CN100549844C - Photoelectric conductor for electronic photography - Google Patents

Abstract

A kind of photoelectric conductor for electronic photography, it comprise conductive substrates and on this substrate the order lamination charge generation layer at least and charge transport layer, wherein charge transport layer comprises charge transport material (M) and adhesive resin (B), and adhesive resin (B) contains compound by general formula (1) expression as major component; And having a layer structure of forming by a plurality of described charge transport layers, its outermost layer is in the surface coating hardness test, by under 25 ℃ environment temperature and 50% relative humidity the top layer being applied the highest elasticity power (η that measures when pushing load 5mN _Hu) be 50% or higher, the hardness number (H of plastic yield _Plast) at 220N/mm ²To 275N/mm ²Scope.The weight ratio M/B of outermost charge transport material (M) and adhesive resin (B) preferably is controlled at 30/70 or lower, more preferably in 7/93 and 20/80 scope; And add preferred enamine type charge transport material (2), good and have a photoelectric conductor for electronic photography of high optical Response to obtain printing durability.

Description

Photoelectric conductor for electronic photography

Technical field

The present invention relates to be used for forming the photoelectric conductor for electronic photography and image processing system of image with this photoelectric conductor for electronic photography by the electrofax mode.

Background technology

The duplicating machine that uses as the image processing system of electrofax mode, printing machine, facsimile unit (below be sometimes referred to as electro-photography apparatus) are by following electrofax operation formation image.At first, the photographic layer of the photoelectric conductor for electronic photography of installing on the device (the following photoconductor that abbreviates as sometimes) to predetermined current potential, and forms electrostatic latent image by exposing according to the light such as laser of image information irradiation from exposure device by charged device uniform charged.Then, supply with developer to the electrostatic latent image that forms, toner that is called toner as the developer composition is deposited on the photoconductor surface, with latent electrostatic image developing and with the toner image visualize from developing apparatus.In addition, by transfer device the toner image that forms is transferred on transfer materials such as the recording chart from photoconductor surface, and carries out photographic fixing by fixing device.

When passing through the transfer operation of transfer device, the toner of photoconductor surface not necessarily all transfer printings transfer on the recording chart, but part remains on the photoconductor surface or the paper powder of the recording chart that contacts with photoconductor during transfer printing may be residual when being attached to photoconductor surface.

Toner that photoconductor surface is residual and foreign matter produce harmful effect as the paper powder that adheres to the quality of the image that forms, therefore are removed by cleaning device (cleaning apparatus).

In recent years, clearer minimizing technology makes progress, and does not use cleaning device independently to reclaim residual toner by the cleaning function that appends on the developing apparatus: promptly, reclaim residual toner by the cleaning systems that have development simultaneously.Then, after cleaning photoconductor surface in this way, remove the static on photographic layer surface, thereby electrostatic latent image is disappeared by static eliminator etc.

The photoelectric conductor for electronic photography that uses in this electrophotographic processes is laminated on the conductive substrates of being made by conductive material by the photographic layer that will contain photoconductive material and constitutes.As photoelectric conductor for electronic photography, the photoelectric conductor for electronic photography that is to use inorganic photoconductive material (hereinafter referred to as inorganic photoconductor) of Shi Yonging in the past.

The representation example of inorganic photoconductor has selenium type photoconductor, and it has the photoconductive layer that comprises amorphous selenium (a-Se) for example or amorphous selenium-arsenic (a-AsSe); Zinc paste type or cadmium sulfide type photoconductor, it has to comprise with sensitizer such as coloured material and is dispersed in the zinc paste (ZnO) in the resin or the photoconductive layer of cadmium sulfide (CdS); With the amorphous silicon type photoconductor, it has the photoconductive layer (hereinafter referred to as the a-Si photoconductor) that comprises amorphous silicon (a-Si).

But inorganic photoconductor has following shortcoming.That is, selenium type photoconductor and cadmium sulfide type photoconductor have problems aspect thermotolerance and storage stability.In addition, selenium and cadmium are for comprising that human biology has toxicity, and it uses existing problems aspect environmental pollution, and therefore, it is also suitably discarded to need to collect the photoconductor that uses them after the use.In addition, zinc paste type photoconductor has the low and low such shortcoming of permanance of sensitivity, and therefore it does not re-use substantially now.

On the other hand, cause that as the environmental friendliness inorganic photoconductor a-Si photoconductor of concern has the advantage of high sensitivity and good endurance, still, because it is unfriendly by the plasma chemical vapor deposition manufactured, therefore be difficult to be formed uniformly photographic layer, be easy to cause image deflects.In addition, the a-Si photoconductor is unfavorable aspect throughput rate, therefore has the high shortcoming of manufacturing cost.

As mentioned above, because inorganic photoconductor has many shortcomings, therefore need to develop the photoconductive material that new photoelectric conductor for electronic photography is used, therefore often using the organic type photoconductive material is that organic photoconductor (organic photoconductor: be abbreviated as OPC) replaces the inorganic type photoconductive material of use in the past.

The photoelectric conductor for electronic photography (hereinafter referred to as organic photoconductor) of use organic type photoconductive material is compared with inorganic photoconductor has many advantages aspect toxicity, manufacturing cost and the material design alternative, but has a little problem aspect sensitivity, permanance and the environmental stability.In addition, organic photoconductor has the advantage that can form its photoconductive layer by the method such as the dip coated method of easy economy.

Have many advantages as mentioned above, so organic photoconductor tends to use as the main flow of photoelectric conductor for electronic photography.In addition, based on recent research and development, the sensitivity and the permanance of organic photoconductor improve, and now except that special circumstances, organic photoconductor has been used for photoelectric conductor for electronic photography.

Especially, the performance of organic photoconductor significantly improves by the exploitation of function divergence type photoconductor, and in described function divergence type photoconductor, the charge generation function is distributed to different materials respectively with the charge transport function.That is, function divergence type photoconductor also has the wide and photoconductor that have a desirable characteristics of the material range of choice that constitutes photoconductive layer and makes more or less freely advantage except that the above-mentioned advantage of organic photoconductor.

This function divergence type photoconductor is divided into laminated-type and single-layer type, in laminated-type function separated light electric conductor, be provided with the laminated-type photoconductive layer that constitutes by charge generation layer that contains the charge generation material of bearing the charge generation function and the charge transport layer that contains the charge transport material of bearing the charge transport function.

Above-mentioned charge generation layer and charge transport layer generally form by charge generation material and charge transport material being dispersed in respectively in the adhesive resin as bonding agent.

On the other hand, single-layer type function divergence type photoconductor has by charge generation material and charge transport material are dispersed in the single-layer type photoconductive layer that forms in the adhesive resin together.

As the charge generation material that is used for function divergence type photoconductor, studied multiple material, as phthalocyanine color, side's sour inner salt (squarylium) coloured material, AZO pigments, perylene dye, encircle quinone pigments, cyanine coloured material, squaric acid dyes and pyrans (pyrylium) type coloured material more, the various materials that photostability is strong, the charge generation ability is high have been proposed.

As the charge transport material, developed pyrazoline compounds, hydrazone compound, triphenyl amine compound, stilbene compounds etc., in addition, in recent years, developed and had pyrene derivatives, naphthalene derivatives and the terphenyl derivant that the fused polycycle hydrocarbon is the center precursor skeleton.

The charge transport material demand:

(1) to light and thermally stable;

(2) active substance that produces by corona discharge when making photoconductor charged such as ozone, oxides of nitrogen (NO _x) and nitric acid be stable;

(3) has high charge delivery capability;

(4) with the compatibility height of organic solvent and adhesive resin; With

(5) easy to manufacture and cost is low;

But the known charge transport material of above-mentioned routine satisfies the part of these requirements, but can not satisfy all these requirements with high level.

Recently, photoconductor need have high sensitivity as the photoconductor characteristic, and the charge transport material demand has miniaturization and the corresponding extra high charge delivery capability of high speed with electro-photography apparatus such as digital duplicating machine and printing machine.In addition, in high-velocity electrons photograph process, since short from the time that is exposed to development, therefore need the photoconductor optical Response good.

If the optical Response of photoconductor is low, promptly, if the rate of decay of exposure rear surface current potential is slow, then residual electric potential rises, photoconductor does not fully use under the state of decay repeatedly at surface potential, the surface charge that should remove is not fully eliminated by exposure, causes the early stage deterioration of undesired consequences such as picture quality.

On the other hand, in function divergence type photoconductor, the electric charge that produces in the charge generation material by light absorption arrives the photographic layer surface by the charge transport mass transport, the surface charge of the rayed part of photoconductor is eliminated, so optical Response depends on the charge delivery capability of charge transport material.Therefore, realizing having aspect the photoconductor of sufficient optical Response, the charge transport material demand has high charge delivery capability.

As the charge transport material that satisfies above-mentioned requirements, the high enamine compound of the charge delivery capability charge transport material more known than above-mentioned routine (for example, referring to Japanese Patent Application Publication (JP) flat 2-51162 number, the flat 6-43674 of JP number and the flat 10-69107 of JP number) has been proposed.In addition, in order to improve the cavity conveying ability of photoconductor, the enamine compound (for example referring to the flat 7-134430 of JP number) that has also proposed in photographic layer, to add polysilane and had ad hoc structure.

In the actual use of electro-photography apparatus, owing in all cases photoconductor is carried out repeatedly the operation of above-mentioned charged, exposure, development, transfer printing, cleaning and elimination static, therefore, except that high sensitivity and good optical Response, also need photoconductor to have environmental stability, electrical stability and to the permanance of mechanical external force.

Particularly, need photoconductor to have to be difficult to be cleaned slip that member etc. brings and friction and the top layer of wearing and tearing.Therefore, satisfy the rerum natura of the photoconductor surface of above-mentioned target, the good photoconductor with high-durability can be provided by regulation.

Hardness is to estimate the extensive rerum natura of the material that comprises the photoelectric conductor for electronic photography surface, particularly estimates one of index of engineering properties.Hardness is defined as the stress of material when pressing son to clamp-on in the material.Trial will constitute the engineering properties quantification of the film on photoelectric conductor for electronic photography surface by using hardness as the physical parameter of knowing material property.For example, scraping strength test, pencil hardness test and Vickers hardness test are widely known by the people as the test method of measuring hardness.But, in any hardness test, as containing organic film, in the mensuration of the engineering properties of the material that shows complex behavior such as plasticity, elasticity (comprise and postpone composition), have problems.

For example, Vickers hardness test is by the impression length evaluation hardness in the mensuration film, but it only reflects the plasticity of film, and can not accurately estimate can be with the organic engineering properties of high resiliency deformation ratio distortion.Therefore, the engineering properties of the film that is made of organism need be considered various characteristics evaluation.

In having the photoelectric conductor for electronic photography of organic photosensitive layer, for example, plasticity power (plastic yield rate, η have been put down in writing as the top layer _Plast, %) with elasticity power (elastic deformation rate, η _HU, %) as the rerum natura (for example, referring to JP2000-10320 and JP2002-6526) that is used to judge long-term abrasion performance, permanance and operational stability.

Plasticity power (plastic power) is the percentage of plastic yield working load to the ratio of plastic yield working load (plastic yield institute energy requirement) and elastic deformation working load (elastic deformation institute energy requirement) sum.

In addition, elasticity power (elastic power) is the percentage of elastic deformation working load to the ratio of plastic yield working load and elastic deformation working load sum.

Therefore, plastic yield working load and elastic deformation working load sum are 100 (%).

JP2000-10320 has put down in writing plasticity power (plastic yield rate) particularly and has been set in 30 to 70% the scope, and the universal hardness (Hu) of the universal hardness test determination by the DIN50359-1 regulation is set in 230 to 700N/mm ²Scope in.In addition, JP2000-10320 has put down in writing by setting such numerical range, prevents the mechanical deterioration on photoconductor top layer.

But the numerical range 30 of plasticity power is one to 70% and covers the general at present almost scope of using of whole organic photosensitive layers that contains adhesive resin.Therefore, even plasticity power in above-mentioned scope, also not necessarily always can access the good organic photosensitive layer of long-term abrasion performance, permanance and operational stability.

In addition, JP2002-6526 has put down in writing and has had organic photosensitive layer and comprise curable resin as the protective seam of adhesive resin and the elasticity power η of this protective seam on conductive supporting member _Hu(=[elastic deformation working load/(plastic yield working load+elastic deformation working load)]) photoelectric conductor for electronic photography in 32 to 60% scopes.

But, numerical range 32 to 60% and plasticity power synonym in 40 to 68% scope of elasticity power, same with JP2000-10320, it has covered nearly all photoelectric conductor for electronic photography with organic photosensitive layer as the top layer of present use.

In addition, the curable resin as adhesive resin also is common in the photoelectric conductor for electronic photography technical field.

Therefore, in fact JP2002-6526 does not have record to obtain the solution of the good organic photosensitive layer of long-term abrasion performance, permanance and operational stability.In addition, the existence of the photoelectric conductor for electronic photography of JP2002-6526 forms the problem that the protective seam that contains curable resin causes cost to increase.

In the past, the resin of attempting increasing the ratio of the adhesive resin that uses in the top layer or using high molecular was as the means that improve printing durability, to improve the permanance of photoelectric conductor for electronic photography.But the increase of resin ratio causes the relative quantity of charge transport material in the top layer to reduce and the sensitivity of photoconductor descends, and is inappropriate for present high-speedization tendency therefore.

As the means that overcome these shortcomings, proposed further the function of charge transport layer to be separated, in the outmost surface layer, add the better resin kind of permanance, and the compensation sensitivity (for example, referring to JP2000-214602) of surface layer down.But, do not have the open character of surface of controlling permanance substantially.In addition, use the high molecular adhesive resin to make that the viscosity of coating fluid increases the problem that causes throughput rate to descend in the dip coated method.

In addition; disclosing the polyarylate type resin of putting down in writing among the JP2004-219922 is the fine resin kind that manifests high printing durability; but; consider from the dissolubility aspect; must use halogeno-benzene such as monochloro-benzene and specific halogen-type organic solvent; consider from effect, be subjected to sizable restriction in the undeniable production for human health and global environmental protection.

Summary of the invention

For with duplicating machine and printing machine miniaturization and make its Maintenance free, for the present actual organic photoconductor that uses, the problem of existence mainly is permanance, therefore, the objective of the invention is to address this problem, and the photoconductor that can use for a long time is provided.

The present inventor has carried out research extensively and profoundly, found that, can address this problem by following photoelectric conductor for electronic photography.Described photoelectric conductor for electronic photography is depressed into few charge generation layer by sequential layer on conductive substrates and obtains with the charge transport layer that contains adhesive resin and charge transport material, its charge transport layer has the layer structure of being made up of a plurality of charge transport layers, and the outermost charge transport layer of described photoelectric conductor for electronic photography has the elasticity power (η of each comfortable particular range in the surface coating hardness test _Hu) and the hardness number of plastic yield.These discoveries cause having finished the present invention.

That is, the invention provides a kind of photoelectric conductor for electronic photography, it has: conductive substrates; Be pressed in charge generation layer at least and charge transport layer on the described substrate with sequential layer, wherein said charge transport layer comprises charge transport material (M) and adhesive resin (B), and described adhesive resin (B) contains by the compound of general formula (1) expression as principal ingredient:

Wherein, R ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇And R ₈Mutually can be identical or different, represent hydrogen atom, halogen atom or replacement or unsubstituted C independently of one another ₁-C ₆Alkyl; R ₉And R ₁₀Mutually can be identical or different, represent hydrogen atom, halogen atom, replacement or unsubstituted C independently of one another ₁-C ₆Alkyl, saturated cyclic C ₄-C ₁₀Alkyl or replacement or unsubstituted aryl; N represents integer;

And has a layer structure of forming by a plurality of described charge transport layers, the outermost layer of wherein said charge transport layer is in the surface coating hardness test, by under 25 ℃ environment temperature and 50% relative humidity the top layer being applied the highest elasticity power (η that measures when pushing load 5mN _Hu) be 50% or higher, and the hardness number (H of plastic yield _Plast) at 220N/mm ²Or it is higher to 275N/mm ²Or in the lower scope.

In addition, the invention provides a kind of aforesaid photoelectric conductor for electronic photography, wherein said charge transport layer contains the charge transport material with enamine structure by following formula (2) expression.

In addition, the invention provides a kind of image processing system, it comprises above-mentioned photoelectric conductor for electronic photography, be used to the Charging system that makes described photoelectric conductor for electronic photography charged, be used to make charged photoelectric conductor for electronic photography to use light to expose to form the exposure device of electrostatic latent image corresponding to image information, be used for developing apparatus by latent electrostatic image developing being made toner image develop, be used for the transfer device of toner image from the photoelectric conductor for electronic photography surface transfer to transfer materials and the cleaning device that is used for cleaning photoelectric conductor for electronic photography surface behind the transfer printing toner image.

According to the present invention, it is good and keep the photoelectric conductor for electronic photography of high-durability for a long time to obtain electrical characteristics and printing durability.

This photoelectric conductor for electronic photography makes and duplicating machine and printing machine miniaturization can be carried out image steadily in the long term and formed, and provide the image processing system that need not frequent maintenance with low cost.

The application's these and other objects will be clearer by following detailed description.But, should be appreciated that,, be only used for illustration although this detailed description and concrete example are represented preferred implementation of the present invention, because it is evident that for a person skilled in the art, can carry out variation and distortion in spirit and scope of the invention from this detailed description.

Description of drawings

Fig. 1 is the part sectional drawing of simplified structure that shows the photoelectric conductor for electronic photography 1 of embodiment of the present invention;

Fig. 2 is the part sectional drawing of simplified structure that shows the photoelectric conductor for electronic photography 2 of embodiment of the present invention;

Fig. 3 is used to illustrate elasticity power η _HuThe figure of computing method;

Fig. 4 shows that the simplified image of the 4th embodiment of the present invention forms the side arrangement plan of device 30.

Embodiment

The invention is characterized in that described charge transport layer comprises adhesive resin (B), described adhesive resin (B) contains by the compound of general formula (1) expression as principal ingredient:

Wherein, R ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇And R ₈Mutually can be identical or different, represent hydrogen atom, halogen atom or replacement or unsubstituted C independently of one another ₁-C ₆Alkyl; R ₉And R ₁₀Mutually can be identical or different, represent hydrogen atom, halogen atom, replacement or unsubstituted C independently of one another ₁-C ₆Alkyl, saturated cyclic C ₄-C ₁₀Alkyl or replacement or unsubstituted aryl; N represents integer.

In above-mentioned general formula (1), can replace by R ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇, R ₈, R ₉And R ₁₀The C of expression ₁-C ₆The substituent example of alkyl has C ₁-C ₄Alkyl such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl or the tert-butyl group, and C ₁-C ₄Alkoxy such as methoxyl, ethoxy, propoxyl group, isopropoxy, butoxy, isobutoxy or tert-butoxy.Wherein, preferable methyl.

As described C ₁-C ₆The example of alkyl has C ₁-C ₆Alkyl such as methyl, ethyl, propyl group, butyl, amyl group and hexyl and their constitutional isomer.Wherein, preferable methyl.

In above-mentioned general formula (1), can replace by R ₉And R ₁₀The substituent example of the aryl of expression has C ₁-C ₄Alkyl such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl or the tert-butyl group, and C ₁-C ₄Alkoxy such as methoxyl, ethoxy, propoxyl group, isopropoxy, butoxy, isobutoxy or tert-butoxy.Wherein, preferable methyl.

The example of described aryl has aryl such as phenyl, tolyl, naphthyl or xenyl.Wherein, preferred phenyl.

Described saturated cyclic C ₄-C ₁₀The example of alkyl has cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group or decyl.

In described general formula (1), n is an integer, and its expression is by the degree of polymerization of the compound of general formula (1) expression, wherein measure the number-average molecular weight (Mn) of (calculating) described compound in 20,000 to 100,000 scope based on polystyrene by GPC, in preferred 30,000 to 80,000 the scope.

This is based on following reason: when the number-average molecular weight (Mn) of the compound of general formula (1) less than 20,000 o'clock, a little less than using described compound to become too as the intensity of the photographic layer of adhesive resin, thereby can not increase the abrasion performance of photographic layer, surpass 100 and work as described Mn, 000 o'clock, bonding agent was difficult to be dissolved in the solvent because of molecular weight becomes greatly, and the dispersiveness of each material of deterioration.

Fig. 1 is the part sectional drawing of simplified structure that shows the photoelectric conductor for electronic photography 1 of embodiment of the present invention.The photoelectric conductor for electronic photography 1 of this embodiment (below, abbreviate photoconductor as) comprises the tubular conductive substrates 11 made by conductive material, contain the charge generation material and at charge generation layer 12 that forms on the outer peripheral face of conductive substrates 11 and the charge transport layer 13 and 14 that contains the charge transport material and further form on charge generation layer 12.Charge generation layer 12 and charge transport layer 13 and 14 constitute photographic layer 15.That is, photoconductor 1 is the laminated-type photoconductor.

Conductive substrates 11 works as the electrode of photoconductor 1, also plays the effect as the supporting member of each layer 12,13 and 14.

The shape of conductive substrates 11 is tubular in this embodiment, still, is not limited thereto, and can be for example cylindric, sheet or endless belt-shaped.

The conductive material that constitutes conductive substrates 11 can be metal simple-substance such as aluminium, copper, zinc and titanium, and alloy such as aluminium alloy and stainless steel.In addition, this material also can be those materials that obtain by on the surface that metal foil layer is pressed in polymeric material such as polyethylene terephthalate, nylon or polystyrene, hard paper or glass; By metal material being deposited on those materials that obtain on these material surfaces; Layer those material that obtains by deposition on these surfaces or formation conductive compound such as conducting polymer, tin oxide or indium oxide.

These conductive materials can be processed as the shape of regulation and use.

If desired, in the scope that does not influence picture quality, the surface of conductive substrates 11 can handle, utilize the surface treatment of chemicals or hot water etc., painted processing or surface coarsening processing carrying out diffuse reflection to handle by anodized coating.

In using the electrophotographic processes of laser as exposure source, because the laser waveform is even, therefore laser light reflected bundle and interfere on photoconductor surface in the laser beam of photoconductor internal reflection, the interference fringe that is caused by this interference appears in the image sometimes, thus the image deflects of causing.But, because the image deflects that the interference of the uniform laser beam of waveform causes can be avoided by above-mentioned processing is carried out on the surface of conductive substrates 11.

Charge generation layer 12 comprises by absorbing light and produces the charge generation material of electric charge as principal ingredient.

Can comprise organic photoconductive material as charge generation material effective substances, for example, azo type pigment such as Monoazo type pigment, bisdiazo type pigment and trisazo-type pigment; Indigo type pigment such as indigo and thioindigo; (peryleneimide) is with perylene acid anhydrides (perylene acid anhydride) for perylene type pigment such as perylene diimide; Many ring quinoid pigment such as anthraquinone and pyrene quinone; Phthalocyanine type pigment such as metal phthalocyanine and nonmetal phthalocyanine; Side's sour inner salt (squarylium) coloured material; Pyranoid form salt and sulfo-pyralium salt; With triphenyl methane type coloured material; With inorganic photoconductive material such as selenium and amorphous silicon.These charge generation materials can use separately or its two or more potpourris that can be used as use.

In above-mentioned charge generation material, preferred phthalocyanine type pigment, more particularly, preferred titanyl phthalocyanine (oxotitanium phthalocyanine) compound that uses by following general formula (A) expression:

Wherein, X ¹, X ², X ³And X ⁴Mutually can be identical or different, represent hydrogen atom, halogen atom, alkyl or alkoxy independently of one another; R, s, y and z represent 0 to 4 integer independently.

In above-mentioned general formula (A), as by X ¹, X ², X ³And X ⁴The example of the halogen atom of expression has fluorine, chlorine, bromine or iodine.

As by X ¹, X ², X ³And X ⁴The example of the alkyl of expression has C ₁-C ₄Alkyl such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl or the tert-butyl group.

As by X ¹, X ², X ³And X ⁴The example of the alkoxy of expression has C ₁-C ₄Alkoxy such as methoxyl, ethoxy, propoxyl group, isopropoxy, butoxy, isobutoxy or tert-butoxy.

Titanyl phthalocyanine compound by above-mentioned general formula (A) expression is the charge generation material with high charge generation efficient and high electric charge injection efficiency, when being used for charge generation layer 12, can produce a large amount of electric charges by absorbing light, and effectively with in the charge transport material contained in the electric charge iunjected charge transfer layer 13 that produces and not in the inside accumulation, thereby swimmingly with the surface of charge transport to photographic layer 15.

Titanyl phthalocyanine compound by above-mentioned general formula (A) expression can pass through known manufacture method such as Moser in the past, Frank H and Arthur L.Thomas, PhthalocyanineCompounds, Reinhold Publishing Corp., New York, the method manufacturing of record in 1963.

Wherein X by above-mentioned general formula (A) expression ¹, X ², X ³And X ⁴The group of expression all is that the example of the titanyl phthalocyanine of hydrogen atom is by with benzene dicarbonitrile and titanium tetrachloride heating and melting or make benzene dicarbonitrile and titanium tetrachloride thermal response in appropriate solvent such as α-chloronaphthalene, synthetic thus dichloro titanium phthalocyanines obtains the hydrolysis in alkali or water of dichloro titanium phthalocyanines then.

Titanyl phthalocyanine can be made as four titanium butoxide thermal response in appropriate solvent such as N-Methyl pyrrolidone by making isoindoline and four titanium alkoxides.

The charge generation material can with sensitizer as being the triphenyl methane type dye of representative with methyl violet, crystal violet, dark blue (night blue) and Victoria blue (Victoria Blue); With erythrosine, rhodamine B, rhodamine 3R, acridine orange and Flaveosine is the acridine dye of representative; Green with methylene blue and methylene is the thiazine dye of representative; With blue (Capryl Blue) and meldola blue (Meldras Blue) in the Kapp is representative De oxazine dye; Cyanine-type dyestuff, styryl dye, pyrans (pyrylium) dyestuff and sulfo-pyrans (thiopyrylium) dyestuff etc. are used in combination.

The formation method of charge generation layer 12 can be by vacuum vapour deposition with above-mentioned charge generation electrodeposition substance in the lip-deep method of conductive substrates 11 or will be dispersed in the charge generation layer that obtains in the appropriate solvent is coated on the surface of conductive substrates 11 with coating fluid method by above-mentioned charge generation material.The preferred use: utilize usual manner that the charge generation material is dispersed in the binder resin solution that obtains by the adhesive resin that mixes as bonding agent in solvent and prepare the charge generation layer coating fluid, then the coating fluid of gained is coated on the lip-deep method of conductive substrates 11.Below, this method is described.

The example of the adhesive resin that uses in the charge generation layer 12 can comprise resin such as vibrin, polystyrene resin, urethane resin, phenol resin, alkyd resin, melamine resin, epoxy resin, silicone resin (silicone resin), acrylic resin (acrylic resin), methacrylic resin (methacrylic resin), polycarbonate resin, polyarylate (polyarylate) resin, phenoxy resin, polyvinyl butyral resin and vinyl-formal resin, and the copolymer resin that contains two or more repetitives that constitute these resins.

The object lesson of copolymer resin can comprise insulating resin such as vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-copolymer-maleic anhydride resin and acrylonitritrile-styrene resin resin.

Adhesive resin is not limited to these illustrative resins, can use normally used resin.These resins can use separately or two or more mix use.

Charge generation layer has halogenated hydrocarbon such as methylene chloride and ethylene dichloride with the example of the solvent of coating fluid; Ketone such as acetone, MEK, cyclohexanone; Ester class such as ethyl acetate and butyl acetate; Ethers such as tetrahydrofuran are with diox; The alkyl ether of ethylene glycol is as 1, the 2-dimethoxy-ethane; Aromatic hydrocarbons such as benzene, toluene and dimethylbenzene; With aprotic polar solvent such as N, dinethylformamide and N,N-dimethylacetamide.In these solvents, consider preferred non-bittern type organic solvent from the angle of global environmental protection.These solvents can use separately or two or more mix use.

Contain the weight W 1 of charge generation material in the charge generation layer 12 of charge generation material and adhesive resin and adhesive resin weight W 2 ratio W1/W2 preferably 10 (10/100) or higher to 400 (400/100) percent or lower scope in.If be lower than 10/100 than W1/W2, the sensitivity of photoconductor reduces, if surpass 400/100 than W1/W2, find that not only the film strength of charge generation layer 12 reduces but also the dispersiveness of charge generation material reduces, thereby oversize grain increases, therefore should reduce by the surface charge of the part beyond the part of eliminating of exposing, thereby cause image deflects, particularly because toner is deposited on the image photographic fog increase that is called blackspot that forms on the white background with minimum stain.Therefore, above-mentioned preferable range than W1/W2 be set in 10/100 or higher to 400/100 or lower scope in.

The charge generation material can be pulverized with comminutor before in being dispersed in binder resin solution in advance.

The example of the comminutor that uses in the pulverization process can be bowl mill, sand mill (sandmill), refiner (attriter), vibration grinding machine (shaking mill) and ultrasonic diverting device.

The example of the diverting device that uses when in addition, being dispersed in the charge generation material in the binder resin solution can be paint jolting machine (paint shaker), bowl mill and a sand mill.The dispersion condition of this moment can suitably be selected, and makes to avoid because the pollution of the impurity that the abrasion of the parts of container that uses and diverting device etc. produce.

Charge generation layer can be that for example, spraying process, scraping article rubbing method (bar coating method), rolling method, scraper plate rubbing method (blade method), ring are coated with method (ring coating method) and dip coated method with the coating process of coating fluid.Can consider that the rerum natura and the throughput rate that are coated with selects best mode from these coating processes.

Especially, in these coating processes, the dip coated method is by substrate being immersed in the coating pan of filling coating fluid, then with constant speed or the speed that gradually changes with the substrate pull-up, thereby cambial method on substrate surface, fairly simple and throughput rate of this method and cost are good, so this method is often used when making photoelectric conductor for electronic photography.The device that the dip coated method is used can be provided with by the coating fluid diverting device of ultrasonic generator as representative, so that the dispersiveness of coating fluid is stable.

The thickness of charge generation layer 12 is preferably in 0.05 μ m or bigger and 5 μ m or littler scope, more preferably in 0.1 μ m or bigger and 1 μ m or littler scope.If find that the thickness of charge generation layer 12 is littler than 0.05 μ m, then efficiency of light absorption descends, thereby reduces the sensitivity of photoconductor 1; If the thickness of charge generation layer 12 surpasses 5 μ m, then the electric charge of charge generation layer 12 inside moves in the process of the surface charge of eliminating photographic layer 15 and becomes rate controlling step, thereby reduces the sensitivity of photoconductor 1.

Therefore, the preferred thickness range of charge generation layer 12 is set at 0.05 μ m or bigger and 5 μ m or littler.

Charge transport layer 13 and 14 forms on charge generation layer 12.Charge transport layer 13 contain the charge transport material that can accept the electric charge that produces by the charge generation material that contains in the charge generation layer 12 and delivered charge ability the charge transport material and be used for the adhesive resin that the charge transport material is bonding.In addition, be formed on the charge transport layer 13 with charge transport layer 13 similar charge transport layers 14.

The charge transport examples of substances of using can be enamine derivates, carbazole derivates oxazole derivant oxadiazole derivant, thiazole, thiadiazoles derivative, triazole derivative, imdazole derivatives, imidazolone (imidazolone) derivant, imidazolidine derivative, two imidazolidine derivatives, compound of styryl, hydrazone compound, polycyclc aromatic compound, indole derivatives, pyrazoline derivative azolactone (oxazolone) derivant, benzimidizole derivatives, quinazoline derivant, benzofuran derivatives, acridine derivatives, the azophenlyene derivant, amino stilbene derivatives, the triarylamine derivant, triarylmethane derivatives, phenylenediamine derivative, stilbene derivatives and benzidine derivative.In addition, also can enumerate the polymkeric substance that has in main chain or the side chain derived from the group of above-claimed cpd, for example, poly-(N-vinylcarbazole), poly-(1-vinylpyrene) and poly-(9-vinyl anthracene).

The adhesive resin that contains in the charge transport layer 13 and 14 can be selected from and contain by the polycarbonate of above-mentioned general formula (1) the expression resin as major component.

Described polycarbonate has polycarbonate resin TS2040 as the object lesson of the resin of major component ^TM(Teijin Chemicals Ltd. system), polycarbonate resin GH 503 ^TM(IdemitsuKosan Co., Ltd. system), polycarbonate resin Z-400 ^TM(Mitsubishi Gas ChemicalCompany, Inc. system).

Wherein, optimization polycarbonate resin TS 2040 ^TM(Teijin Chemicals Ltd. system) as the binder resin of charge transport layer 13, because the homogeneity of the solubleness in solvent, the coating layer after forming and good abrasion performance.

In addition, optimization polycarbonate resin GH 503 ^TM(Idemitsu Kosan Co., Ltd. system) as the binder resin of outmost surface layer charge transfer layer 14, because the good mar resistance of the charge transport layer 14 of the abrasion performance of described resin self and contact toner, paper or cleaning balde scraper plate (cleaning blade).

The example of the resin that can be used as the use of second composition beyond those resins can be that vinyl polymer resins is as poly-(methacrylic acid ester methyl ester) resin, polystyrene resin and poly-(vinylidene chloride) resin; Contain 2 or the copolymer resin of more a plurality of repetitives constituting vinyl polymer resins; Vibrin; Polyestercarbonate resin, polysulfone resin, phenoxy resin, epoxy resin, silicone resin, polyarylate resin, polyamide, polyether resin, urethane resin, polyacrylamide resin and phenol resin.Also can comprise by with the partial cross-linked thermoset resin that obtains of these resins.

The weight ratio M/B of charge transport material (M) and adhesive resin (B) has sizable relation with the printing durability of photoconductor as mentioned above in the charge transport layer 13 and 14.The M/B weight ratio of charge transport layer 14 (outmost surface layer) is 30/70 or lower, preferred M/B weight ratio more preferably 7/93 or higher and 20/80 or lower.This is made in above-mentioned scope and the rerum natura on following surface can be set in the required scope than being controlled at.

Charge transport layer 13 needs to increase the M/B weight ratio, to obtain the sensitivity of photoconductor reliably; That is, improve the ratio of charge transport material, preferred M/B weight ratio is 50/50 or higher.On the other hand, consider the even coating and the solubleness of charge transport material in adhesive resin of layer, the rising of M/B is restricted, and stipulates this limit value according to the kind of charge transport material.

Therefore, by suitably the M/B weight ratio of charge transport layer 13 and 14 being set within the limits prescribed, can provide to have excellent durability and highly sensitive photoconductor 1.

If desired, can in charge transport layer 13 and 14, add various adjuvants.For example, in order to improve film forming, pliability and surface smoothing, can in charge transport layer 13, add plastifier or levelling agent.

Plastifier can comprise dibasic acid ester such as phthalic acid ester; Fatty acid ester; Phosphate; Chlorinated paraffin; And epoxy plasticizer.Levelling agent can comprise, for example, and the silicone-type levelling agent.

In addition, for enhance mechanical strength and raising electrical characteristics, for example, can go up and add mineral compound such as titanium dioxide in charge transport layer 13 and 14; With contain fluorine atoms polymeric microsphere such as tetrafluoro ethylene polymer particulate.

Similar with above-mentioned situation by coating formation charge generation layer, charge transport layer 13 and 14 can for example pass through: by in appropriate solvent, above-mentioned adjuvant dissolving with charge transport material and binder substance and when needing or disperse, make the charge transport layer coating fluid, and the coating fluid that obtains is coated on the charge generation layer 12 and forms.

Charge transport layer can be for example arene such as benzene,toluene,xylene and monochloro-benzene with the solvent that uses in the coating fluid; Halogenated hydrocarbon such as methylene chloride and ethylene dichloride; Ethers such as tetrahydrofuran, diox and dimethoxy methyl ether; With aprotic polar solvent such as N, dinethylformamide.These solvents can use separately or two or more mix use.If desired, this solvent can with such as the solvent of alcohol, acetonitrile or MEK in use.In these solvents, consider, preferably use the non-bittern type organic solvent from the angle of global environmental protection.

Charge transport layer can be that for example spraying process, scraping article rubbing method, rolling method, scraper plate method, ring are coated with method and dip coated method with the coating process of coating fluid.Especially, in these rubbing methods, the dip coated method is good in every respect as mentioned above, is therefore forming charge transport layer 13 and the most frequent use in 14 o'clock.

Charge transport layer 13 and 14 thickness separately is preferably in 1 μ m or bigger and 20 μ m or littler scope, more preferably in 5 μ m or bigger and 15 μ m or littler scope. Charge transport layer 13 and 14 gross thickness are preferably in 5 μ m or bigger and 40 μ m or littler scope, more preferably in 10 μ m or bigger and 30 μ m or littler scope.If the gross thickness of finding charge transport layer 13 and 14 is less than 5 μ m, the electric charge hold facility descends, if the gross thickness of charge transport layer 13 and 14 surpasses 50 μ m, the resolution of photoconductor 1 descends.

Therefore, charge transport layer 13 and 14 gross thickness are set in 5 μ m or bigger and 40 μ m or the littler scope.

Then, elasticity power η will be described _HUWhen solid material being applied load, the machine work load W that in the process of pushing, consumes _TotalPart is used for plastic yield working load Wplast, remaining when removing load as recovery of elasticity working load (elastic deformation working load) W _ElastDischarge.

Recovery of elasticity working load (elastic deformation working load) W _ElastComprise instantaneous elasticity distortion composition and delayed elasticity distortion composition.

Elasticity power η _HUThe viscoelasticity of expression material, particularly relevant parameter with recovery of elasticity.Elasticity power η in this embodiment _HUFollowing calculating.

Hysteresis line 8 expression as shown in Figure 3 loads maximum that beginning to load arrives regulation and pushes the process of pushing of load Fmax and (A → B), load (the load dispose procedure of B → C) and the release concluding time when discharging load beginning to load and reach zero (the 0) (hysteresis of the distortion (pushing change in depth) of C → D) of maintenance process pushing load that peak load Fmax keeps stipulated time t from push load to the surface of photoconductor 1.

Because the load of the machine work in the hysteresis line 8 W _TotalRepresent with W=∫ Fdh, so it is defined as and pushes depth curve (A → B) and push degree of depth h in being increased by load ₁The area that surrounds.Recovery of elasticity working load W _ElastBe defined as and push curve (C → D) and push degree of depth h in discharging by load ₂The area that surrounds.The ratio of working load is elasticity power η _HU, and express by following formula (1):

η _HU＝W _elast/W _total×100(％) (1)

Wherein, W _Total=W _Elast+ W _Plast

On the other hand, the hardness number (H of plastic yield _Plast) also by identical determination of experimental method.That is, in Fig. 3, plasticity hardness number H _PlastCan be by the intercept of pushing the load release profiles of position (C) when discharging load from maximum and the intersection point of X-axis: hr calculates.

Hplast＝Fmax/A(hr)

Wherein, Fmax: maximum is pushed load, A (hr): the impression surface area at depth H r place is pushed in bounce-back.

Elasticity power η _HUCan contact with object by the quadrangular pyramid adamas being pressed son (Vickers presses son) with the hardness number Hplast of plastic yield, and use the equipment such as the Fisher Scope H100V that can estimate hysteresis to measure.

The principal element of the high-durability of photoconductor considers it is to follow the slip of the photoconductor surface when contacting with toner with cleaning balde to minimize effectively.That is, to be applied to the masterpiece on surface when sliding be that elastic body plays a role to photoconductor surface is desirable.But, for the photoconductor surface that mainly constitutes by organic polymer, be difficult to set the such condition on the molecular structure, and forcing to apply under the situation of caoutchouc elasticity (under the situation that instantaneous elasticity fall delay elasticity improves), infer easily and cause other problem, for example, spatter property reduces.

On the other hand, mainly contain thermoplastic polymer improves plastic yield as the raising of the instantaneous elasticity of filming of polycarbonate hardness number.But the excessive raising of hardness causes fragility, and therefore the generation owing to cut causes concentration (density) inhomogeneous, as a result the printability resistance deterioration of photoconductor.

Therefore, the present inventor considers that the above-mentioned material characteristic of organic photoconductive surface carried out research extensively and profoundly, found that elasticity power (η _HU) be 50% or hardness number Hplast higher, plastic yield be 220N/mm ²Or higher and 275N/mm ²Or lower situation is suitable.

Surface coating rerum natura with photoconductor 1 of said structure, that is, the surface coating rerum natura with the photographic layer 14 of membranaceous formation is set at: elasticity power η when pushing load measurement by the maximum that applies 5mN to the surface of layer in the environment of 25 ℃ of environment temperatures, relative humidity 50% _HUBe 50% or higher, and the hardness number of plastic yield (Hplast) is 220N/mm ²Or higher and 275N/mm ²Or it is lower.

Can in each layer of photographic layer 15, add one or more kind sensitizer such as electron-acceptor material and coloured materials in order to improve sensitivity and to suppress owing to use the residual electric potential that causes to rise repeatedly and fatigue etc.

The example of the electron-acceptor material that uses has acid anhydrides such as succinic anhydride, maleic anhydride, phthalate anhydride, 4-chlorobenzene dicarboxylic acid anhydride; Cyano compound such as TCNE and tetracyano-p-quinodimethane (terephthalomalondinitrile); Aldehydes such as 4-nitrobenzaldehyde; Anthraquinone class such as anthraquinone and 1-nitroanthraquinone; Many rings or heterocycle nitro compound be as 2,4,7-trinitro-fluorenes and 2,4,5,7-tetranitro Fluorenone; With electrophilic material such as diphenoquinone compound.In addition, the polymerizable compound of these electrophilic materials also can use.

In addition, as coloring material, can use organic photoconductive compound such as xanthene type coloring material, thiazine type coloring material, triphenyl methane type coloring material, quinoline type pigment and copper phthalocyanine.These organic photoconductive compounds work as optical sensitizer.

Each layer 12,13 and 14 of photographic layer 15 can contain antioxidant, UV absorbing agent etc.Particularly, preferably in charge transport layer 13 and 14, add antioxidant, UV absorbing agent etc.Add these adjuvants inhibition because the deterioration that oxidizing gas such as ozone and oxides of nitrogen cause.The stability of coating fluid when in addition, it can improve by each layer of coating formation.

Example as antioxidant can be phenol type compound, hydroquinone type compound, tocopherol type compound and amine type compound.Wherein, preferred especially phenol type compound and amine type compound, more preferably hindered phenol derivant and hindered amine derivant and composition thereof in addition.

The use amount of these antioxidant is preferably 0.1 weight portion or more and be 50 weight portions or lower with respect to per 100 weight portion charge transport materials.When finding that if use amount with respect to per 100 weight portion charge transport material antioxidant is lower than 0.1 weight portion, can not improve the stability of coating fluid and the effective effect of photoconductor permanance raising performance, if surpass 50 weight portions, the photoconductor characteristic caused harmful effect.Therefore, to be set at respect to per 100 weight portion charge transport materials be 0.1 weight portion or more and be 50 weight portions or lower scope to the preferable range of the use amount of antioxidant.

Fig. 2 is the part sectional drawing of the simplified structure of the photoelectric conductor for electronic photography 2 of demonstration second embodiment of the present invention.About the photoelectric conductor for electronic photography 2 of this embodiment, identical symbol gives the photoelectric conductor for electronic photography 1 similar corresponding part with first embodiment, and omits its explanation.

The noticeable point of photoelectric conductor for electronic photography 2 is to form middle layer 16 between conductive substrates 11 and photographic layer 15.

Between conductive substrates 11 and photographic layer 15, do not form under the situation in middle layer 16, electric charge injects photographic layer 15 from conductive substrates 11, sometimes cause the charging property of photographic layer 15 to descend, should descend by the surface charge of the part beyond the part of exposure elimination, and in image, produce defective such as photographic fog.Especially, when forming image by reversal development, owing to form image by adhering toner on the part of exposed electric charge minimizing, if descend owing to the reason beyond the exposure makes surface charge, then toner with superfine stain (black points) attached on the white background, producing the image photographic fog is so-called blackspot (black flickers), and picture quality deterioration widely sometimes.

Promptly, when between conductive substrates 11 and photographic layer 15, not forming middle layer 16, because the defective of conductive substrates 11 or photographic layer 15 causes the charging property of tiny area to descend, and may cause image photographic fog such as blackspot (black flickers), causes significant image deflects.

In the photoelectric conductor for electronic photography 2 of present embodiment,, can prevent that electric charge from injecting photographic layer 15 from conductive layer 11 owing between conductive substrates 11 and photographic layer 15, form middle layer 16 as mentioned above.Therefore, can prevent that the charging property of photographic layer 15 from descending, can suppress the decline of the surface charge of the part part in addition that passing through exposes eliminates, and therefore can prevent the generation of defective such as image photographic fog.

In addition, form the defective that middle layer 16 can cover conductive substrates 11 surfaces, make the surface evenly, therefore, the formability of photographic layer 15 can improve.Also prevent separating of photographic layer 15 and conductive substrates 11, and can improve the adhesiveness of conductive substrates and photographic layer 15.

Can use the resin bed that contains various resin materials or alumite (alumite) layer etc. as middle layer 16.

The example that forms the resin material of resin bed can be resin such as polyvinyl resin, acrylic resin, polystyrene resin, acrylic resin, vestolit, vinyl acetate resin, urethane resin, epoxy resin, vibrin, melamine resin, silicone resin, polyvinyl butyral resin, polyamide and the copolymer resin that contains two or more repetitives that constitute these resins.In addition, also can comprise casein, gelatin, polyvinyl alcohol (PVA) and ethyl cellulose.

The preferred polyamide that uses especially, preferably uses the alcohol soluble nylon resin in these resins.The preferred example of alcohol soluble nylon resin is by nylon such as 6-nylon, 6,6-nylon, 6, the so-called multipolymer nylon that 10-nylon, 11-nylon, 2-nylon and the copolymerization of 12-nylon obtain and resin such as the nylon of N-alkoxy methyl modification and the nylon of N-alkoxyethyl modification by the nylon chemical modification is obtained.

Particle such as metal oxide particle can be contained in middle layer 16.In middle layer 16, add the feasible volume resistance that can regulate middle layer 16 of these particles, and prevent that effectively electric charge from injecting photographic layers 15 from conductive substrates 11, simultaneously, keeps the electrical characteristics of photoconductor under various environment.

The example that uses as metal oxide particle can be the particle of titanium dioxide, aluminium oxide, aluminium hydroxide and tin oxide.

Middle layer 16 can be passed through, for example, and with above-mentioned resin dissolves or be scattered in the appropriate solvent preparation middle layer with coating fluid and the coating fluid of gained is applied on the surface of conductive substrates 11 and forms.When in middle layer 16, adding particle such as metal oxide particle, middle layer 16 can form as follows: particle is scattered in by with above-mentioned resin dissolves or be scattered in the resin solution that obtains in the appropriate solvent preparation middle layer coating fluid, and coating fluid is applied to the surface of conductive substrates 11.

The middle layer with the solvent that uses in the coating fluid can be, for example, and single solvent such as water, methyl alcohol, ethanol or butanols; The potpourri of potpourri, chlorine kind solvent such as ethylene dichloride, chloroform or trichloroethanes and the alcohols of the potpourri of water and alcohol, two or more pure potpourris or alcohol and acetone or dioxolanes.In these solvents, consider, preferably use the non-bittern type organic solvent from the angle of global environmental protection.

When interbed is used coating fluid in the mill, above-mentioned particle is scattered in the common method that method in the resin solution can be to use bowl mill, sand mill, refiner, vibrating mill, ultrasonic diverting device, paint jolting machine etc.

In the coating fluid in middle layer, the general assembly (TW) C of resin and metal oxide and middle layer with the ratio C/D of the weight D of the solvent that uses in the coating fluid preferably in (1/99) to the scope of (40/60), more preferably in (2/98) to the scope of (30/70).The ratio E/F of the weight E of resin and the weight F of metal oxide preferably in (90/10) to the scope of (1/99), more preferably in (70/30) to the scope of (5/95).

The middle layer can comprise that with the coating process of coating fluid spraying process, scraping article rubbing method, rolling method, scraper plate rubbing method, ring are coated with method and dip coated method.Especially, in these rubbing methods, the preferred dipping stain cloth method of using forms middle layer 16, because this method is fairly simple and throughput rate and cost are good.

The thickness in middle layer 16 is preferably in 0.01 μ m or bigger and 20 μ m or littler scope, more preferably in 0.05 μ m or bigger and 10 μ m or littler scope.

If the thickness of finding middle layer 16 is less than 0.01 μ m, in fact middle layer 16 can not work well, and the uniform outer surface character that covers conductive substrates 11 can not be provided fully and prevent that electric charge from injecting photographic layer 15 from conductive substrates 11, thereby reduce the charging property of photographic layer 15.In addition, surpass 20 μ m if also find the thickness in middle layer 16, when forming middle layer 16 by the dip coated method, become and be difficult to form middle layer 16, and can not on middle layer 16, form photographic layer 15 equably, thereby cause the sensitivity of photoconductor to descend, therefore not preferred.Therefore, the thickness in middle layer 16 is preferably in 0.01 μ m or bigger and 20 μ m or littler scope.

It is charge generation layer 12, charge transport layer 13 and 14 and middle 16 the drying steps of leading that the manufacture method of photoconductor of the present invention preferably includes each layer.Be lower than about 50 ℃ if find the baking temperature of photoconductor, prolong drying time, and if baking temperature surpass 140 ℃, the electrical characteristics when using repeatedly may worsen, and the image that uses this photoconductor to obtain may deterioration.

Therefore, the baking temperature of photoconductor is preferably in about 50 ℃ to 140 ℃ scope, more preferably in about 80 ℃ to 130 ℃ scope.

Fig. 4 shows that the simplified image of the 4th embodiment of the present invention forms the side view of the structure of device 30.Image processing system 30 shown in Figure 4 is the laser printer with photoconductor 1 of first embodiment of the present invention.Below, with reference to Fig. 4, illustrate that the structure of laser printer 30 and image form operation.Laser printer as shown in Figure 4 is for being used to illustrate example of the present invention, and still, image processing system of the present invention is not limited to the following description.

As the laser printer 30 of image processing system, comprise photoconductor 1, semiconductor laser 31, polygonal rotating mirror 32, lens 34, mirror 35, as the corona charging device 36 of Charging system, as developing apparatus developer 37, transfer printing carton 38, paper-feed roll 39, registration roller (resist roller) 40, as transfer device transfer belt electric installation 41, separating charged device 42, conveying belt 43, fixing device 44, row's paper disc 45 and as the clearer 46 of cleaning device.Semiconductor laser 31, polygonal rotating mirror 32, lens 34 and mirror 35 constitute exposure device 49.

Photoconductor 1 is can be arranged on the laser printer 30 along the mode of the rotation of the direction shown in the arrow 47 by not shown drive unit.By polygonal rotating mirror 32 and repeatedly scan surface from semiconductor laser 31 emitted laser bundles 33 at photoconductor 1 at vertically (main scanning direction).Lens 34 have f-θ characteristic, by mirror 35 reflection lasering beams 33, form image and expose on the surface of photoconductor 1.Rotation photoconductor 1 formed image when laser beam 33 as above scanned, and therefore formed the electrostatic latent image corresponding with image information on the surface of photoconductor 1.

Above-mentioned corona charging device 36, developer 37, transfer belt electric installation 41, separating charged device 42 and clearer 46 are arranged from the upstream along the sense of rotation of the photoconductor 1 shown in the arrow 47 downstream with this order.

Corona charging device 36 is arranged on the upstream of the imaging point of laser beam 33 on the sense of rotation of photoconductor 1, the surface of photoconductor 1 is charged equably.Therefore, laser beam 33 is the face exposure of the photoconductor 1 of uniform charged, and created a difference mutually by the quantity of electric charge of the part of laser beam 33 exposures and the quantity of electric charge of unexposed portion, thereby forms above-mentioned electrostatic latent image.

Developer 37 is arranged on the downstream of the imaging point of laser beam 33 on the sense of rotation of photoconductor 1, supply with toner to the electrostatic latent image that forms on the surface of photoconductor 1, and electrostatic latent image is developed as toner image.The transfer paper 48 that holds in the transfer printing carton 38 is taken out by paper-feed roll 39 one by one, and synchronously delivers to transfer belt electric installation 41 by the registration roller 40 and the exposure of photoconductor 1.By transfer belt electric installation 41 the toner image is transferred on the transfer paper 48.Being arranged near transfer belt electric installation 41 separating charged devices 42 has transfer printing the static of the transfer paper of toner image to eliminate, and paper is separated with photoconductor 1.

The transfer paper 48 that separates with photoconductor 1 is delivered to fixing device 44 by conveying belt 43, by fixing device 44 with toner image.The transfer paper 48 that has formed image is in the above described manner discharged to row's paper disc 45.After transfer paper 48 being separated,, photoconductor 1 cleaning of rotation continuously will be kept by remove foreign matter such as remaining toner and paper powder from the surface by clearer 46 by separating charged device 42.Be cleaned from the surface after the photoconductor 1 of device 46 cleanings removes static by the not shown lamp that destatics that is provided with clearer 46, photoconductor 1 further keeps rotation, and repeats to form step from a series of images of the charged beginning of photoconductor 1.

Be set to the surface free energy that has in above-mentioned preferable range owing to be arranged on the surface of the photoconductor 1 in the laser printer 30, therefore forming in the image by laser printer 30, the toner that forms toner image is transferred to transfer paper 48 from the surface of photoconductor 1 easily, remain on the photoconductor 1 as remaining toner hardly, paper powder of the transfer paper 48 that contacts during transfer printing etc. also is attached to the surface of photoconductor 1 hardly in addition.

In addition, even foreign matter such as toner and paper powder are attached to the surface of photoconductor 1, it is also removed by the cleaning balde (cleaning blade) that is provided for the clearer 46 on clear light electric conductor 1 surface after the toner transfer printing easily.

Therefore, in image processing system of the present invention, the grainding capacity of cleaning balde can be set lowlyer, and the contact force on cleaning balde and photoconductor 1 surface can set lowly, thereby can prolong the serviceable life of photoconductor 1.In addition, owing to make and therefore make the surface of photoconductor 1 non-cohesive foreign matter such as toner and paper powder and always keep clean after cleaning to form image steadily in the long term with excellent picture quality.

That is, can form image under various conditions steadily in the long term, simultaneously deterioration picture quality not as the laser printer 30 of within the scope of the present invention image processing system.The life-span of photoconductor 1 is long, and makes clearer 46 can have simple structure, and therefore can low-costly make does not need the often image processing system 30 of maintenance.In addition, even because also deterioration not of photoconductor 1 exposure electrical characteristics, therefore can suppress because the deterioration in image quality that the exposure of the photoconductor 1 when safeguarding causes.

Above image processing system laser printer 30 as the embodiment of the present invention explanation is not limited to structure shown in Figure 4, uses those devices of photoconductor of the present invention also can have other following alternative construction.

That is, when photoconductor has 40nm or littler external diameter, separating charged device 42 can be installed.In addition, photoconductor 1 can with corona discharge assembly 36, developing apparatus 37 and clearer 46 at least one incorporate while form with the form of artistic box (process cartridge).

Artistic box for example can be, has assembled the box of photoconductor 1, corona discharge assembly 36, developing apparatus 37 and clearer 46; Assembled the box of photoconductor 1, corona discharge assembly 36 and developing apparatus 37; Assembled the box of photoconductor 1 and clearer 46; With the box of having assembled photoconductor 1 and developing apparatus 37.

Use makes that with the incorporate in the above described manner artistic box of some parts the control of safeguarding and installing is easy.

Charging system is not limited to corona discharge assembly 36, can use corotron Charging system, scorotron Charging system, sawtooth (sawtooth) Charging system, roll-type Charging system etc.

Developer 37 can be contact or contactless developer.

Clearer 46 can be brush clearer (brush cleaner).

In addition, the time that applies noble potential such as development bias voltage can be regulated with omission and destatic lamp.That is, under the little situation of the diameter of photoconductor or under the situation of low speed low side printing machine, consider, can not install and destatic lamp from the angle of saving installing space.

Embodiment

Below, embodiment illustrates in greater detail the present invention by reference, still, in any case the present invention is not limited to illustrative embodiment.

At first, each photoconductor of embodiment and comparative example is by forming photographic layer manufacturing under various conditions on the aluminum conductive substrates of diameter 30mm, length 340mm, and each photoconductor of making is described.

Embodiment 1

At first, by with 3 weight portion TTO-MI-1 (TM, Ishihara Sangyo Kaisha, Ltd. 3 weight portion CM-8000 (the TM titanium oxide microparticle of Zhi Zaoing),, the alcohol soluble nylon resin, Toray Industries, Inc. system), 60 weight portion methyl alcohol and 40 weight portions 1, the 3-dioxolanes is painted the jolting machine and is disperseed to prepare in 10 hours bottom coating fluid 3kg.This coating fluid is coated on the aluminum tubular support of diameter 30mm, length 340mm by the dip coated method, makes that the thickness of undercoat is 0.9 μ m.

Then, by with 10 weight portion butyral resin (TM:S-lec BM-2, SekisuiChemical Co., Ltd. the system), 1400 weight portions 1, the titanyl phthalocyanine of 3-dioxolanes and the following general formula of 15 weight portions (A) expression disperses to prepare in 72 hours charge generation layer coating fluid 3kg with bowl mill

Wherein, X ¹, X ², X ³And X ⁴The same separately definition; R, s, y and z represent 0 independently of one another.

Use this coating fluid having the charge generation layer that forms thickness 0.2 μ m on the aluminum tubular support of above-mentioned undercoat by the dip coated method.

Then, by 5 weight portions have been made charge transport layer coating fluid (M/B=60/40) as the Irganox 1010 (Ciba Specialty Chemicals Co., Ltd. system) and 32 weight portions of antioxidant as the tetrahydrofuran mixing of solvent as polycarbonate resin TS 2040 (Teijin Ltd. system), 0.125 weight portion of adhesive resin (B) as the enamine type compound by above-mentioned general formula (2) expression, 3.4 weight portions of charge transport material (M).Use this coating fluid,, further form charge transport layer on the charge generation layer that formerly forms, make that the coating thickness after the thermal treatment is 15 μ m by the dip coated method.In addition, by with the enamine type compound by above-mentioned general formula (2) expression of 5 weight portions as the charge transport material, 45 weight portions are as polycarbonate resin GH 503 (the Idemitsu Kosan Co. of adhesive resin, Ltd. make), 0.125 weight portion is as Irganox 1010 (the Ciba Specialty Chemicals Co. of antioxidant, Ltd. system) and 200 weight portions as the tetrahydrofuran of solvent mixing made 3kg charge transport layer coating fluid, and form charge transport layer (M/B=10/90) on the charge transport layer that uses this coating fluid formerly to form by the dip coated method.At this moment, carry out thermal treatment in 1 hour, the gross thickness of charge transport layer is adjusted to 25 μ m, made the photoconductor of embodiment 1 thus 130 ℃ of temperature.

Embodiment 2

Remove when forming charge transport layer, the weight ratio of charge transport material (M) and adhesive resin (B) is become beyond the M/B=20/80, made photoelectric conductor for electronic photography in mode similarly to Example 1 as the outmost surface layer.

Embodiment 3

Remove when forming charge transport layer, the weight ratio of charge transport material (M) and adhesive resin (B) is become beyond the M/B=27/73, made photoelectric conductor for electronic photography in mode similarly to Example 1 as the outmost surface layer.

Embodiment 4

Except when forming two charge transport layers, the butadiene-type compound that uses following formula (3) expression has been made photoelectric conductor for electronic photography as beyond the charge transport material in mode similarly to Example 1.

Embodiment 5

Except when forming two charge transport layers, the styrene fundamental mode compound that uses following formula (4) expression has been made photoelectric conductor for electronic photography as beyond the charge transport material in mode similarly to Example 1.

Comparative example 1

Except making charge transport layer is to have the simple layer of the composition identical with the composition of the outmost surface layer of embodiment 3, has made photoelectric conductor for electronic photography in mode similarly to Example 1.

Comparative example 2

Except the adhesive resin in the outmost surface layer being changed to 25 weight part polycarbonate resin GH 503 (Idemitsu Kosan Co., Ltd. make) and 20 weight portion M300 (IdemitsuKosan Co., Ltd. make) outside, photoelectric conductor for electronic photography made in mode similarly to Example 1.

Comparative example 3

Charge transport material (M) is changed to the M/B=35/65 with the weight ratio of adhesive resin (B) in the outmost surface layer is formed, and has made photoelectric conductor for electronic photography in mode similarly to Example 1.

Comparative example 4

Charge transport material (M) is changed to the M/B=6/94 with the weight ratio of adhesive resin (B) in the outmost surface layer is formed, and has made photoelectric conductor for electronic photography in mode similarly to Example 1.

Each photoelectric conductor for electronic photography about embodiment 1～5 and comparative example 1～4 manufacturing changes charge transport material and the charge transport layer kind with adhesive resin, thereby the hardness number Hplast of elasticity power η HU and plastic yield is adjusted to the value of hope.

Under the surrounding environment of 25 ℃ of temperature and 50% relative humidity, use Fisher ScopeH100V (Fisher Instruments manufacturing) to measure these values.Condition determination is: maximum pushes load 5mN, to maximum to push required 5 seconds time, the duration of load t of load is 5 seconds, be 5 seconds the release time of loading.

Each photoconductor of embodiment 1～5 and comparative example 1～4 to be arranged in order being used to test improved digital copier AR-450 (Sharp Corporation's system), carry out image and form, estimate sensitivity, printing durability and image unevenness.The following explanation of the evaluation method of each performance.

[initial stage electrical characteristics]

Take off developer from test with duplicating machine, replace in development position installation surface pot (344 types: Trek Japan system).Use this duplicating machine, in the environment of the normal temperature of 25 ℃ of temperature, relative humidity 50%/normal wet (N/N:Normal temperature/normal humidity), the surface potential that does not carry out photoconductor under the situation of laser beam lithography is adjusted to-650V, and measured under this state, carried out photoconductor under the laser beam lithography situation surface potential as exposure voltage VL (V).The absolute value of exposure current potential VL is more little, sensitivity is evaluated as high more.

[printing durability]

Is that so-called cleaning balde pressure is adjusted to 21gf/cm (2.06 * 10 with the cleaning balde that is installed in the cleaning unit among the machine AR-450 of transformation to the pressure of photoconductor ^-1N/cm) as the initial stage line pressure.In the N/N environment,, on 100,000 recording charts, form the literal Test Drawing and carry out the printing durability test for each photoreceptor.

Before the test of beginning printing durability and after forming image on 100,000 recording charts, use instantaneous multichannel photometric system MCPD-1100 (Otsuka Electronics Co., Ltd. system) measure the thickness of photographic layer by optical interferometry, and by the abrasion value of 100,000 photographic layers of photographic layer thickness difference calculating photoconductor drum (drum) revolution before the test of beginning printing durability and after forming image on 100,000 recording charts.Abrasion value is many more, and printing durability is evaluated as poor more.

[image color unevenness]

In order to investigate the decrease in image quality level of each photoconductor of printing durability test back, estimated the unevenness of concentration in the half tone image.The evaluation criterion of the even property of density unevenness is as described below.

Sparing property of＜density unevenness 〉

Zero: it is even not observe density unevenness by visual inspection in half tone image: preferable image

*: it is even to observe density unevenness by visual inspection in half tone image: the unevenness that the problem level is arranged on actual the use

[evaluation result]

The evaluation result of each evaluation test that above-mentioned each photoelectric conductor for electronic photography of making for embodiment 1～5 and comparative example 1～4 carries out is as shown in table 1.

In printing durability as shown in table 1 was estimated, the elasticity power of the charge transport layer of superficial layer was that the hardness number Hplast of 50 (%) or higher and plastic yield is 220N/mm in the scope of the invention ²Or higher and 275N/mm ²Or the photoconductor of the embodiment 1～5 in the lower scope, the abrasion value that shows per 100,000 rotations all is evaluated as good in the scope of 0.60 to 0.95 μ m.

Especially, shown in embodiment 1 and 2, the M/B of outmost surface layer weight ratio optimum range promptly 7/93 or higher and 20/80 or lower scope in the time, the result is good especially.

On the other hand, at elasticity power (η _HUBut) be under the situation of photoconductor of the high comparative example 1 of the hardness number Hplast of preferable range plastic yield and 2, may be the cut owing to photoconductor surface has caused image color inhomogeneous.In addition, discovery is under the situation of the photoconductor of comparative example 1, the sensitivity extreme difference, and required sensitivity and printing durability only utilize the sensitivity compensation in the second surface layer that forms by a plurality of charge transport layers that form within the scope of the present invention just to be achieved.

On the other hand, find that the abrasion value of per 100,000 rotations surpasses 1 μ m, shows that printing durability has problem for the comparative example 3 and 4 photoconductor of physics value outside the scope of the invention.

In the comparison of embodiment 1 and embodiment 5, can confirm to use the photoconductor of enamine type compound to have better sensitivity.

As mentioned above, under the situation that forms a plurality of charge transport layers, outermost elasticity power is set at 50% or higher, and the hardness number Hplast of plastic yield is set in 220N/mm ²Or higher and 275N/mm ²Or in the lower scope, the M/B weight ratio is suitably controlled, and selects preferred enamine type charge transport material, can obtain the photoelectric conductor for electronic photography of printing durability and high optical Response thus.

According to the present invention,, can there be the image of deterioration in image quality to form under various conditions steadily in the long term if photoelectric conductor for electronic photography of the present invention is installed in the laser printer as image processing system.In addition, because the clearer of installing can be simplified, therefore image processing system of the present invention can low-costly be made by long photoconductor of life-span is set, and does not need frequent maintenance.In addition, though because photoconductor exposes also deterioration not of its electrical characteristics, therefore the image processing system that uses this photoconductor to obtain have for when safeguarding because the patience of the deterioration in image quality that the exposure of photoconductor causes.

Claims (5)

1. photoelectric conductor for electronic photography, it comprise conductive substrates and on this substrate the order lamination charge generation layer at least and charge transport layer, wherein said charge transport layer comprises charge transport material M and adhesive resin B, and described adhesive resin B contains by the compound of general formula (1) expression as major component:

Wherein, R ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇And R ₈Mutually can be identical or different, represent hydrogen atom, halogen atom or replacement or unsubstituted C independently of one another ₁-C ₆Alkyl; R ₉And R ₁₀Mutually can be identical or different, represent hydrogen atom, halogen atom, replacement or unsubstituted C independently of one another ₁-C ₆Alkyl, saturated cyclic C ₄-C ₁₀Alkyl or replacement or unsubstituted aryl; N represents integer, and the number-average molecular weight that the compound of its expression general formula (1) calculates based on polystyrene by gel permeation chromatography is in 20,000 to 100,000 scope;

And has a layer structure of forming by a plurality of described charge transport layers, the outermost layer of wherein said charge transport layer is in the surface coating hardness test, by under 25 ℃ environment temperature and 50% relative humidity the top layer being applied the highest elasticity power η that measures when pushing load 5mN _HuBe 50% or higher, and the hardness number H of plastic yield _PlastAt 220N/mm ²Or it is higher to 275N/mm ²Or in the lower scope.

2. according to the photoelectric conductor for electronic photography of claim 1, the weight ratio M/B of wherein outermost charge transport material M and adhesive resin B is 30/70 or lower.

3. according to the photoelectric conductor for electronic photography of claim 2, wherein wt is 7/93≤M/B≤20/80 than M/B.

4. according to the photoelectric conductor for electronic photography of claim 1 or 2, wherein charge transport layer contains the charge transport material with enamine structure by following formula (2) expression:

5. image processing system, it comprises each the photoelectric conductor for electronic photography according to claim 1-4, be used to the Charging system that makes described photoelectric conductor for electronic photography charged, be used to make charged photoelectric conductor for electronic photography to use light to expose to form the exposure device of electrostatic latent image corresponding to image information, be used for developing apparatus by latent electrostatic image developing being made toner image develop, be used for toner image from the photoelectric conductor for electronic photography surface transfer to transfer materials transfer device and be used for behind the transfer printing toner image cleaning device on cleaning photoelectric conductor for electronic photography surface.

Images