the above mean value in 20 positions, as the matching rate of this Electrophtography photosensor.Its relation is shown below.

100×(Rvn2/Rvn1+Ln2/Ln1)/2＝Fn％

(: the matching rate of sample No.n)

(F1+F2+F3+......+Fn)/n＝F％

(: the matching rate of the Electrophtography photosensor of being measured)

In the present invention, if the recess of the shallow concave shape that forms on the surface of superficial layer is more than 50% with the matching rate of the recess of the shallow concave shape of the formation of the interface between superficial layer and surperficial lower floor, then shape, pattern reach much at one state as can be known from the permanance actual conditions.Promptly, because the thickness of the superficial layer of the recess with shallow concave shape on the surface of Electrophtography photosensor becomes even, thereby in Electrophtography photosensor long-term durable, slowly wear and tear and penetrate superficial layer and make the damage of superficial layer reach surperficial lower floor and then produce the probability of the image of damage in the surface of superficial layer, and the surface of the superficial layer probability that reaches surperficial lower floor but the degree of depth damage of the superficial layer that takes place suddenly penetrates superficial layer that weares and teares hardly diminishes.Promptly, be difficult for being created in the caused image deflects of damage under the durable condition, and close with the anticipation life-span numerical value of the Electrophtography photosensor that calculates according to the damage growth rate of the reduction of the unit number at durable initial stage of Electrophtography photosensor and the unit number at durable initial stage, and can continue to use Electrophtography photosensor until the superficial layer of this Electrophtography photosensor near the original due life-span.

Present inventors discover, more preferably matching rate is more than 70%, can be more near the life-span number of envisioning.

In the present invention, as mentioned above,, then can use any film-forming method or surface roughening process as long as can on superficial layer, form the recess of above-mentioned shallow concave shape.

Wherein, in order to be met easily as the recess of the shallow concave shape of above-mentioned matching rate of the presently claimed invention surface configuration as superficial layer, it all is effective using any mechanical surface roughening method.In various mechanical surface roughening methods, as method, preferred dry sand-blast and the wet type honing method of the recess that forms shallow concave shape.In addition, owing to can carry out surface roughening under the Electrophtography photosensor of damp condition sensitivity and the condition that the water equal solvent contacts not making, more preferably use the dry type sand-blast.

As the sandblast method for processing, the method that comprises the method for using pressurized air to spray, sprays as power with motor etc., but in order critically to control the surface roughening of Electrophtography photosensor, and on the simplification this point of equipment, preferably use compressed-air actuated method.

As employed abrasive substance in the sandblast, can list ceramic-like such as aluminium oxide, zirconia, silit, glass, metal species such as stainless steel, iron, zinc, resenes such as nylon, polycarbonate, epoxy resin, polyester.Particularly consider preferred glass, aluminium oxide, zirconia from the efficient and the cost aspect of surface roughening.

The example of sandblast processing unit (plant) used in the present invention as shown in Figure 2.Be stored in abrasive substance in the container (not shown) from the passage distributing nozzle of 2-4, use the pressurized air that imports from the passage of 2-3 to spray, impact by workpiece support body 2-6 and supported the also Electrophtography photosensor 2-7 of rotation from injection nozzle 2-1.At this moment, nozzle and workpiece distance is determined by nozzle stationary fixture, the arm adjustment of 2-2 and 2-9.The common limit of nozzle is moved the limit with respect to the turning axle direction of workpiece and is carried out surface roughening and handle, and moves along the turning axle direction of workpiece by nozzle support body 2-8, can carry out uniform surface roughening to workpiece and handle.

At this moment, the bee-line on the surface of nozzle and Electrophtography photosensor must be adjusted into proper spacing.If hypotelorism or far away excessively then exists working (machining) efficiency to reduce or can not carry out the situation of desirable surface roughening.The employed compressed-air actuated pressure of power that sprays also must be adjusted to suitable pressure.Like this, can establish by after finishing the system film, the electrophotographic photoreceptor being carried out surface roughening and the good manufacture method of throughput rate.

The surface configuration of the electric conductivity matrix of surface configuration of the present invention or surface roughening and Electrophtography photosensor ground is irrelevant.Particularly the system embrane method at organic photosensitive layer is in the situation of dip coating, and the surface of common made film is very level and smooth, even ground has carried out surface roughening, can not reflect its surface configuration.

By implementing in the situation of recess surface shape that the mechanical surface roughening forms shallow concave shape of the present invention, preferably to electrophotographic sensitization system film after the final layer that uses, carry out surface roughening from the superficial layer of Electrophtography photosensor.

In the present invention, it is important using the electrophotographic photoreceptor.The electrophotographic photoreceptor has following advantage: its thickness, elastic property etc. are suitable for carrying out surface roughening behind the Electrophtography photosensor system film usually, and by the condition of control surface roughening, can be at random in the final surface configuration of using of control on a large scale.At this moment, especially can make the Electrophtography photosensor in the scope of the present invention have special surface of good shape from the elastic deformation rate of the surface measurements of Electrophtography photosensor.

Surface roughening technology of the present invention is the effective ways that form the good Electrophtography photosensor of wear properties.Even the variation of initial surface shape also seldom has the tendency that keeps shape in good long-term use of the Electrophtography photosensor permanance that particularly the elastic deformation rate is high.It is important from initial stage such Electrophtography photosensor being controlled at best geometry.

The elastic deformation rate of superficial layer is on the Electrophtography photosensor behind the surface roughening, promptly to measure from superficial layer.The elastic deformation rate of surface lower floor is the surface measurements of the Electrophtography photosensor of never described superficial layer.

Wherein, elastic deformation rate We% is by using micro-hardness measurement device Fischerscope H100V (manufacturing of Fischer company), under 25 ℃, the environment of humidity 50%, be the load that applies 6mN on 136 ° the Vickers tetragonal pyramid diamond penetrator continuously at the opposite face angle, directly read the compression distance under the load and the value that determines.Specifically, till reaching 6mN, final load carries out interim mensuration (following 273 points of the retention time of each point 0.1S).The synoptic diagram of the output chart of Fischer scope H100V (manufacturing of Fischer company) as shown in Figure 1.Among Fig. 1, the longitudinal axis F (mN) that represents to load.Transverse axis is represented compression distance h (μ m).

In the present invention, the compression distance of universal hardness value (below be also referred to as HU) under can the 6mN load when under final load 6mN, being pressed into, and try to achieve by following formula (1).

H: the compression distance under the test load (mm)

The working load (energy) that the elastic deformation rate can apply film from pressure head, be that pressure head is tried to achieve the variation of the energy that increase and decrease caused of the load of film, specifically, can try to achieve from following formula (2).

Elastic deformation rate=We/Wt (2)

In the following formula, the area that A-B-D-A surrounded in total working load Wt (nJ) presentation graphs 1, elastic deformation working load We (nJ) the expression area that C-B-D-C surrounded.

In the present invention, the elastic deformation rate of preferred superficial layer is that We% is more than 46%, more preferably more than 50% and below 63%.

If the elastic deformation rate of superficial layer is lower than 46%, the variation of the surface configuration after using repeatedly increases, even suitably carry out the surface roughening of superficial layer, can not keep its surface configuration for a long time, be stranded and can not keep the effect of surface roughening for a long time, it is bad or damage etc. takes place to be easy to generate cleaning.In addition, when carrying out surface roughening by blasting treatment, the energy of the particle of collimeter surface layer disperses in superficial layer easily, thereby power is difficult to be delivered to surperficial lower floor equably, has the concaveconvex shape tendency different with the concaveconvex shape of superficial layer of surperficial lower floor, and the result is that matching rate reduces, the variation of the effective thickness in the face of superficial layer increases, and then when durable, the probability that damage reaches surperficial lower floor increases.

In addition, when particularly carrying out surface roughening by blasting treatment, the concavo-convex protuberance that the granule impact surface forms increases, image produces damaged probability and increases.

If elastic deformation rate We% reaches the scope more than 50%, the variation of the surface configuration after then using repeatedly diminishes on the contrary, and it is more effective that the present invention becomes.In addition, when carrying out surface roughening by blasting treatment, the impact energy of the particle of shock surface can not disperseed in superficial layer, and be delivered to surperficial lower floor easily equably, concavo-convex and superficial layer concavo-convex close of surface lower floor, therefore matching rate increases, and the variation of the effective thickness in the face of superficial layer reduces, and the probability that damage reaches surperficial lower floor reduces.

Otherwise, if We% is greater than 63% for the elastic deformation rate, then between butt parts such as Electrophtography photosensor and live part or cleaning member, carry paper powder or toner easily secretly, the surface of friction Electrophtography photosensor, thereby produce damage on the surface of Electrophtography photosensor easily, meanwhile also wear and tear easily.In addition; when carrying out surface roughening by blasting treatment; because the energy of the particle of collimeter surface layer is absorbed at superficial layer easily; therefore, power is difficult to evenly be delivered to surperficial lower floor, has the concaveconvex shape tendency different with the concaveconvex shape of superficial layer of surperficial lower floor; matching rate reduces as a result, the variation of the effective thickness in the face of protective seam increases for it; and then when durable, the probability that damage reaches surperficial lower floor increases.

In Electrophtography photosensor of the present invention, the elastic deformation rate of surperficial lower floor is preferably below 45%, and universal hardness value (HU) is preferably 230N/mm ²Below.

In above-mentioned blasting method, when the recess of shallow concave shape is processed and made to superficial layer, the matching rate of the recess of the shallow concave shape that forms for the recess that improves the shallow concave shape that forms on the surface of superficial layer and interface in superficial layer and surperficial lower floor, the elastic deformation rate of surface lower floor is preferably below 45%, and universal hardness value (HU) is preferably 230N/mm ²Below.

When the universal hardness value (HU) of surperficial lower floor greater than 230N/mm ²The time, when sandblast, when accepting peening particle at the interface of surperficial lower floor, not deforming to the impact of superficial layer very much, the result causes matching rate to worsen.In addition, according to circumstances, also occur in problems such as superficial layer or interface crack easily.

In addition, the elastic deformation rate of surperficial lower floor was greater than 45% o'clock, and when sandblast, peening particle is absorbed with interface photographic layer the impact of superficial layer is under superficial layer, at this moment, occurs in problems such as superficial layer surface or interface crack easily.

The thickness of superficial layer of the present invention is preferably below the 10 μ m, more preferably below the 6 μ m.

When thickness is blocked up, even form the surface configuration of superficial layer by blasting treatment, also since the power of peening particle in superficial layer by dispersion, attenuate the interface that is difficult to be delivered under the superficial layer, so matching rate significantly worsens.

Electrophtography photosensor with surface configuration of the present invention is the most effective when superficial layer uses curable resin.This is because the wearing and tearing on the surface of the Electrophtography photosensor that contains curable resin in superficial layer when durable the use are little, the shape on surface no change during in the early stage with durable uses, the only surface configuration of the initial stage of maintenance for a long time formation.For example, can list the superficial layer that the hole transport ability compound that uses curable resin (monomer) or use and have polymerism functional group (chain polymerization functional group or progressively polymerism functional group etc.) (polymerism functional group chemistry is combined on the part of molecule of hole transport ability compound) forms Electrophtography photosensor.In the situation of using the curable resin do not have charge transport ability, also can hybrid charge transmission property material and use.

Especially, in order to obtain the Electrophtography photosensor of elastic deformation rate in above-mentioned scope of superficial layer, can be cured the superficial layer that polymerization (following crosslinked polymerization) forms Electrophtography photosensor by making the hole transport ability compound with chain polymerization functional group, particularly to be cured the superficial layer that polymerization forms Electrophtography photosensor with the hole transport ability compound that has 2 above chain polymerization functional groups in a part be especially effective by making.In addition, when use has the hole transport ability compound of polymerism functional group progressively,, preferably in a part, has more than 3 the progressively hole transport ability compound of polymerism functional group as this compound.

Below, the hole transport ability compound that has a chain polymerization functional group at use forms the method for the superficial layer of Electrophtography photosensor and carries out specific description.In addition, use and to have progressively that the situation of the hole transport ability compound of polymerism functional group also is same.

The superficial layer of Electrophtography photosensor can comprise the hole transport ability compound with chain polymerization functional group and the superficial layer coating fluid of solvent by coating, make this hole transport ability compound be cured polymerization, so that the superficial layer that is coated with is solidified to form with coating fluid with chain polymerization functional group.

When the coating surface layer is used coating fluid, can use for example coating processes such as dip coating (dip coated method), spraying process, curtain formula rubbing method, method of spin coating.In these coating processes, from the viewpoint of efficient and yield-power, preferred dip coating, spraying process.

As making hole transport ability compound be cured the method for polymerization, can list and use heat with chain polymerization functional group; Light such as visible light, ultraviolet ray; The method of electron ray or gamma-rays isoradial.As required, also can contain polymerization initiator in coating fluid at superficial layer.

In addition,, preferably use electron ray or gamma-rays isoradial, especially preferably use the method for electron ray as making hole transport ability compound be cured the method for polymerization with chain polymerization functional group.This is because utilize the polymerization of radioactive ray not need polymerization initiator especially.Be cured polymerization by the hole transport ability compound that does not use polymerization initiator to make to have chain polymerization functional group, the superficial layer of very highly purified three-dimensional matrice can be formed, the Electrophtography photosensor that demonstrates the good electron photographic property can be accessed.In addition, in radioactive ray, especially utilize the polymerization of electron ray, it is considerably less by the caused damage to Electrophtography photosensor of irradiation, can demonstrate the good electron photographic property.

Obtain universal hardness value (HU) and the of the present invention Electrophtography photosensor of elastic deformation rate in above-mentioned scope in order to make hole transport ability compound be cured polymerization, consider that the illuminate condition of electron ray is important with chain polymerization functional group by the irradiation electron ray.

When the irradiation electron ray, can use accelerators such as sweep type, electronics curtain type, broad-beam condition type, impulse type and thin layer type to carry out.Accelerating potential is preferably below the 250kV, is preferably below the 150kV especially.Quantity of X-rays X is preferably 1～1000kGy (0.1～100Mrad) scope, especially more preferably 5～200kGy (scope of 0.5～20Mrad).If accelerating potential, quantity of X-rays X are excessive, the situation that then exists the electrical specification of Electrophtography photosensor to worsen.If quantity of X-rays X is too small, the curing polymerization of hole transport ability compound that then has chain polymerization functional group is insufficient, thereby has the curing inadequate situation of superficial layer with coating fluid.

In addition, in order to promote superficial layer with the curing of coating fluid, when the hole transport ability compound that utilizes electron ray to make to have chain polymerization functional group is cured polymerization, preferably irradiated body (object that electron ray shone) is heated.Can be in electron ray pre-irradiation, the irradiation opportunity of heating, postradiation arbitrary stage, preferably the free radical of hole transport ability compound with chain polymerization functional group exist during, make irradiated body reach certain temperature.The temperature that heating preferably proceeds to irradiated body reaches room temperature～250 ℃ (more preferably 50～150 ℃).If the temperature of heating is too high, then exist the material of Electrophtography photosensor can produce the situation of deterioration.If the temperature of heating is low excessively, then by heating resultant effect with insufficient.The time of heating is preferably about several seconds to about tens of minutes, specifically, is preferably 2 seconds～30 minutes.

Atmosphere when electron ray when irradiation and irradiated body heating can be in air, in non-active gas such as nitrogen or helium, in a vacuum any, but from the viewpoint of the inactivation of the free radical that can suppress to cause, preferably in non-active gas or in a vacuum by oxygen.

In addition, from the viewpoint of electrofax characteristic, the thickness of the superficial layer of Electrophtography photosensor is preferably below the 30 μ m, more preferably below the 20 μ m, more preferably below the 10 μ m, more preferably below the 7 μ m.On the other hand, from the viewpoint of the permanance of Electrophtography photosensor, thickness is preferably more than the 0.5 μ m, more preferably more than the 1 μ m.

In addition, so-called chain polymerization is represented is that reaction of formation at polymer substance is divided into chain polymerization and the preceding a kind of polyreaction form during polymerization progressively substantially, specifically, be meant unsaturated polymerization, ring-opening polymerization or the isomerization polymerization etc. that its reaction form is mainly reacted via intermediates such as free radical or ions.

Chain polymerization functional group is meant the functional group that can carry out above-mentioned reaction form.Below, enumerate the unsaturated polymerization functional group of applied range and the example of ring-opening polymerization functional group.

Unsaturated polymerization is meant by free radical or ion etc. and makes unsaturated group, for example C=C, C ≡ C, C=O, C=N, C ≡ N etc. carry out the reaction of polymerization, wherein, is mainly C=C.Below, enumerate the instantiation of unsaturated polymerization functional group.

In following formula, R ¹Expression hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted aryl, replacement or unsubstituted aralkyl etc.Wherein, as alkyl, can list methyl, ethyl, propyl group etc.As aryl, can list phenyl, naphthyl, anthryl etc.As aralkyl, can list benzyl, phenethyl etc.

So-called ring-opening polymerization is meant that carbocyclic ring or oxo ring or azacyclo-etc. have the unsettled ring structure of strain, carry out polymerization in open loop repeatedly, generates the high molecular reaction of chain, and is as spike mostly with ion.Below, enumerate the instantiation of ring-opening polymerization functional group.

In the following formula, R ²Expression hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted aryl, replacement or unsubstituted aralkyl etc.Wherein, as alkyl, can list methyl, ethyl, propyl group etc.As aryl, can list phenyl, naphthyl, anthryl etc.As aralkyl, can list benzyl, phenethyl etc.

In the above-mentioned chain polymerization functional group of enumerating, the chain polymerization functional group that preferably has the structure shown in following formula (1)～(3).

In formula (1), E ¹¹Expression hydrogen atom, halogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted aryl, replacement or unsubstituted aralkyl, replacement or unsubstituted alkoxy, cyano group, nitro ,-COOR ¹¹Perhaps-CONR ¹²R ¹³W ¹¹That expression replaces or unsubstituted alkylidene, replacement or unsubstituted arlydene ,-COO-,-O-,-OO-,-S-or CONR ¹⁴-.R ¹¹～R ¹⁴Represent independently of one another hydrogen atom, halogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted aryl or that replace or unsubstituted aralkyl.Subscript letter x represents 0 or 1.Wherein, as halogen atom, can list fluorine atom, chlorine atom, bromine atoms etc.As alkyl, can list methyl, ethyl, propyl group, butyl etc.As aryl, can list phenyl, naphthyl, anthryl, pyrenyl, thiophenyl, furyl etc.As aralkyl, can list benzyl, phenethyl, menaphthyl, furfuryl group, thienyl etc.As alkoxy, can list methoxyl, ethoxy, propoxyl group etc.As alkylidene, can list methylene, ethylidene, butylidene etc.As arlydene, can list phenylene, naphthylene, anthrylene etc.

As above-mentioned each group the substituting group that can have, can list halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atom, alkyl such as methyl, ethyl, propyl group, butyl, aryl such as phenyl, naphthyl, anthryl, pyrenyl, aralkyl such as benzyl, phenethyl, menaphthyl, furfuryl group, thienyl, alkoxys such as methoxyl, ethoxy, propoxyl group, aryloxy group such as phenoxy group, naphthoxy, nitro, cyano group, hydroxyl etc.

In the formula (2), R ²¹, R ²²Represent independently of one another hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted aryl or that replace or unsubstituted aralkyl.Subscript letter Y represents 1～10 integer.Wherein, as alkyl, can list methyl, ethyl, propyl group, butyl etc.As aryl, can list phenyl, naphthyl etc.As aralkyl, can list benzyl, phenethyl etc.

As above-mentioned each group the substituting group that can have, can list halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atom, alkyl such as methyl, ethyl, propyl group, butyl, aryl such as phenyl, naphthyl, anthryl, pyrenyl, aralkyl such as benzyl, phenethyl, menaphthyl, furfuryl group, thienyl, alkoxys such as methoxyl, ethoxy, propoxyl group, aryloxy group such as phenoxy group, naphthoxy etc.

In the formula (3), R ³¹, R ³²Represent independently of one another hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted aryl or that replace or unsubstituted aralkyl.Subscript letter Z represents 0～10 integer.Wherein, as alkyl, can list methyl, ethyl, propyl group, butyl etc.As aryl, can list phenyl, naphthyl etc.As aralkyl, can list benzyl, phenethyl etc.

In chain polymerization functional group, more preferably has the chain polymerization functional group of the structure shown in the following formula (P-1)～(P-11) with the structure shown in following formula (1)～(3).

In the chain polymerization functional group of the structure shown in the following formula (P-1)～(P-11), the chain polymerization functional group that the chain polymerization functional group that more preferably has the structure shown in the following formula (P-1) is acryloxy, have a structure shown in the following formula (P-2) is a methacryloxy.

In the present invention, in the hole transport ability compound with above-mentioned chain polymerization functional group, preferred (in a part) has the hole transport ability compound of 2 above chain polymerization functional groups.Below enumerate the instantiation of hole transport ability compound with 2 above chain polymerization functional groups.

(P ⁴¹) _a-A ⁴¹-[R ⁴¹-(P ⁴²) _d] _b (4)

In the following formula (4), P ⁴¹, P ⁴²Represent chain polymerization functional group independently of one another.R ⁴¹Expression divalent group.A ⁴¹Expression hole transport ability group.Subscript letter a, b, d represent the integer more than 0 independently of one another.Wherein, a+b * d is more than 2.In addition, when a is 2 when above, a P ⁴¹Can be identical also can be different; B is 2 when above, b [R ⁴¹-(P ⁴²) _d] can be identical also can be different; When d is 2 when above, d P ⁴²Can be identical also can be different.

If enumerate (the P in the following formula (4) ⁴¹) _aAnd [R ⁴¹-(P ⁴²) _d] _bWhole examples for compounds that is replaced by hydrogen atom, can be listed as and lift out oxazole derivant, oxadiazole derivant, imdazole derivatives, triarylamine derivant (triphenylamine etc.), 9-(to the diethylamino styryl) anthracene, 1,1-is two-(the amino phenyl of 4-benzhydryl) propane, styryl anthracene, styryl pyrazoline, phenyl hydrazones class, thiazole, triazole derivative, azophenlyene derivant, acridine derivatives, benzofuran derivatives, benzimidizole derivatives, thiophene derivant, N-phenyl carbazole derivant etc.At these ((P in the following formula (4) ⁴¹) _aAnd [R ⁴¹-(P ⁴²) _d] _bWhole compounds that is replaced by hydrogen atom) in, the compound that preferably has the structure shown in the following formula (5).

In the following formula (5), R ⁵¹That expression replaces or unsubstituted alkyl, replacement or unsubstituted aryl or that replace or unsubstituted aralkyl.Ar ⁵¹, Ar ⁵²Replace or the unsubstituted aryl of expression independently of one another.R ⁵¹, Ar ⁵¹, Ar ⁵²Can directly combine with N (nitrogen-atoms), also can combine or can combine with N (nitrogen-atoms) by-CH=CH-with alkylidene (methylene, ethylidene, propylidene etc.), heteroatoms (oxygen atom, sulphur atom etc.).Wherein, as alkyl, preferred carbon number is 1～10, can list methyl, ethyl, propyl group, butyl etc.As aryl, can list phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, thiophenyl, furyl, pyridine radicals, quinolyl, benzoquinoline base, carbazyl, phenothiazinyl, benzofuranyl, benzo thiophenyl, dibenzofuran group, dibenzo thiophenyl etc.As aralkyl, can list benzyl, phenethyl, menaphthyl, furfuryl group, thienyl etc.In addition, the R in the following formula (5) ⁵¹Be preferably replacement or unsubstituted aryl.

As above-mentioned each group the substituting group that can have, can list fluorine atom, the chlorine atom, bromine atoms, halogen atoms such as iodine atom, methyl, ethyl, propyl group, alkyl such as butyl, phenyl, naphthyl, anthryl, aryl such as pyrenyl, benzyl, phenethyl, menaphthyl, furfuryl group, aralkyl such as thienyl, methoxyl, ethoxy, alkoxys such as propoxyl group, phenoxy group, aryloxy group such as naphthoxy, dimethylamino, diethylamino, benzhydryl amino, diphenyl amino, the amino that two (p-methylphenyl) amino etc. replace, styryl, aryl vinyls such as naphthyl vinyl, nitro, cyano group or hydroxyl etc.

As the R in the following formula (4) ⁴¹The divalent group, can list replacement or unsubstituted alkylidene, replacement or unsubstituted arlydene ,-CR ⁴¹¹=CR ⁴¹²-(R ⁴¹¹, R ⁴¹²Represent independently of one another hydrogen atom, replacement or unsubstituted alkyl or that replace or unsubstituted aryl.) ,-C O-,-SO-,-SO ₂-, oxygen atom, sulphur atom etc., and their combination.Wherein, be preferably the divalent group of the structure shown in (6) that has following formula, the divalent group that more preferably has the structure shown in the following formula (7).

-(X ⁶¹) _p6-(Ar ⁶¹) _q6-(X ⁶²) _r6-(Ar ⁶²) _s6-(X ⁶³) _t6- (6)

-(X ⁷¹) _p7-(Ar ⁷¹) _q7-(X ⁷²) _r7- (7)

In the following formula (6), X ⁶¹～X ⁶³That expression independently of one another replaces or unsubstituted alkylidene ,-(CR ⁶¹=CR ⁶²) _N6-(R ⁶¹, R ⁶²Represent independently of one another hydrogen atom, replacement or unsubstituted alkyl or that replace or unsubstituted aryl.Subscript letter n6 represents that the integer more than 1 is (preferred below 5.)。) ,-CO-,-SO-,-SO ₂-, oxygen atom or sulphur atom.Ar ⁶¹, Ar ⁶²Replace or the unsubstituted arlydene of expression independently of one another.Subscript letter p6, q6, r6, s6, t6 represent independently of one another more than 0 integer (preferred below 10, more preferably below 5.)。Wherein, p6, q6, r6, s6, t6 all are not 0.Wherein, as alkylidene, preferred carbon atom is 1～20, is preferably 1～10 especially, can list methylene, ethylidene, propylidene etc.As arlydene, can list the divalent group of removing 2 hydrogen atoms from benzene, naphthalene, anthracene, phenanthrene, pyrene, benzothiophene, pyridine, quinoline, benzoquinoline, carbazole, benzothiazine, coumarone, benzothiophene, dibenzofurans, dibenzothiophene etc.As alkyl, can list methyl, ethyl, propyl group etc.As aryl, can list phenyl, naphthyl, thiophenyl etc.

In the following formula (7), X ⁷¹, X ⁷²That expression independently of one another replaces or unsubstituted alkylidene ,-(CR ⁷¹=CR ⁷²) _N7-(R ⁷¹, R ⁷²Represent independently of one another hydrogen atom, replacement or unsubstituted alkyl or that replace or unsubstituted aryl.Subscript letter n7 represents that the integer more than 1 is (preferred below 5.)。) ,-CO-or oxygen atom.Ar ⁷¹Replace or the unsubstituted arlydene of expression.Subscript letter p7, q7, r7 represent independently of one another more than 0 integer (preferred below 10, more preferably below 5.)。Wherein, p7, q7, r7 all are not 0.Wherein, as alkylidene, carbon atom is preferably 1～20, is preferably 1～10 especially, can list methylene, ethylidene, propylidene etc.As arlydene, can list the divalent group of removing 2 hydrogen atoms from benzene, naphthalene, anthracene, phenanthrene, pyrene, benzothiophene, pyridine, quinoline, benzoquinoline, carbazole, benzothiazine, coumarone, benzothiophene, dibenzofurans, dibenzothiophene etc.As alkyl, can list methyl, ethyl, propyl group etc.As aryl, can list phenyl, naphthyl, thiophenyl etc.

Below, enumerate the suitable example (compound example) of hole transport ability compound with 2 above chain polymerization functional groups.

Below, at Electrophtography photosensor of the present invention, the layer outside the superficial layer is described in detail in being also included within.

As mentioned above, Electrophtography photosensor of the present invention is the cylindric Electrophtography photosensor that has supporter (cylindric supporter) and be arranged on the organic photosensitive layer (following only be called " photographic layer ") on this supporter.

Photographic layer can be the single-layer type photographic layer that contains charge transport materials and charge generation material in one deck, also can be to be separated into charge generation layer that contains the charge generation material and cascade type (function divergence type) photographic layer that contains the charge transport layer of charge transport materials, but, from the viewpoint of electrofax characteristic, preferred cascade type photographic layer.In addition, in the cascade type photographic layer, comprise the suitable stratotype photographic layer that stacks gradually charge generation layer, charge transport layer from supporter one side, and the contrary stratotype photographic layer that stacks gradually charge transport layer, charge generation layer from supporter one side, but from the viewpoint of electrofax characteristic, preferably along the stratotype photographic layer.In addition, charge generation layer stepped construction can be made, also charge transport layer stepped construction can be made.

In Fig. 4 A to Fig. 4 I, shown the layer structure of Electrophtography photosensor of the present invention.

The Electrophtography photosensor of the layer structure shown in Fig. 4 A is provided with layer (charge generation layer) 441 that contains the charge generation material, layer (the 1st charge transport layer) 442 that contains charge transport materials successively on supporter 41, be provided with thereon by polymerization to have layer 45 (the 2nd charge transport layer) that the hole transport ability compound of chain polymerization functional group forms as superficial layer again.At this moment, 442 the 1st charge transport layers are surperficial lower floor.

In addition, the Electrophtography photosensor of the layer structure shown in Fig. 4 B is provided with the layer 44 that contains charge generation material and charge transport materials on supporter 41, be provided with thereon by polymerization to have layer 45 that the hole transport ability compound of chain polymerization functional group forms as superficial layer again.

In addition, the Electrophtography photosensor of the layer structure shown in Fig. 4 C is provided with layer (charge generation layer) 441 that contains the charge generation material on supporter 41, be provided with thereon by polymerization to have layer 45 that the hole transport ability compound of chain polymerization functional group forms as superficial layer again.At this moment, charge generation layer is surperficial lower floor.

In addition, shown in Fig. 4 D～Fig. 4 I, can and contain layer (charge generation layer) 441 of charge generation material or contain between the layer 44 of charge generation material and charge transport materials at supporter 41, the conductive layer 42 etc. have the middle layer (being also referred to as " undercoat ") 43 of barrier functionality or binding function and to be used to prevent interference fringe etc. is set.

In addition, though can be any layer of structure (for example, having the layer that the hole transport ability compound of chain polymerization functional group forms by polymerization can not be provided with), but in the situation of layer that the hole transport ability compound that will have chain polymerization functional group by polymerization forms as the superficial layer of Electrophtography photosensor, in the layer structure shown in Fig. 4 A～4I, the layer structure shown in preferred Fig. 4 A, 4D, the 4G.

As supporter,, for example, can use metal supporters such as iron, copper, gold, silver, aluminium, zinc, titanium, lead, nickel, tin, antimony, indium so long as it is just passable to demonstrate the supporter (electric conductivity supporter) of electric conductivity.In addition, can use have by aluminium, aluminium alloy, indium oxide-tin oxide alloy equal vacuum evaporation are formed film the layer above-mentioned metallic supporter or plastics system supporter.In addition, also can use conductive particles such as carbon black, granules of stannic oxide, titan oxide particles, silver-colored particle are contained the supporter that is dipped in paper or the plastics with suitable binder resin, perhaps use has the plastic supporter of electric conductivity binder resin etc.

In addition, in order to prevent because the interference fringes that scattering caused of laser etc. etc. can be implemented cutting processing, surface roughening processing, alumite processing etc. to supporting body surface.

As mentioned above, between supporter and photographic layer (charge generation layer, charge transport layer) or aftermentioned middle layer, can also be provided for preventing because the interference fringe that the scattering of laser etc. causes or be used to covers the conductive layer of the damage of supporter.

Conductive layer can form by conductive particles such as disperse black carbon in binder resin, metallic particles, metal oxide particles.

The thickness of conductive layer is preferably 1～40 μ m, especially more preferably 2～20 μ m.

In addition, as mentioned above, between supporter or conductive layer and photographic layer (charge generation layer, charge transport layer), the middle layer with isolation features, binding function can be set.The middle layer is for the cementability that improves photographic layer, improve coating, improve electric charge injection, protection photographic layer from supporter avoids electric destruction etc. and forms.

Vibrin mainly can be used in the middle layer, urethane resin, polyacrylate resin, polyvinyl resin, polystyrene resin, polybutadiene, polycarbonate resin, polyamide, acrylic resin, polyimide resin, phenolics, acryl resin, silicone resin, epoxy resin, carbamide resin, allyl resin, alkyd resin, polyamide-imide resin, nylon resin, polysulfone resin, the polyallyl ether resin, polyacetal resin, binder resins such as butyral resin form.In addition, in the middle layer, can also contain metal or alloy or their oxide, salt, surfactant etc.

The thickness in middle layer is preferably 0.05～7 μ m, more preferably 0.1～2 μ m.

As employed charge generation material in the Electrophtography photosensor of the present invention, can list for example selenium-tellurium, pyrans, sulfo-pyrans class dyestuff, phthalocyanine color with various central metals and various crystallographic system (α, β, γ, ε, X type etc.), anthanthrone pigment, the dibenzo pyrene quinone pigments, pyranthrone pigments, and the AZO pigments of monoazo, bisdiazo, trisazo-etc., indigo pigment, quinacridone pigment, asymmetric quino cyanine (quinocyanine) pigment, amorphous silicon etc.These charge generation materials can only use a kind, also can use more than 2 kinds.

As employed charge transport materials in the Electrophtography photosensor of the present invention, except above-mentioned hole transport ability compound with chain polymerization functional group, can also list pyrene compound, N-alkyl carbazole compound, hydrazone compound, N, N-dialkyl benzene amines, diphenylamine compound, triphenylamine compound, triphenyl methane compound, pyrazoline compounds, compound of styryl, stilbene compounds etc.

The photographic layer function is being separated in the situation of charge generation layer and charge transport layer, charge generation layer can make its dry formation after with the coating fluid coating by the charge generation layer that charge generation material and binder resin and solvent disperseed together get.As process for dispersing, can list the method for using homogenizer, ultrasonic dispersing machine, bowl mill, vibromill, sand milling, roller mill, sleeker, hydraulic shock type high speed dispersor etc.The ratio of the charge generation material in the charge generation layer is preferably 0.1～100 weight % with respect to the general assembly (TW) of binder resin and charge generation material, more preferably 10～80 weight %.In addition, with respect to the general assembly (TW) of charge generation layer, the ratio of charge generation material is preferably 10～100 weight %, more preferably 50～100 weight %.In addition, also can make charge generation layer by vapour deposition method etc. with the independent film forming of above-mentioned charge generation material.

The thickness of charge generation layer is preferably 0.001～6 μ m, more preferably 0.01～2 μ m.

The photographic layer function is being separated in the situation of charge generation layer and charge transport layer, charge transport layer, particularly not as the charge transport layer of the superficial layer of Electrophtography photosensor, can be by charge transport materials and binder resin being dissolved in the charge transport layer that gets in the solvent with the coating fluid coating and make its dry formation.In addition, the material that has independent film forming in the above-mentioned charge transport materials can place an order in the condition of not using binder resin and alone become film, makes charge transport layer.The ratio of the charge transport materials in the charge transport layer is preferably 0.1～100 weight % with respect to the general assembly (TW) of binder resin and charge transport materials, and more preferably 10～80%.In addition, with respect to the charge transport layer general assembly (TW), the ratio of charge transport materials is preferably 20～100 weight %, more preferably 30～90 weight %.

Charge transport layer particularly is not preferably 5～70 μ m as the thickness of the charge transport layer of the superficial layer of Electrophtography photosensor, further 10～30 μ m more preferably.If the thickness of charge transport layer is thin excessively, then be difficult to retainer belt electric energy power, if blocked up, the tendency that then exists residual electric potential to raise.

When containing charge transport materials and charge generation material in identical layer, this layer can be by being coated with and making its dry formation with above-mentioned charge generation material and above-mentioned charge transfer matter with this layer that binder resin and solvent disperse to get with coating fluid.In addition, the thickness of this layer is preferably 8～40 μ m, more preferably 12～30 μ m.In addition, the ratio of the photoconductivity material in this layer (charge generation material and charge transport materials) is preferably 20～100 weight % with respect to the general assembly (TW) of this layer, further 30～90 weight % more preferably.

As photographic layer (charge transport layer, charge generation layer) employed binder resin in can use for example acryl resin, allyl resin, alkyd resin, epoxy resin, silicone resin, phenolics, butyral resin, the benzal resin, polyacrylate resin, poly-acetal resin, polyamide-imide resin, polyamide, the polyallyl ether resin, polyarylate resin, polyimide resin, urethane resin, vibrin, polyvinyl resin, polycarbonate resin, polysulfone resin, polystyrene resin, polybutadiene, acrylic resin, carbamide resin etc.These resins can use, mix use separately or use more than a kind or 2 kinds with the form of multipolymer.

In addition, on photographic layer,, protective seam can be set in order to protect this photographic layer.The thickness of protective seam is preferably 0.01～10 μ m, further 0.1～6 μ m more preferably.In protective seam, the curable resin of polymerization etc. is solidified in preferred use by heating or irradiation radioactive ray.As the resin monomer of this curable resin, preferably has the resin monomer of chain polymerization functional group.In addition, in protective seam, can also contain metal and oxide thereof, nitride, salt, alloy, and conductive material such as carbon black.As metal, can enumerate tap a blast furnace, copper, gold, silver, lead, zinc, nickel, tin, aluminium, titanium, antimony, indium etc.More particularly, can use ITO, TiO ₂, ZnO, SnO ₂, Al ₂O ₃Deng.Conductive material preferably disperses to contain granular material in protective seam, and its particle diameter is preferably 0.001～5 μ m, further 0.01～1 μ m more preferably.The ratio of the conductive material in the protective seam is preferably 1～70 weight % with respect to the protective seam general assembly (TW), further 5～50 weight % more preferably.As these spreading agent, can use titanium coupling agent, silane coupling agent, various surfactants etc.

In addition, in constituting each layer of above-mentioned Electrophtography photosensor, can add antioxidant or anti-light aging agent etc.In addition, in the superficial layer of Electrophtography photosensor,, can add various fluorine compounds, silane compound, metal oxide etc. for the lubricity or the water proofing property of the outer peripheral face that improves Electrophtography photosensor.In addition, they can be disperseed to contain in protective seam with graininess.In addition, the spreading agent as these can use surfactant etc.The ratio of the above-mentioned various adjuvants in the superficial layer of Electrophtography photosensor is preferably 1～70 weight % with respect to the general assembly (TW) of superficial layer, further 5～50 weight % more preferably.

In the formation method of each layer of Electrophtography photosensor of the present invention, can adopt the whole bag of tricks such as vapour deposition method or rubbing method, but rubbing method most preferably wherein.Rubbing method can form from film the layer to thick film the layer various compositions the layer.Specifically, can list the rubbing method that rod is coated with method, knife coating, rolling method and uses sleeker, dip coating, spraying process, bundle rubbing method, electrostatic applications method, powder coated method etc.

In Fig. 5, shown the brief configuration example of the common transfer-type electro-photography apparatus that uses Electrophtography photosensor of the present invention.

In Fig. 5,1 is the of the present invention cylindric Electrophtography photosensor as image-carrier, and to be the center with axle 2 drive along the speed rotation of the direction of arrow with regulation.Above-mentioned Electrophtography photosensor 1 makes its outer peripheral face accept the uniform charged of the regulation current potential of plus or minus by charged elements 3 in rotary course, then is subjected to image exposure (slit exposure, laser beam scan exposure etc.) by the image exposure unit 4 that is positioned at the exposure position.On the outer peripheral face of Electrophtography photosensor, form and the corresponding electrostatic latent image of exposure image successively thus.

This electrostatic latent image is then supplied with toner by developing cell 5 from development sleeve, this toner development image through toner development, be transferred to successively on the surface of the transfer materials P that is sent by transfer printing unit 6, this transfer materials P is and the synchronously never illustrated paper feed part of rotation of Electrophtography photosensor 1 takes out between Electrophtography photosensor 1 and transfer printing unit 6 and paper supply.

The transfer materials P that has accepted the image transfer printing is from the Electrophtography photosensor surface isolation, carries out photographic fixing and outputs to outside the machine with the form of duplicating thing (duplicate) thereby import to fixation unit 8.

The surface of the Electrophtography photosensor 1 after the image transfer printing is removed the transfer printing remaining toner by cleaning unit 7 and carry out cleaning surfacesization, again by pre-exposure unit 11 electric treatment that disappears, forms thereby be used for image repeatedly.

As electro-photography apparatus, a plurality of one in above-mentioned Electrophtography photosensor and the inscapes such as developing cell, cleaning unit are combined into device unit and make the handle box of the structure that can freely load and unload with respect to apparatus main body this unit.The example that in Fig. 6, has shown handle box.For example, Electrophtography photosensor 1 and cleaning unit 7 one are changed into a device unit, make the structure that guide rail 10 guidance units such as grade of operative installations main body can freely load and unload.At this moment, on the said apparatus unit, can also have charged elements and/or developing cell.

When using electro-photography apparatus as duplicating machine or printer, image exposure 4 reads from the reflected light of original copy or transmitted light or original copy and signalling, carries out the scanning of laser beam, the driving of led array or the driving of liquid crystal light valve array etc. by this signal.When being used as the printer of facsimile recorder, image exposure 4 becomes the exposure that is used for print signal reception data.

In Fig. 6, shown the example of the brief configuration of an electro-photography apparatus that possesses handle box with Electrophtography photosensor of the present invention.

In Fig. 6,1 is Electrophtography photosensor cylindraceous, and to be the center with axle 2 drive with fixing peripheral speed rotation along the direction of arrow.

The outer peripheral face of the Electrophtography photosensor 1 that is driven in rotation is by charged elements (charged elements: charged roller etc.) 3, the current potential of the regulation of charged equably one-tenth plus or minus, then, accept from the exposure light (image exposure light) 4 of exposing units (not shown) such as slit exposure or laser beam flying exposure output.Like this, form electrostatic latent image successively at the outer peripheral face of Electrophtography photosensor 1 corresponding to target image.

Being formed on electrostatic latent image on the outer peripheral face of Electrophtography photosensor 1 is developed by the toner in the developer that is included in developing cell 5 and forms toner image.Then, form and be carried on the toner image on the outer peripheral face of Electrophtography photosensor 1, by transfer bias from transfer printing unit (transfer roll etc.) 6, be transferred to successively on transfer materials (paper etc.) P that transports out, this transfer materials P is and the rotation of Electrophtography photosensor 1 synchronously is fetched into (butt position) between Electrophtography photosensor 1 and the transfer printing unit 6 from transfer printing feed unit (not shown).

Accepted the transfer materials P of toner image transfer printing, the outer peripheral face separation from Electrophtography photosensor 1 imports to fixation unit 8, accepts image fixing, thereby forms thing (print, duplicate) printout outside device as image.

The outer peripheral face of the Electrophtography photosensor 1 after the toner image transfer printing, carry out the removing of the residual developer of transfer printing (toner) by cleaning unit (cleaning balde etc.) 7, thereby cleaning surfacesization, by the electric treatment that disappears of the pre-exposure light (not shown) from pre-exposure unit (not shown), be used for image then repeatedly and form again.In addition, as shown in Figure 6, in charged elements 3 situation for the contact charged elements of using charged roller etc., pre-exposure is not must be necessary.

In the inscapes such as above-mentioned Electrophtography photosensor 1, charged elements 3, developing cell 5, transfer printing unit 6 and cleaning unit 7, can be with a plurality of one that are housed in the container in conjunction with constituting handle box, this handle box can be freely with respect to electro-photography apparatus main bodys such as duplicating machine or laser beam printers formation with loading and unloading.In Fig. 6, Electrophtography photosensor 1 and charged elements 3, developing cell 5 and cleaning unit 7 one are supported and form box, make the handle box 9 that the guiding devices such as guide rail 10 that use the electro-photography apparatus main body can freely load and unload with respect to the electro-photography apparatus main body.

Electrophtography photosensor of the present invention not only can be used for electrophotographic copier, can also be widely used in electrofax applications such as laser beam printer, CRT printer, LED printer, liquid crystal printer, laser plate-making.

Below, the present invention will be described in detail by embodiment.But the present invention is not limited to these embodiment.

[embodiment]

Below, illustrate in greater detail the present invention by embodiment.But the present invention is not limited to these embodiment.

[embodiment 1]

The Electrophtography photosensor that is used for embodiment 1 by following manufacturing.At first, the aluminum barrel (alloy of JIS A3003 aluminium) by the long 370mm of cut manufacturing, external diameter 84mm, wall thickness 3mm.Result in the surfaceness of this tube of turning axle direction detection is Rzjis=0.08 μ m.In the pure water that comprises washing agent (trade name: ケミコ one Le CT, often coil KCC and make), this tube is carried out ultrasonic washing, then after through the operation of washing washing agent, further in pure water, carry out ultrasonic washing and carry out ungrease treatment.

Use bowl mill, the titanium dioxide powder (trade name: Network ロノス ECT-62 that antimony-doped tin oxide is filmed that has with 60 weight portions, the manufacturing of チ Application Industrial Co., Ltd), the titanium dioxide powder (trade name: titone SR-1T of 60 weight portions, the manufacturing of Sakai KCC), the first rank novolac type phenolic resin (trade name: Off ェノライト J-325 of 70 weight portions, Dainippon Ink. ﹠ Chemicals Inc makes, solid constituent 70%), the 2-methoxyl-1-propyl alcohol of 50 weight portions, the solution that the methyl alcohol of 50 weight portions is formed disperseed about 20 hours.The mean grain size of the filling agent that is contained in this dispersion liquid is 0.25 μ m.

By infusion process, the dispersion liquid of preparation like this is applied on the above-mentioned aluminum barrel, by heat drying in adjusting to 150 ℃ air drier 48 minutes, make it to be solidified to form the conductive layer of thickness 15 μ m.

Then, to in the mixed liquor of 500 weight portion methyl alcohol and 250 weight portion butanols, dissolve the copolymer polyamide resin (trade name: ァミラ Application CM8000 of 10 weight portions, east レ Co., Ltd. makes) and the methoxy nylon resin (trade name: トレジ Application EF30T of 30 weight portions, Teikoku Chemical Industries Co., Ltd's manufacturing) the solution dip-coating that obtains is to above-mentioned conductive layer, put into the air drier heat drying 22 minutes of adjusting to 100 ℃, form the undercoat of thickness 0.45 μ m.

Then, to being 7.4 ° and 28.2 ° and locating the hydroxyl phthalocyanine gallium dyestuff at strong peak, the polyvinyl butyral resin of 2 weight portions (trade name: ェスレッ Network BX-1 Bragg angle 2 θ of CuK alpha ray diffraction spectrum ± 0.2 ° by 4 weight portions, Sekisui Chemical Co., Ltd's manufacturing), the mixed liquor of the cyclohexanone composition of 90 weight portions, use the beaded glass of diameter 1mm to make it to disperse 10 hours, add the ethyl acetate of 110 weight portions then and prepare the charge generation layer coating fluid with sand milling.This coating fluid dip-coating to above-mentioned undercoat, is put into the air drier heat drying 22 minutes that is adjusted to 80 ℃, and forming thickness is the charge generation layer of 0.17 μ m.

Then, triarylamine compounds shown in the 35 weight portion following structural formula (11) and 50 weight portion bisphenol z-polycarbonate resins (trade name: ュ one ピロ Application Z400, Mitsubishi engineering Plastics Co., Ltd make) are dissolved in the dimethoxymethane of 320 weight portion monochloro benzene and 50 weight portions, prepare the first electrolysis transfer layer coating fluid.

Structural formula (11)

With this first charge transport layer with coating fluid dip-coating to above-mentioned charge generation layer, put into the air drier heat drying 40 minutes that is adjusted to 100 ℃, forming thickness is first charge transport layer of 20 μ m.

Then, with the hole transport ability compound dissolution shown in the 30 weight portion following structural formula (12) with polymerism functional group in 35 weight portion 1-propyl alcohol and 35

weight portions

1,1,2,2,3,3,4-seven fluorine cyclopentane (trade name: ゼォロ one ラ H, Japanese ゼォ Application Co., Ltd. makes) in, 0.5 μ m film filter by the PTFE system carries out pressure filtration then, thereby prepares the second charge transport layer coating fluid.This coating fluid is applied to second charge transport layer that forms curable on the above-mentioned charge transport layer by dip coating.Then, in nitrogen, with accelerating potential 150kV, quantity of X-rays X 1.5 * 10 ⁴The condition irradiation electron ray of Gy.Then, under reaching 120 ℃ condition, the temperature of Electrophtography photosensor carries out 90 seconds heat treated.At this moment oxygen concentration is 10ppm.Electrophtography photosensor being carried out 20 minutes heat treated in air in being adjusted to 100 ℃ air drier, is second charge transport layer of the curable of 6 μ m thereby form thickness again.

Structural formula (12)

Then, surface roughening being carried out on resulting Electrophtography photosensor surface handles.Use dry type sand blasting unit shown in Figure 2 (only smart machine is made manufacturing), carry out blasting treatment under the following conditions.

The abrasive substance abrasive particle that uses is globular glass pearl, mean grain size 30 μ m (trade name: UB-01L, ュニォ Application Co., Ltd. makes).Blow gas pressure: 3.5kgf/cm ²Spray gun translational speed: 430mm/min, workpiece (Electrophtography photosensor) rotational speed: 288rpm, the distance of lance ejection mouth and Electrophtography photosensor: 100mm, the abrasive particle injection angle: 90 °, abrasive particle quantity delivered: 200g/min, sandblast number of times: one way * 2 time, further, remove residual lip-deep abrasive substance by spraying pressurized air attached to Electrophtography photosensor.

The サ one Off コ one ダ one SE3500 type surface roughness measurement device that the mensuration of the surface configuration of the superficial layer of this Electrophtography photosensor is to use (strain) little slope research institute to make carries out.The circumference roughness determinator that the mensuration of the Electrophtography photosensor circumferencial direction of Rzjis and RSm is to use said apparatus to use carries out.With measured length: 0.4mm, finding speed: 0.1mm/s measures as condition determination.The baseline values setting value that abates the noise when measuring RSm is to measure with the condition of level set=10%.

10 mean roughness Rzjis (A) of resulting Electrophtography photosensor, Rzjis (B), concavo-convex equispaced RSm (C), RSm (D) are respectively 0.55 μ m, 0.60 μ m, 42 μ m, 43 μ m.

In addition, maximum peak height Rp is 0.2 μ m, and the maximum peak height Rp of maximum valley depth Rv/ is 2.02.

In addition, the average aspect ratio of the area ratio of the number of the recess of the shallow concave shape that per 100 μ m of the superficial layer of this Electrophtography photosensor are square, the recess of shallow concave shape, the recess of shallow concave shape is to use the surface shape measuring system (SurfaceExplorer SX-520DR type, water chestnutization システ system is made) of above-mentioned record to measure and calculate.

The result is that the average aspect ratio of the area ratio of the number of the recess of the shallow concave shape that per 100 μ m are square, the recess of shallow concave shape, the recess of shallow concave shape is respectively 15,12.2,0.68.

Further, carry out the mensuration of the matching rate of this Electrophtography photosensor.In this is measured, owing to be to carry out actual measurement with the cross-section photograph that SEM takes first charge transfer/second charge transport layer, thereby must destroy Electrophtography photosensor.Therefore, prepare an Electrophtography photosensor of under the condition identical, making again with above-mentioned condition, and with it as the matching rate test sample.

At first, in the face of Electrophtography photosensor, cut the sample about the about 5mm of the length of side arbitrarily at 9 positions.Therein, observe the cross section of 1 sample by SEM, from wherein selecting the recess part of 3 shallow concave shape arbitrarily, on each aspect, measure second charge transport layer shallow concave shape recess Rv11max (maximum valley depth), L11 (diameter) and with first charge transport layer of the corresponding part of this depression and Rv12max (maximum valley depth), the L12 (diameter) of the recess of the shallow concave shape of the interface formation of second charge transport layer.This operation is that the recess to the shallow concave shape that amounts to 27 points carries out, and by getting the processing of its mean value, calculates matching rate, and the result is 80%.Table 1 provides its result.

Then, under the environment of 23 ℃ of temperature, humidity 50%, Electrophtography photosensor was placed 24 hours, as hardness test usefulness, use the microsclerometry device Fischer scope H100V (manufacturing of Fischer company) of above-mentioned record then, obtain the elastic deformation rate.

The elastic deformation rate is by pressure head is applied load continuously, and the compression distance that directly reads under the load is tried to achieve continuous hardness.As pressure head, can use the opposite face angle is 136 ° Vickers tetragonal pyramid diamond penetrator.It is specifically, interim that to measure until final load be 6mN (each retention time of 0.1 second of point, 273 points).

The mensuration of elastic deformation rate comprises the second charge transfer laminar surface as superficial layer, as 2 kinds of mensuration of the first charge transfer laminar surface of surperficial lower floor.

The mensuration of the second charge transfer laminar surface is: after the blasting treatment of second charge transport layer second charge transport layer surface is pressed into pressure head, measures.

The mensuration of the first charge transfer laminar surface is: with said method similarly make formed first charge transport layer, but not with the Electrophtography photosensor of second charge transport layer, the surface of this first charge transport layer is pressed into pressure head, measure.

Its measurement result is shown in table 1, table 2.

For electrophotographic copier (trade name: iR C6800, Canon Co., Ltd makes), it is transformed into electronegative electrophotographic photoreceptor can be installed and can not have problems at aspects such as spatter property and developments, make the device that to export desirable image continuously, thereby carry out the endurancing evaluation of the Electrophtography photosensor of present embodiment.

At first, under the environment of 23 ℃/5%RH, use A4 to test visual full color, per 2 intermittences once, carry out 50000 durability test, measure the maximum lesion depths in per 10000 bulging faces, measure the reduction of drum, and observe bad on the image by test patterns such as output medium tone images.

Use the サ one Off コ one ダ one SE3500 type surface roughness measurement device of (strain) little slope research institute manufacturing of above-mentioned record in the mensuration of maximum lesion depths, and under imposing a condition same as described above, carry out.Assay method makes with the following method: by the darker position of visual definite damage, measure a plurality of positions in the damage, get maximum value.

The mensuration of the reduction of Electrophtography photosensor is to measure by the minimizing of the thickness when durable use.The mensuration of the thickness of Electrophtography photosensor is to unite the determining film thickness machine パ one マスコ one プ E111 type (manufacturing of Fischer company) of use vortex flow mode and utilize the interfere type film thickness gauge (big mound electronics is made) of the moment MCPD-3000 of multi-site determination system to carry out.

Measure the maximum lesion depths that is produced on per 10000 Electrophtography photosensors in durable use, confirm this damage growth situation, its degree of depth is tended to the state of reaching capacity when 20000 left and right sides, and the lesion depths during 50000 durable finish is identical during with 20000.

At this moment value is that Rmax is 1.1 μ m.

On the other hand, the reduction in the time of 50000 is 1.2 μ m.

As mentioned above, the number the when life-span of drum can reach photographic layer with damage calculates, and the life-span of damage is measurable to be 306000.

After 50000 durable uses, proceed durability test, on the medium tone image, show as defective until the damage of Electrophtography photosensor, continuing durable result is, in the time of 305000, produce image deflects, thereby confirm the life-span of this Electrophtography photosensor.

That is, can confirm that the Electrophtography photosensor of present embodiment is almost equal with the life-span number of anticipation originally.

[embodiment 2]

In the manufacturing of the Electrophtography photosensor of the foregoing description 1, except the thickness with second charge transport layer is made as 10 μ m, carry out similarly to Example 1 coating, curing.Then, condition to the surface roughening disposal route identical with embodiment 1 is optimized, so that form the surface configuration that resulting Electrophtography photosensor can not have problems to cleaning when putting into electro-photography apparatus, and carry out surface roughening and handle, Electrophtography photosensor made.

Prepared Electrophtography photosensor is installed in the electro-photography apparatus identical with embodiment 1, estimates similarly to Example 1, the result is shown in table 1, table 2.

[embodiment 3]

In the manufacturing of the Electrophtography photosensor of the foregoing description 1, except the thickness with second charge transport layer is made as 15 μ m, carry out similarly to Example 1 coating, curing.Then, condition to the surface roughening disposal route identical with embodiment 1 is optimized, so that the surface configuration that can not have problems to cleaning when forming resulting Electrophtography photosensor and putting into electro-photography apparatus, and carry out surface roughening and handle, make Electrophtography photosensor.

[embodiment 4]

In the manufacturing of the Electrophtography photosensor of the foregoing description 1, except the thickness with second charge transport layer is made as 4 μ m, carry out similarly to Example 1 coating, curing.Then, condition to the surface roughening disposal route identical with embodiment 1 is optimized, so that the surface configuration that can not have problems to cleaning when forming resulting Electrophtography photosensor and putting into electro-photography apparatus, and carry out surface roughening and handle, make Electrophtography photosensor.

[embodiment 5]

In the manufacturing of the Electrophtography photosensor of the foregoing description 1, till first charge transport layer, all make similarly to Example 1.Then, make second charge transport layer as follows.

With the fluorine resin (trade name: GF-300 of 0.15 weight portion as spreading agent, Toagosei Co., Ltd's manufacturing) is dissolved in 1 of 35 weight portions, 1,2,2,3,3,4-seven fluorine cyclopentane (trade name: ゼォロ one ラ H, Japan ゼォ Application Co., Ltd. makes) and the 1-propyl alcohol of 35 weight portions in, add the tetrafluoroethylene resin powder (trade name: Le Block ロ Application L-2, ダイキ Application Industrial Co., Ltd manufacturing) of 3 weight portions then as lubricant, use high pressure dispersion machine (trade name: マイ Network ロ Off Le イダイザ one M-110EH, the manufacturing of U.S. Microfluidics company) at 600kgf/cm ²Pressure under carry out 3 processing it be uniformly dispersed.Use the PTFE film filter of 10 μ m that it is carried out pressure filtration and prepare the lubricant dispersion liquid.Then, add the hole transport ability compound shown in the 27 weight portion following formulas (12) in the lubricant dispersion liquid, 5 μ m film filters by the PTFE system carry out pressure filtration, prepare the second charge transport layer coating fluid.Use this coating fluid on above-mentioned first charge transport layer, to be coated with second charge transport layer by dip coating.

Then, through electron ray irradiation and heating treatment step similarly to Example 1, forming thickness is second charge transport layer of 6 μ m, condition to the surface roughening disposal route identical with embodiment 1 is optimized, so that the surface configuration that can not have problems to cleaning when forming resulting Electrophtography photosensor and putting into electro-photography apparatus, and carry out surface roughening and handle, make Electrophtography photosensor.

[embodiment 6]

In the manufacturing of the Electrophtography photosensor of the foregoing description 1, till charge transport layer, all make similarly to Example 1.Then, make second charge transport layer as follows.

With the fluorine resin (trade name: GF-300 of 0.45 weight portion as spreading agent, Toagosei Co., Ltd's manufacturing) is dissolved in 1 of 35 weight portions, 1,2,2,3,3,4-seven fluorine cyclopentane (trade name: ゼォロ one ラ H, Japan ゼォ Application Co., Ltd. makes) and the 1-propyl alcohol of 35 weight portions in, add the tetrafluoroethylene resin powder (trade name: Le Block ロ Application L-2, ダイキ Application Industrial Co., Ltd manufacturing) of 9 weight portions then as lubricant, use high pressure dispersion machine (trade name: マイ Network ロ Off Le イダイザ one M-110EH, the manufacturing of U.S. Microfluidics company) at 600kgf/cm ²Pressure under carry out 3 processing it be uniformly dispersed.Use the PTFE film filter of 10 μ m that it is carried out pressure filtration and prepare the lubricant dispersion liquid.Then, add the hole transport ability compound shown in the 27 weight portion following formulas (12) in the lubricant dispersion liquid, 5 μ m film filters by the PTFE system carry out pressure filtration, prepare protective layer used coating fluid.Use this coating fluid on above-mentioned first charge transport layer, to be coated with second charge transport layer by dip coating.

Then, through electron ray irradiation and heating treatment step similarly to Example 1, forming thickness is the curing type superficial layer of 6 μ m, condition to the surface roughening disposal route identical with embodiment 1 is optimized, so that the surface configuration that can not have problems to cleaning when forming resulting Electrophtography photosensor and putting into electro-photography apparatus, and carry out surface roughening and handle, make Electrophtography photosensor.

[embodiment 7]

In the manufacturing of the Electrophtography photosensor of embodiment 1, till first charge transport layer, all make similarly to Example 1.

Except the compound shown in the formula among the embodiment 1 (12) is replaced with the hole transport ability compound shown in the following formula (13), same amount uses the tetrafluoroethylene resin dispersion liquid identical with embodiment 5, make Electrophtography photosensor similarly to Example 6, condition to the surface roughening disposal route identical with embodiment 1 is optimized, so that the surface configuration that can not have problems to cleaning when forming resulting Electrophtography photosensor and putting into electro-photography apparatus, and carry out surface roughening and handle, make Electrophtography photosensor.The result is shown in table 1, table 2.

Structural formula (13)

[embodiment 8]

In the manufacturing of the Electrophtography photosensor of embodiment 1, till charge transport layer, all make similarly to Example 1.Then, as first charge transport layer, with the bisphenol Z type of the triarylamine compounds shown in triarylamine compounds shown in the employed structural formula (11) in 36 weight portion the foregoing descriptions 1 and the 4 weight portion following structural formula (14), 50 weight portions and the polyarylate resin that the bisphenol-c type forms with 1/1 copolymerization (weight-average molecular weight: 130000) be dissolved in the dimethoxymethane of the monochloro benzene of 350 weight portions and 50 weight portions, make the first charge transport layer coating fluid.Its dip-coating to above-mentioned charge generation layer, is put into the air drier heat drying 60 minutes of adjusting to 110 ℃, form first charge transport layer of thickness 20 μ m.

Structural formula 14

On this surface, form second charge transport layer similarly to Example 6, condition to the surface roughening disposal route identical with embodiment 1 is optimized, so that the surface configuration that can not have problems to cleaning when forming resulting Electrophtography photosensor and putting into electro-photography apparatus, and carry out surface roughening and handle, make Electrophtography photosensor.

[embodiment 9]

In embodiment 1, form after first charge transport layer, in the mixed solvent of the methylene chloride of monochloro benzene that the bisphenol z-polycarbonate resin of 10 weight portions (trade name: ュ one ピロ Application Z200, Mitsubishi engineering Plastics Co., Ltd make) is dissolved in 100 weight portions and 60 weight portions and in the solution of making, mix, disperse the hydrophobic silica particles of 1 weight portion, make coating fluid, to above-mentioned first charge transport layer, form dried thickness is second charge transport layer of 1.0 μ m to the use flush coater with this coating fluid coating fluid.

Further, on this surface, as the tricharged transport layer, make the charge transport layer of the curable that become superficial layer identical with embodiment 6, condition to the surface roughening disposal route identical with embodiment 1 is optimized, so that the surface configuration that can not have problems to cleaning when forming resulting Electrophtography photosensor and putting into electro-photography apparatus, and carry out surface roughening and handle, make Electrophtography photosensor.

[embodiment 10]

Till charge generation layer, make similarly to Example 1.

Then, with fluorine resin (trade name: the サ one Off ロ Application S-381 of 0.68 weight portion as spreading agent, セイミケミカ Le Co., Ltd. makes) be dissolved in the ethanol of the methyl alcohol of 35 weight portions and 35 weight portions, add the tetrafluoroethylene resin powder (Le Block ロ Application L-2) of 6 weight portions then as lubricant, use high pressure dispersion machine (trade name: マイ Network ロ Off Le イダイザ one M-110EH, the manufacturing of U.S. Microfluidics company) at 600kgf/cm ²Pressure under carry out 3 processing it be uniformly dispersed.Use the PTFE film filter of 10 μ m that it is carried out pressure filtration and prepare the lubricant dispersion liquid.First rank novolac type phenolic resin varnish (trade name: PL-4852 to these liquid mixing 21.2 weight portions, Gunsaka Chem. Industry Co., Ltd. makes, the involatile composition: 75%) and 11.1 weight portions have the structure shown in the following formula (16) charge-transporting compound, stir and make its dissolving.5 μ m film filters by the PTFE system carry out pressure filtration to this liquid, prepare the first charge transport layer coating fluid.

Structural formula (16)

This coating fluid dip-coating to charge generation layer, is carried out 1 hour the processing that is heating and curing in adjusting to 145 ℃ air drier, forming thickness is first charge transport layer of 20 μ m.

On first charge transport layer of making like this, make second charge transport layer similarly to Example 6, carry out similarly to Example 1 coating, curing, condition to the surface roughening disposal route identical with embodiment 1 is optimized, so that the surface configuration that can not have problems to cleaning when forming resulting Electrophtography photosensor and putting into electro-photography apparatus, and carry out surface roughening and handle, make Electrophtography photosensor.

[embodiment 11]

Then, to the coating of the embodiment 6 that uses the hole transport ability compound shown in the 27 weight portion following formulas (12), add 3 weight portions following structural formula (17) Photoepolymerizationinitiater initiater and prepare the second charge transport layer coating.To above-mentioned first charge transport layer, use metal halide lamp this coating dip coating with 500mW/cm ²Light intensity shine it solidified, in air, in being adjusted to 120 ℃ air drier, Electrophtography photosensor carried out 60 minutes heat treated, forming thickness is second charge transport layer of 6 μ m.Condition to the surface roughening disposal route identical with embodiment 1 is optimized, so that the surface configuration that can not have problems to cleaning when forming resulting Electrophtography photosensor and putting into the electro-photography apparatus identical, and Electrophtography photosensor is carried out surface roughening handle with embodiment 1.Prepared Electrophtography photosensor is installed in the electro-photography apparatus identical with embodiment 1, estimates similarly to Example 1, the result is shown in table 1, table 2.

Structural formula (17)

[embodiment 12]

Till charge generation layer, make similarly to Example 1.

Then, use 7 weight portions to have the fluorochemicals (trade name: LS-1090 of the structure shown in the following formula (18), Shin-Etsu Chemial Co., Ltd makes) to the antimony-doped tin oxide particle (trade name: T-1 of 100 weight portions, マテリァ Le Co., Ltd. of Mitsubishi makes, mean grain size: 0.02 μ m) carry out surface treatment and (hereinafter, be designated as treatment capacity: 7%).

Structural formula (18)

Use the sand milling device with 50 weight portions after this surface treatment the antimony-doped tin oxide particle and the ethanol of 150 weight portions disperseed 60 hours, add the tetrafluoroethylene resin particle (Le Block ロ Application L-2) of 20 weight portions again, utilize the sand milling device to disperse again 8 hours.

Then, dissolve the resol type bakelite varnish (trade name: PL-4802, Gunsaka Chem. Industry Co., Ltd. makes) of 30 weight portions, the coating fluid that the preparation superficial layer is used.The disperse state of coating fluid is good.

The coating fluid dip-coating that this superficial layer is used is carried out 1 hour the processing that is heating and curing in being adjusted to 145 ℃ air drier to charge transport layer, forming thickness is the superficial layer of 6 μ m.

According to the dry type blasting treatment identical, the superficial layer of the Electrophtography photosensor that obtains is like this carried out surface roughening handle with embodiment 1.

[embodiment 13]

Then; as second charge transport layer; with copoly type polyarylate resin (the copolymerization ratio m: n=7: 3 shown in the structural formula (15) of triarylamine compounds shown in triarylamine compounds shown in 5 weight portion the foregoing descriptions, the 1 employed structural formula (11) and 4 weight portion the foregoing descriptions, the 8 employed structural formulas (14) and 8 weight portions; weight-average molecular weight: 130000) be dissolved in the dimethoxymethane of the monochloro benzene of 240 weight portions and 160 weight portions, make protective layer used coating fluid.It is sprayed on the charge transport layer, put into the air drier heat drying 60 minutes that is adjusted to 110 ℃, forming thickness is second charge transport layer of 6 μ m.

Condition to the surface roughening disposal route identical with embodiment 1 is optimized, so that the surface configuration that can not have problems to cleaning when forming resulting Electrophtography photosensor and putting into the electro-photography apparatus identical, and carry out surface roughening and handle with embodiment 1.Prepared Electrophtography photosensor is installed in the electro-photography apparatus identical with embodiment 1, estimates similarly to Example 1, the result is shown in table 1, table 2.

[embodiment 14]

Then, the solution (solid constituent 67 weight %) that charge-transporting compound shown in 10 weight portion embodiment, the 10 employed structural formulas (16) and 20 weight portions are had the biuret modified body of structure shown in the following formula (19) is dissolved in the mixed solvent of 350 weight portion tetrahydrofurans and 150 weight portion cyclohexanone, prepares the coating fluid that second charge transport layer is used.

Structural formula (19)

The coating fluid that this second charge transport layer that becomes superficial layer is used sprays on first charge transport layer, at room temperature places 30 minutes, by the hot blast that blew 1 hour it is solidified under 145 ℃ then, and forming thickness is the protective seam of 6 μ m.

[embodiment 15]

Compound shown in the formula (12) of the hole transport ability compound replacement embodiment 1 that use following formula (20) is represented.In addition, (the trade name: GF-300 of the fluorine resin as spreading agent with 0.3 weight portion, Toagosei Co., Ltd's manufacturing) is dissolved in 1 of 35 weight portions, 1,2,2,3,3, in the 1-propyl alcohol of 4-seven fluorine cyclopentane (trade name: ゼォロ one ラ H, Japanese ゼォ Application Co., Ltd. makes) and 35 weight portions, (the trade name: Le Block ロ Application L-2 of the tetrafluoroethylene resin powder as lubricant that adds 6 weight portions then, ダイキ Application Co., Ltd. makes), use high pressure dispersion machine (trade name: マイ Network ロ Off Le イダイザ one M-110EH, the manufacturing of U.S. Microfluidics company) at 600kgf/cm ²Pressure under carry out 3 processing it be uniformly dispersed.Use the PTFE film filter of 10 μ m that it is carried out pressure filtration and prepare the lubricant dispersion liquid.Then, the hole transport ability compound shown in the following formula (20) of adding 27 weight portions in the lubricant dispersion liquid, 5 μ m film filters by the PTFE system carry out pressure filtration, add the Photoepolymerizationinitiater initiater of the formula (17) of embodiment 11 then with amount, prepare the coating fluid that second charge transport layer is used.

Structural formula (20)

To above-mentioned first charge transport layer, it is solidified this coating fluid dip-coating, carry out heated-air drying and handle under the condition identical with embodiment 10, forming thickness is second charge transport layer of 6 μ m.Condition to the surface roughening disposal route identical with embodiment 1 is optimized, so that the surface configuration that can not have problems to cleaning when forming resulting Electrophtography photosensor and putting into the electro-photography apparatus identical with embodiment 1, and carry out surface roughening and handle, make Electrophtography photosensor.Prepared Electrophtography photosensor is installed in the electro-photography apparatus identical with embodiment 1, estimates similarly to Example 1, the result is shown in table 1, table 2.

[embodiment 16]

In the manufacturing of the Electrophtography photosensor of the foregoing description 1, till first charge transport layer, all make similarly to Example 1.

Change the hole transport ability compound of the structural formula (12) of embodiment 1 the hole transport ability compound of following structural formula (21) into, use this coating fluid on above-mentioned first charge transport layer, to be coated with second charge transport layer by dip coating.Then, in nitrogen, under the condition of accelerating potential 150kV, quantity of X-rays X 10Mrad, shine electron ray.Then under reaching 120 ℃ condition, the temperature of Electrophtography photosensor carries out the heat treated in 90 seconds.At this moment oxygen concentration is 10ppm.Then, Electrophtography photosensor carried out 20 minutes heat treated in being adjusted to 100 ℃ air drier in air, forming thickness is second charge transport layer of 6 μ m.

Structural formula (21)

[embodiment 17]

In embodiment 1, form after first charge transport layer, the compound of the following structural formula (22) of the hole transport ability compound of the said structure formula (12) of 30 weight portions, 10 weight portions is dissolved in the mixed solvent of methylene chloride of the monochloro benzene of 50 weight portions and 50 weight portions, prepares the second charge transport layer coating fluid.

This coating fluid is applied on above-mentioned first charge transport layer, uses the method identical then, but in nitrogen, under the condition of accelerating potential 150kV, quantity of X-rays X 10Mrad, shine electron ray with embodiment 1.Then, under becoming 120 ℃ condition, the temperature of Electrophtography photosensor carries out the heat treated in 90 seconds.At this moment oxygen concentration is 10ppm.Then, Electrophtography photosensor carried out 20 minutes heat treated in being adjusted to 100 ℃ air drier in air, forming thickness is second charge transport layer of 2 μ m.

Structural formula (22)

[comparative example 1]

Electrophtography photosensor at the foregoing description 1 manufacturing, be coated with second charge transport layer, drying is 15 minutes under 50 ℃, then before the irradiation electron ray is cured, the condition of the blasting treatment method of embodiment 1 is optimized and carries out surface roughening and handle, so that form the identical surface configuration of surface configuration with the Electrophtography photosensor of embodiment 1.After finishing surface roughening, under the condition identical, carry out electron ray irradiation, heating with embodiment 1, second charge transport layer is solidified, make the Electrophtography photosensor of comparative example 1.

This Electrophtography photosensor is carried out the SEM cross section take a picture to observe, the concavo-convex interface between first charge transport layer and second charge transport layer of the second charge transport layer shape does not form fully as a result, is that smooth, matching rate is 0%.

This Electrophtography photosensor is at aspects such as clean-up performances, all do not have problems after durable from the initial stage.But in for a long time durable, the life-span number when producing damage image does not satisfy the life-span number of anticipation.

[comparative example 2]

Electrophtography photosensor at the foregoing description 13 manufacturings, after being coated with second charge transport layer, drying is 15 minutes under 50 ℃, then the condition of the surface roughening facture identical with embodiment 13 is optimized and carries out surface roughening and handle, so that form the surface configuration identical with embodiment 13.After finishing surface roughening, under the condition identical, second charge transport layer is carried out heat drying with embodiment 13, make Electrophtography photosensor.

This Electrophtography photosensor is at aspects such as clean-up performances, can continue without a doubt since the initial stage, and reduction, damage growth rate is identical with embodiment 13.But in durable, the life-span number when producing damage image does not satisfy the life-span number of anticipation.

[comparative example 3]

Identical with the foregoing description 1 till the curing of second charge transport layer.Then, according to surface roughening process as shown in Figure 7, carry out surface roughening.

This be a kind of have utilize abrasive sheet to carry out the surface roughening process of the structure of surface roughening.Abrasive sheet is that a kind of abrasive particle that will grind is dispersed in the material that forms in the binder resin and is applied to thin slice on the base material.Abrasive sheet 6-1 twists on the axle 6-a in cavity, is equipped with the not shown motor that in the opposite direction abrasive sheet 6-1 is applied tension force along the side with the transmission thin slice on axle 6-a.Abrasive sheet 6-1 is transmitted along the direction of arrow, and by backing roll 6-3, the thin slice after the grinding utilizes not shown motor to be rolled onto on the take-up mechanism 6-5 by guide reel 6-2 (3), 6-2 (4) by guide reel 6-2 (1), 6-2 (2).Grinding is carried out in the following way: untreated basically abrasive sheet always keeps crimping with the surface of Electrophtography photosensor, and surface roughening is carried out on the surface of Electrophtography photosensor handle.The position that abrasive sheet 6-1 is contacted is to be grounding to ground or to have electric conductivity.

Under condition shown below, carry out the roughening on the surface of Electrophtography photosensor.

Abrasive sheet: name of an article C-2000 (manufacturing of the Off イ of Fuji Le system Co., Ltd.)

Grind abrasive particle: SiC (mean grain size: 9 μ m)

Base material: mylar is (thick: 75 μ m)

Abrasive sheet transfer rate: 200mm/ second

The rotating speed of Electrophtography photosensor: 25rpm

Contact pressure: 3N/m ²

The sense of rotation of thin slice and Electrophtography photosensor: equidirectional

(hereinafter, equidirectional is called " identical ", reverse direction is called " on the contrary ")

The external diameter of backing roll: diameter 40cm

The Asker of backing roll (ァスカ one) C hardness: 40

Processing time: 150 seconds

Handle by this surface roughening, measure density, well width and the surfaceness of groove on the surface of Electrophtography photosensor, the result is that groove density is 420, well width is that 10.4 μ m are following, Rz is 0.62 μ m, and Rmax is 0.83 μ m.

Carry out the SEM cross section photograph of this Electrophtography photosensor and observe, the concavo-convex interface between first charge transport layer and second charge transport layer of the second charge transport layer shape does not form fully as a result, is smooth.Matching rate can not be tried to achieve according to calculating definition, but matching rate is 0%.

This Electrophtography photosensor is installed in the embodiment 1 employed electro-photography apparatus, estimates similarly to Example 1, the result is shown in table 1, table 2.

This Electrophtography photosensor is at aspects such as spatter properties, and before reaching the life-span number, it is bad to produce slight cleaning, and is final, and the life-span number when producing the loss image does not satisfy the life-span number of anticipation.

[comparative example 4]

At the Electrophtography photosensor of the foregoing description 1 manufacturing, under the condition of superficial layer not being implemented blasting treatment, measure surface configuration etc., attach it in the embodiment 1 employed electro-photography apparatus and carry out same evaluation.The result is shown in table 1, table 2.

On this Electrophtography photosensor surface, do not form the recess of shallow concave shape, have an even surface.

This Electrophtography photosensor is installed in the embodiment 1 employed electro-photography apparatus, estimates similarly to Example 1, the result is as shown in table 1.

The durable number of this Electrophtography photosensor is 100, and it is bad that cleaning takes place, and what can not continue is durable.

[comparative example 5]

Electrophtography photosensor at the foregoing description 1 manufacturing, after coating first charge transport layer, the blasting treatment method of embodiment 1 is optimized and the first charge transfer laminar surface is carried out surface roughening handle, so that form the identical surface configuration of surface configuration with the superficial layer of the Electrophtography photosensor of embodiment 1.After finishing the surface roughening processing, be coated with second charge transport layer similarly to Example 1, carry out electron ray irradiation, heating, solidify second charge transport layer, make the Electrophtography photosensor of comparative example 5.

This Electrophtography photosensor is carried out the SEM cross section take a picture to observe, the second charge transport layer shape is compared with the interface between first charge transport layer and second charge transport layer as a result, concavo-convex very little, almost be smooth, matching rate is 5%.

This Electrophtography photosensor is installed in the electro-photography apparatus identical with embodiment 1, estimates similarly to Example 1, the result is shown in table 1, table 2.

The durable number of this Electrophtography photosensor is 3000, and it is bad that cleaning takes place, and can not continue durable.

Table 1

	Matching rate (F:%)	Superficial layer elastic modulus (WeA:%)	Surface lower floor's elastic modulus (WeB:%)	Superficial layer HU (N/mm ²)	Surface HU (the N/mm of lower floor ²)	Superficial layer thickness (μ m)	Superficial layer main composition material (structural formula No)	Superficial layer create conditions (solidification method)
	Matching rate (F:%)	Superficial layer elastic modulus (WeA:%)	Surface lower floor's elastic modulus (WeB:%)	Superficial layer HU (N/mm ²)	Surface HU (the N/mm of lower floor ²)	Superficial layer thickness (μ m)		Superficial layer create conditions (solidification method)	Embodiment 1	80	58	41	204	215	6	12	Electron ray
Embodiment 2	78	58	↑	203	↑	10	↑	↑	Embodiment 1	80	58	41	204	215	6	12	Electron ray
Embodiment 2	78	58	↑	203	↑	10	↑	↑	Embodiment 3	62	59	↑	202	↑	15	↑	↑
Embodiment 4	80	58	↑	205	↑	4	↑	↑	Embodiment 3	62	59	↑	202	↑	15	↑	↑
Embodiment 4	80	58	↑	205	↑	4	↑	↑	Embodiment 5	78	54	↑	198	↑	6	↑	↑
Embodiment 6	75	50	↑	192	↑	↑	↑	↑	Embodiment 5	78	54	↑	198	↑	6	↑	↑
Embodiment 6	75	50	↑	192	↑	↑	↑	↑	Embodiment 7	72	50	↑	190	↑	↑	13	↑
Embodiment 8	69	50	44	194	240	↑	12	↑	Embodiment 7	72	50	↑	190	↑	↑	13	↑
Embodiment 8	69	50	44	194	240	↑	12	↑	Embodiment 9	71	50	38	193	237	↑	↑	↑
Embodiment 10	62	50	47	194	210	↑	16	↑	Embodiment 9	71	50	38	193	237	↑	↑	↑
Embodiment 10	62	50	47	194	210	↑	16	↑	Embodiment 11	71	49	41	183	215	↑	12	UV
Embodiment 12	62	45	41	205	↑	↑	18	Heat	Embodiment 11	71	49	41	183	215	↑	12	UV
Embodiment 12	62	45	41	205	↑	↑	18	Heat	Embodiment 13	57	43	↑	219	↑	↑	15	Heat
Embodiment 14	66	46	41	211	↑	↑	19	Heat	Embodiment 13	57	43	↑	219	↑	↑	15	Heat
Embodiment 14	66	46	41	211	↑	↑	19	Heat	Embodiment 15	68	46	41	182	↑	↑	20	UV
Embodiment 16	70	60	41	220	↑	↑	21	Electron ray	Embodiment 15	68	46	41	182	↑	↑	20	UV
Embodiment 16	70	60	41	220	↑	↑	21	Electron ray	Embodiment 17	57	68	41	255	↑	2	22	↑
									Embodiment 17	57	68	41	255	↑	2	22	↑
									Comparative example 1	0	58	41	204	215	6	12	↑
Comparative example 2	0	41	41	205	↑	↑	15	↑	Comparative example 1	0	58	41	204	215	6	12	↑
Comparative example 2	0	41	41	205	↑	↑	15	↑	Comparative example 3	0	58	41	204	↑	↑	12	↑
Comparative example 4	0	58	41	204	↑	↑	12	↑	Comparative example 3	0	58	41	204	↑	↑	12	↑
Comparative example 4	0	58	41	204	↑	↑	12	↑	Comparative example 5	5	58	41	204	↑	↑	12	↑

Table 1 (continuing)

	Damage growth rate (μ m/10000 opens)	Reduction speed (μ m/10000 opens)	Anticipation life-span number (α: K opens)	Actual number endurance life (β: K opens)	β/α	Reach life-span number image evaluation result and other special item before
	Damage growth rate (μ m/10000 opens)	Reduction speed (μ m/10000 opens)	Anticipation life-span number (α: K opens)	Actual number endurance life (β: K opens)	β/α		Embodiment 1	Saturated under max1.1	0.16	306	305	0.99	No problem
Embodiment 2	Saturated under max1.5	0.16	530	510	0.96	↑	Embodiment 1	Saturated under max1.1	0.16	306	305	0.99	No problem
Embodiment 2	Saturated under max1.5	0.16	530	510	0.96	↑	Embodiment 3	Saturated under max1.9	0.16	810	575	0.71	↑
Embodiment 4	Saturated under max1.2	0.16	175	170	0.97	↑	Embodiment 3	Saturated under max1.9	0.16	810	575	0.71	↑
Embodiment 4	Saturated under max1.2	0.16	175	170	0.97	↑	Embodiment 5	Saturated under max1.4	0.19	242	225	0.93	↑
Embodiment 6	Saturated under max2	0.25	160	145	0.91	↑	Embodiment 5	Saturated under max1.4	0.19	242	225	0.93	↑
Embodiment 6	Saturated under max2	0.25	160	145	0.91	↑	Embodiment 7	Saturated under max2	0.24	166	144	0.87	↑
Embodiment 8	Saturated under max2.1	0.13	300	258	0.86	↑	Embodiment 7	Saturated under max2	0.24	166	144	0.87	↑
Embodiment 8	Saturated under max2.1	0.13	300	258	0.86	↑	Embodiment 9	Saturated under max2.1	0.14	279	248	0.89	↑
Embodiment 10	Saturated under max2.0	0.13	308	228	0.74	↑	Embodiment 9	Saturated under max2.1	0.14	279	248	0.89	↑
Embodiment 10	Saturated under max2.0	0.13	308	228	0.74	↑	Embodiment 11	Saturated under max2.6	0.3	113	97	0.86	↑
Embodiment 12	0.1	0.43	113	85	0.75	↑	Embodiment 11	Saturated under max2.6	0.3	113	97	0.86	↑
Embodiment 12	0.1	0.43	113	85	0.75	↑	Embodiment 13	0.8	0.88	35.7	25	0.7	No problem (being designated as the life-span in the time of will showing CTL owing to damage)
Embodiment 14	0.15	0.58	71	55	0.77	No problem	Embodiment 13	0.8	0.88	35.7	25	0.7
Embodiment 14	0.15	0.58	71	55	0.77	No problem	Embodiment 15	Saturated under max2.3	0.4	93	78	0.84	↑
Embodiment 16	0.12	0.42	105	87	0.83	↑	Embodiment 15	Saturated under max2.3	0.4	93	78	0.84	↑
Embodiment 16	0.12	0.42	105	87	0.83	↑	Embodiment 17	Saturated under max1.0	0.15	333	240	0.72	↑
							Embodiment 17	Saturated under max1.0	0.15	333	240	0.72	↑
							Comparative example 1	1.2	0.16	300	180	0.6	No problem
Comparative example 2	0.9	1.3	27.7	13	0.47	↑	Comparative example 1	1.2	0.16	300	180	0.6	No problem
Comparative example 2	0.9	1.3	27.7	13	0.47	↑	Comparative example 3	2.5	0.17	205	105	0.51	It is bad to produce slight CLN near 70K opens
Comparative example 4	-	-	-	-	-	It is bad to produce cleaning in the time of 100	Comparative example 3	2.5	0.17	205	105	0.51	It is bad to produce slight CLN near 70K opens
Comparative example 4	-	-	-	-	-	It is bad to produce cleaning in the time of 100	Comparative example 5	-	-	-	-	-	It is bad to produce cleaning in the time of 3000

Table 2

	Rzjis(A) (μm)	Rzjis(B) (μm)	RSm(C) (μm)	RSm(D) (μm)	RSm(D)/RSm(C)	Rp(F) (μm)	Rv(E)/Rp(F)
	Rzjis(A) (μm)	Rzjis(B) (μm)	RSm(C) (μm)	RSm(D) (μm)	RSm(D)/RSm(C)	Rp(F) (μm)	Rv(E)/Rp(F)	Embodiment 1	0.55	0.6	42	43	1.02	0.2	2.02
Embodiment 2	0.53	0.61	41	43	1.05	0.2	2.05	Embodiment 1	0.55	0.6	42	43	1.02	0.2	2.02
Embodiment 2	0.53	0.61	41	43	1.05	0.2	2.05	Embodiment 3	0.53	0.59	42	44	1.04	0.19	2.15
Embodiment 4	0.6	0.66	45	44	0.98	0.22	2.2	Embodiment 3	0.53	0.59	42	44	1.04	0.19	2.15
Embodiment 4	0.6	0.66	45	44	0.98	0.22	2.2	Embodiment 5	0.68	0.64	45	46	1.02	0.2	2.7
Embodiment 6	0.72	0.72	49	47	0.96	0.22	3.55	Embodiment 5	0.68	0.64	45	46	1.02	0.2	2.7
Embodiment 6	0.72	0.72	49	47	0.96	0.22	3.55	Embodiment 7	0.68	0.69	43	48	1.12	0.22	3.2
Embodiment 8	0.75	0.88	38	40	1.05	0.24	2.5	Embodiment 7	0.68	0.69	43	48	1.12	0.22	3.2
Embodiment 8	0.75	0.88	38	40	1.05	0.24	2.5	Embodiment 9	0.73	0.8	40	43	1.08	0.24	2.7
Embodiment 10	0.72	0.77	44	50	1.14	0.3	2	Embodiment 9	0.73	0.8	40	43	1.08	0.24	2.7
Embodiment 10	0.72	0.77	44	50	1.14	0.3	2	Embodiment 11	0.71	0.69	46	46	1	0.25	3.11
Embodiment 12	1.16	1.2	61	53	1.04	0.36	2.88	Embodiment 11	0.71	0.69	46	46	1	0.25	3.11
Embodiment 12	1.16	1.2	61	53	1.04	0.36	2.88	Embodiment 13	1.33	1.6	35	30	0.86	0.4	2.1
Embodiment 14	1.41	1.45	72	77	1.07	0.46	2.2	Embodiment 13	1.33	1.6	35	30	0.86	0.4	2.1
Embodiment 14	1.41	1.45	72	77	1.07	0.46	2.2	Embodiment 15	0.77	0.8	46	50	0.64	0.25	2.1
Embodiment 16	0.4	0.41	70	66	0.94	0.1	1.5	Embodiment 15	0.77	0.8	46	50	0.64	0.25	2.1
Embodiment 16	0.4	0.41	70	66	0.94	0.1	1.5	Embodiment 17	0.25	0.27	80	95	1.19	0.1	1.1
								Embodiment 17	0.25	0.27	80	95	1.19	0.1	1.1
								Comparative example 1	0.55	0.6	42	43	1.02	0.2	2.02
Comparative example 2	1.8	2.5	15	20	1.3	0.9	1.3	Comparative example 1	0.55	0.6	42	43	1.02	0.2	2.02
Comparative example 2	1.8	2.5	15	20	1.3	0.9	1.3	Comparative example 3	0.98	0.88	31	110	3.55	0.83	1.1
Comparative example 4	0.17	0.15	-	-	-	0.1	0.9	Comparative example 3	0.98	0.88	31	110	3.55	0.83	1.1
Comparative example 4	0.17	0.15	-	-	-	0.1	0.9	Comparative example 5	0.2	0.18	-	-	-	0.11	0.9

The right of priority that Japanese patent application 2004-131660 number that the application requires to enjoy Japanese patent application 2004-092099 number submitted on March 26th, 2004, submitted on April 27th, 2004 and the Japanese patent application submitted on October 22nd, 2004 are 2004-308308 number, and quote the part of its content as the application.

Claims

1. Electrophtography photosensor, it has supporter and is arranged on organic photosensitive layer on this supporter, it is characterized in that,

Be formed with the recess of a plurality of shallow concave shape on the surface of the superficial layer of this Electrophtography photosensor, in the recess of this shallow concave shape, the surface of the superficial layer of this Electrophtography photosensor that per 100 μ m are square, longest diameter the scope of 1～50 μ m and the degree of depth more than 0.1 μ m and volume at 1 μ m ³The number of the recess of above shallow concave shape is 5～50,

And this superficial layer and and following one deck of this superficial layer next-door neighbour between the interface be formed with the corresponding recess of recess of the shallow concave shape on a plurality of and the surface that is formed on this superficial layer,

The recess of the shallow concave shape that forms on the surface of this superficial layer with this superficial layer and and following one deck of this superficial layer next-door neighbour between the matching rate of recess of interface formation be 50～100%,

The thickness of this superficial layer is below the above 15 μ m of 2 μ m,

The elastic deformation rate on the surface of this superficial layer is more than 43% below 68%,

With the universal hardness value (HU) of this superficial layer next-door neighbour's following one layer surface be 240N/mm ²Below.

2. Electrophtography photosensor according to claim 1, wherein, the matching rate of the recess of the recess of the shallow concave shape that forms on the surface of described superficial layer and the interface formation between following one deck of described superficial layer and described and superficial layer next-door neighbour is 70～100%.

3. Electrophtography photosensor according to claim 1, wherein, the elastic deformation rate on the surface of described superficial layer is more than 46%.

4. Electrophtography photosensor according to claim 3, wherein, the elastic deformation rate on the surface of described superficial layer is more than 50%.

5. Electrophtography photosensor according to claim 4, wherein, the elastic deformation rate on the surface of described superficial layer is below 63%.

6. Electrophtography photosensor according to claim 1, wherein, the universal hardness value (HU) on the surface of described superficial layer is 150～230N/mm ²Below.

7. Electrophtography photosensor according to claim 1, wherein, the elastic deformation rate of described and superficial layer next-door neighbour's following one layer surface is 45% below, universal hardness value (HU) is 230N/mm ²Below.

8. Electrophtography photosensor according to claim 1, wherein, the thickness of described superficial layer is below the 10 μ m.

9. Electrophtography photosensor according to claim 8, wherein, the thickness of described superficial layer is below the 6 μ m.

10. Electrophtography photosensor according to claim 1, wherein, described superficial layer is a cured layer.

11. Electrophtography photosensor according to claim 1, wherein, described superficial layer is to contain the cured layer that is selected from least a kind of curable resin in the group that acryl resin, phenolics, epoxy resin, silicone resin and urethane resin form.

12. Electrophtography photosensor according to claim 1, wherein, described superficial layer contains by making with the hole transport ability compound that has 2 above chain polymerization functional groups in a part and is cured the solidfied material that polymerization obtains.

13. Electrophtography photosensor according to claim 12, wherein, described solidfied material is to make by heating or irradiation radioactive ray describedly to be cured the solidfied material that polymerization obtains with the hole transport ability compound that has 2 above chain polymerization functional groups in a part.

14. Electrophtography photosensor according to claim 13, wherein, described radioactive ray are electron ray.

15. Electrophtography photosensor according to claim 1, wherein, described superficial layer is the layer that forms by coating.

16. Electrophtography photosensor according to claim 1, wherein, described superficial layer is the layer that forms by dip-coating.

17. Electrophtography photosensor according to claim 1, wherein, described photographic layer is from the described stacked charge generation layer of supporter one side and charge transport layer and the cascade type photographic layer that forms, described superficial layer is this charge transport layer, and described following one deck with the superficial layer next-door neighbour is this charge generation layer.

18. Electrophtography photosensor according to claim 1, wherein, described photographic layer is the cascade type photographic layer that forms from the stacked charge generation layer of described supporter one side, first charge transport layer and second charge transport layer, described superficial layer is this second charge transport layer, and described following one deck with the superficial layer next-door neighbour is this first charge transport layer.

19. Electrophtography photosensor according to claim 1; wherein; described Electrophtography photosensor also has the protective seam that is arranged on the described photographic layer; described photographic layer is from the described stacked charge generation layer of supporter one side and charge transport layer and the cascade type photographic layer that forms; described superficial layer is this protective seam, and described following one deck with the superficial layer next-door neighbour is this charge transport layer.

20. the manufacture method of the described Electrophtography photosensor of claim 1 is characterized in that, comprises following operation:

Recess forms operation: handle by the surface that is formed the formed described superficial layer of operation by this superficial layer being carried out dry type blasting treatment or wet type honing, thereby form the recess of a plurality of shallow concave shape on the surface of described superficial layer, and the interface between following one deck of described superficial layer and described and superficial layer next-door neighbour forms and the corresponding recess of recess this shallow concave shape a plurality of.

21. handle box, it is characterized in that, be with described Electrophtography photosensor of claim 1 or the Electrophtography photosensor by the described manufacture method manufacturing of claim 20 and be selected from least a kind of handle box that the unit one supports in charged elements, developing cell and the cleaning unit, and this handle box can freely load and unload with respect to the electro-photography apparatus main body.

22. electro-photography apparatus, it is characterized in that the Electrophtography photosensor and charged elements, exposing unit, developing cell, transfer printing unit and the cleaning unit that possess the described Electrophtography photosensor of claim 1 or make by the described manufacture method of claim 20.