CN1241730A - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents
Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus Download PDFInfo
- Publication number
- CN1241730A CN1241730A CN98111651A CN98111651A CN1241730A CN 1241730 A CN1241730 A CN 1241730A CN 98111651 A CN98111651 A CN 98111651A CN 98111651 A CN98111651 A CN 98111651A CN 1241730 A CN1241730 A CN 1241730A
- Authority
- CN
- China
- Prior art keywords
- photographic layer
- aluminium
- surface portion
- photosensitive element
- electric photosensitive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/10—Bases for charge-receiving or other layers
- G03G5/104—Bases for charge-receiving or other layers comprising inorganic material other than metals, e.g. salts, oxides, carbon
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0525—Coating methods
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/10—Bases for charge-receiving or other layers
- G03G5/102—Bases for charge-receiving or other layers consisting of or comprising metals
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Photoreceptors In Electrophotography (AREA)
Abstract
An electrophotographic photosensitive member is disclosed which has an aluminum substrate and a photosensitive layer. The substrate contains aluminum, oxygen and titanium, or aluminum, oxygen and zirconium, at the surface portion on the side of the photosensitive layer. Also, a process for producing the electrophotographic photosensitive member, and a process cartridge and an electrophotographic apparatus using the photosensitive member are disclosed.
Description
The present invention relates to electric photosensitive element, the method for the electric photosensitive element of preparation and handle box and Electrophotographingapparatus apparatus with above-mentioned photo-sensitive cell.
Electricity photosensitive element is to be used for forming the photographic layer of sub-image thereon and substrate that one deck is arranged this photographic layer constitutes by electrostatic charging and exposure by one deck basically.
Simultaneously, require electric photosensitive element to have photonasty, electrical property and the optical characteristics that adapts to used electrophotographic process.
Also require electric photosensitive element to have good environmental stability, be enough to any environment of high temperature/high humidity, show its performance at low temperature/low humidity.
In the equipment that the light source of use single wavelengths such as digital copier and laser printer exposes, typical defective image is the blackspot of image line, white background area, the hickie in black background district, the background fog of white background area, and the interference edge that is caused by for example multiple factors such as inhomogeneous bed thickness of substrate surface shape and photo-sensitive cell.Therefore when the preparation photo-sensitive cell, must take the precautionary measures in advance, defective image can not occurred.
It may be the surface state of substrate that a kind of most probable causes the factor of defective image.
Basic not processed substrate needn't have the surface state of any the most suitable photo-sensitive cell usually after the molding.So the problem that surface state causes may occur in a lot of occasions.
In order to address the above problem, several different methods has been proposed at present, for example a kind of method is as Japanese Unexamined Patent Publication No 54-12733 and 57-62056 are disclosed, makes aluminium matter substrate surface be subjected to chromaking and handles, and forms the chemical transformation coating of chromaking; A kind of method is as Japanese Unexamined Patent Publication No 58-14841 and 64-29852 are disclosed, forms one deck boehmite coating on aluminium matter substrate surface; Another kind method is as Japanese Unexamined Patent Publication No 57-29051 is disclosed, makes aluminium matter substrate surface be subjected to forced oxidation by pyroprocessing, forms layer oxide film.
As for the chromaking method, can obtain to have the substrate of certain performance.But, because Treatment Solution contains chromium, the intractable waste liquid, and can endanger environment.
Handle as for boehmite, not talkative surface crystal state is suitable for the substrate of electric photosensitive element.This is effective to electric photographic property to a certain extent, but for image, because surface structure and shape are not suitable for, can not obtain satisfied picture quality.Therefore, under existing situation, the material that satisfies all properties is non-existent.
Above-mentioned surface-treated purpose is to be used in that film that substrate surface forms prevents because electric charge injects any inhomogeneous of electric photographic property that photographic layer produced and image from substrate is local.
Prevent local injection of electric charge and cause the method for defective image that as a kind of a kind of feasible method is to make aluminium matter substrate surface be subjected to anodic oxidation, preparation one deck aluminium oxide (as Japanese Unexamined Patent Publication No 2-7070 and 5-34964).
This method is a good method that can achieve the above object.But be formed uniformly this layer, and can not cause that on substrate surface bed thickness is inhomogeneous, just must make thickness enough big, bed thickness is about 5 or 6 μ m or bigger under the normal condition of its formation.Therefore the thickness of this layer should liken to the thickness of the electric charge injection actual requirement in restraining barrier much biggerly, causes the cost rising.
Therefore, an object of the present invention is to provide a kind of electric photosensitive element with good electrical photographic property, it can not cause defective image at low temperature/low humidity under any environment of high temperature/high humidity, also seldom cause potential change, a kind ofly be easy to prepare above-mentioned electric photosensitive element, the low and stable method of cost, and have a handle box and a kind of Electrophotographingapparatus apparatus of above-mentioned photo-sensitive cell.
As a kind of for addressing the above problem the result of the research of carrying out, the inventor finds to handle by carry out special chemical transformation on substrate surface, that is to say and do not use any electric power that adds, by employed aluminium matter substrate in electric photosensitive element with contain chemical reaction between the aqueous acid solution of particulate metal element, form the insoluble coating or the film of the special composition of one deck in substrate, this is a kind of very effective method.In view of the adverse effect of can obtained performance fabulous electric photosensitive element, cost and environment reduces greatly, production equipment is than the advantage such as simpler in anodic oxidation, this is very effective.
That is to say, the invention provides a kind of electric photosensitive element that comprises the substrate of aluminium matter and be arranged in the suprabasil photographic layer of aluminium matter;
The surface portion of photographic layer one side of this substrate contains aluminium, oxygen and titanium, or aluminium, oxygen and zirconium.
The present invention also provides a kind of method for preparing electric photosensitive element, may further comprise the steps:
Making the substrate of aluminium matter be subjected to chemical transformation with the aqueous acid solution that contains titanium salt or zirconates handles; And
Form one deck photographic layer.
The present invention also provides handle box and the Electrophotographingapparatus apparatus with above-mentioned electric photosensitive element.
Fig. 1 illustrates the structure example of the Electrophotographingapparatus apparatus that has the handle box with electric photosensitive element of the present invention.
The curve map of Fig. 2 ratio of components of the element of electric photosensitive element substrate surface part of the present invention for explanation constitutes.
Electric photosensitive element of the present invention has the substrate of layer of aluminum matter and at the suprabasil photographic layer of this aluminium matter, the surface portion of photographic layer one side of this substrate contains aluminium, oxygen and titanium, or aluminium, oxygen and zirconium.
Can handle by make the substrate of aluminium matter be subjected to chemical transformation with the aqueous acid solution that contains titanium salt or zirconates; Form one deck photographic layer then and make above-mentioned electric photosensitive element.
Chemical transformation among the present invention is meant and does not apply any electric power that adds that resembles in anodic oxidation, allows substrate contact with special solution, forms the processing of the coating with special composition in substrate.
Metal in the slaine that the present invention uses is titanium and zirconium.Have among the present invention that any in the titanium and zirconium exists with aluminium and oxygen in the aluminium matter substrate of chemical transformation coating, substrate has very good performance as electric photosensitive element in this substrate.
This titanium salt and zirconates are preferably fluorine compounds.Titanium salt can comprise hydrofluorite titanium, its sodium salt, sylvite or ammonium salt, and titanium sulfate.Zirconates can comprise potassium zirconium fluoride and zirconium sulfate.
Aqueous acid solution preferably contains the slaine of 0.01-2g (metal is heavy)/L concentration.
Aqueous acid solution also preferably contains the fluorine ion of 0-10g/L concentration.In this concentration range, etching reaction can suitably take place at substrate surface, and forms uniform coating easily.
Preferred available ammonia of aqueous acid solution of the present invention or NaOH are adjusted to the pH value and are 1.0-5.5.If its pH value is below 1.0, etching reaction can be very strong, is difficult to obtain good coating.If its pH value is more than 5.5, the speed that coating forms is very slow, so that can only obtain very thin coating, is difficult to reach remarkable result of the present invention.
In the present invention, stably take place, preferably aqueous acid solution is heated to 30-90 ℃ in use for making etching reaction.
As for the method that substrate is contacted with aqueous acid solution, both can use dipping method also can use injection method.Consider production efficiency, the preferred dipping that uses.
The substrate of handling through chemical transformation is used after washing and drying.
The composition of substrate surface part of the present invention utilizes the Auger electron ray spectrometer to measure, and is limited to upper space to 50 (5 * 10
-3μ m) the degree of depth.
In the present invention, the content of titanium or zirconium can be 4-100 atom %.
Total bed thickness of the chemical transformation coating of titaniferous that forms on substrate surface or zirconium is preferably 1 μ m or littler, is more preferably 50 (5 * 10
-3μ m) or bigger.If the bed thickness of coating is greater than 1 μ m, electric charge is difficult to excessive effusion, causes that rest potential raises, or causes ghost image.If bed thickness is less than 50 (5 * 10
-3μ m), inaccessible remarkable result of the present invention.
In the present invention, consider the corrosion resistance and the tack of coated film, aqueous acid solution is preferably gone back phosphoric acid, phosphate, tannin or tannic acid.
Phosphoric acid and phosphate can comprise the sodium salt or the sylvite of phosphoric acid or sodium phosphate, potassium phosphate or ammonium phosphate and pyrophosphoric acid, tripolyphosphate, hexa metaphosphoric acid or hexa metaphosphoric acid.And, can use the organic phosphoric acid compound, as phytic acid, nitro diethanol vinylphosphonic acid, 2-hydroxyethyl metering system-1-acid phosphonic acids, 2-ethylhexyl acid phosphonic acids and ethane-1-hydroxyl-1,1-di 2 ethylhexyl phosphonic acid.
Phosphoric acid in the aqueous acid solution or phosphatic phosphorus acid ion concentration be 0.05-50g/L preferably.In this concentration range, can form especially all even good especially chemical transformation coating, and processing there is good especially stability with solution.
Tannin or tannic acid can comprise quebracho wood tannic acid, depside tannic acid, Chinese tannin acid, Turkey's tannic acid, hamameli tannin acid, chebulinic acid, sumach tannin, Chinese gallotannin and Ellagitannins.
Tannin in the aqueous acid solution or tannic acid concentration is 0.1-10g/L preferably.
In the present invention, the preferred hydrofluoric acid containing of aqueous acid solution, fluoboric acid, silicofluoric acid or above-mentioned any one salt.These compounds have the function of corrosion substrate surface when substrate stands chemical transformation, therefore can form chemical transformation coating very uniformly.
In sum, the preferred phosphorous and fluorine of chemical transformation coating of the present invention.
Substrate just is not particularly limited to aluminium matter, as long as contain aluminium, this aluminium can be fine aluminium or aluminium alloy, as Al-Mn, Al-Mg, Al-Cu, Al-Si, Al-Mg-Si, Al-Cu-Si etc.More particularly, can use 6000 type aluminium such as JIS A6063 and 3000 type aluminium such as JIS A3003.Its shape there is not particular restriction yet.Preferred employing is columnar.
To describe the photographic layer of electric photosensitive element of the present invention below in detail.
The structure of photographic layer of the present invention is divided into charge generating material and charge transport material substantially and is included in the single-layer type of one deck and has one and contain the charge generation layer of charge generating material and the multi-layered type of the charge transport layer that one deck contains charge transport material.
The electric photosensitive element that below description is had the multi-layered type photographic layer.
Photographic layer can be stacked in the substrate or be stacked in suprabasil mode with opposite order in proper order according to this and constitute with charge generation layer and charge transport layer.
By being coated with the coating solution of carrying material to prepare by dissolved charge, be dried then to form charge transport layer, charge transport material is as containing the poly-ring aromatic compounds of biphenylene, anthracene, pyrene or luxuriant and rich with fragrance structure, nitrogenous ring compound, as indoles, carbazole, oxadiazole or dihydropyazolo, hydrazone compound or the compound of styryl in having the resin of filming performance.
Resin with filming performance comprises polyester, polycarbonate-based, polystyrene type, polymethacrylate and polyarylate class.
The bed thickness of charge transport layer is 5-40 μ m preferably, and 10-30 μ m is then better.
Charge generation layer is the dispersion liquid that disperses charge generating material to prepare by coating, be dried then and form, or vacuum deposition by following pigment forms, this charge generating material is AZO pigments such as tonyred or Dyan indigo plant, quinones pigment such as pyrene, benzoquinones or dibenzo [cd, jk] pyrene-5, the 10-diketone, quino phthalocyanine pigments perylene dye, the phthalocyanine color in indigo pigment such as indigo or thioindigo or the resin is as polyvinyl butyral, polystyrene, polyvinyl acetate or polyacrylate.
The bed thickness of charge generation layer is 5 μ m or littler preferably, and 0.1-3 μ m is then better.
The single-layer type photographic layer is to disperse and coating liquid that dissolved charge generation material and charge transport material prepare by being coated in the resin, is dried then to form.
The bed thickness of this photographic layer is 5-40 μ m preferably, and 10-30 μ m is then better.
In the present invention, can between supporting course and photographic layer, be provided with and have as the function on restraining barrier and the glue-line of adhesion function.This glue-line forms by being coated with the solution that solubilising casein, polyvinyl alcohol (PVA), nitrocellulose, ethylene acrylic acid co polymer, pure dissolubility polyamide, polyurethane or gelatin prepare, being dried then.
The bed thickness of this glue-line is 0.1-3 μ m preferably.
In the present invention, protective seam can be arranged on the photographic layer.
This protective seam can be made of the material that comprises polyester, polyacrylate, tygon, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, polyamide-imides, polysulfones, polyacrylic acid ether, polyacetal, phenol, acrylic acid, siloxane, epoxy, urea, allyl, alkyd, butyraldehyde, phenoxy group, phosphorus piperazine (phosphazene), acryloyl group modified epoxy, acryloyl group modified polyurethane, acryloyl group modified polyester resin lipid.
The bed thickness of this protective seam is 0.2-10 μ m preferably.
In order to improve spatter property and wearing quality, can in above-mentioned each layer, add lubricant, as teflon, Kynoar, fluorine class graft polymer, type siloxane graft polymer, fluorine kind block polymer, type siloxane block polymer or silicone oil.
In order to improve weather resisteant, can also add adjuvant, as antioxidant.
For controlling resistance, can be in protective seam the dispersed electro-conductive powder, as the tin oxide of conduction or the titania of conduction.
Fig. 1 illustrates the structure of a kind of Electrophotographingapparatus apparatus that has the handle box with electric photosensitive element of the present invention.
The electrostatic latent image of Xing Chenging then passes through the operation of developing apparatus 5 by toner development like this.The operation of the toner development image that develop to form by transfer device 6 be transferred to from the paper-supply section (not shown) and photo-sensitive cell 1 and and the transfer device 6 that rotates synchronously of photo-sensitive cell 1 between the surface of offset medium 7.
The offset medium 7 that has received image separates from photosensitive member surface, and by image forming apparatus 8, image obtains photographic fixing, prints out from this device then and duplicates good material (portion).
After photo-sensitive cell 1 lip-deep image is transferred away, utilizes cleaning device 9 to remove after the transfer printing photo-sensitive cell 1 surface and go up remaining toner.Therefore, the surface of photo-sensitive cell is cleaned, and further removes electric charge by the pre-exposure light 10 that the pre-exposure equipment (not shown) sends, and photo-sensitive cell is recycled and reused for imaging then.When elementary charging device 3 is a kind of contact charging device that uses charging roller, just no longer need pre-exposure.
In the present invention, this equipment can constitute a handle box by a plurality of parts merging, as several may be incorporated in together in above-mentioned electric photosensitive element 1, elementary charging device 3, developing apparatus 5 and the cleaning device 9, so that dismounting easily on the main body of electric photographic equipments such as duplicating machine or laser printer.For example, self-contained in box to one of the elementary charging device 3 of major general, developing apparatus 5 and cleaning device 9 with photo-sensitive cell 1, can be to form one by the handle box 11 of guide piece on the equipment body such as guide rail 12 slave unit main body dismounting easily.
Be used at Electrophotographingapparatus apparatus under the occasion of duplicating machine or printer, exposure light 4 is the light by reflection of original copy or transmission, or relies on sensor to read original copy and be the original copy information translation that the signal that signal obtains comes the light of scanning laser beam, driven for emitting lights diode array or the radiation of driving liquid crystal shutter array institute.
Electric photosensitive element of the present invention not only can be used for electrophotographic copier, and can be widely used in the field of answering electricity consumption to take a picture, as laser printer, cathode ray tube printer, light emitting diode printer, liquid crystal printer and laser engraving machine.
To describe the present invention in detail by the embodiment that provides below.
The aluminum barrel of preparation external diameter 29.92mm, internal diameter 28.5mm, long 254mm.
To contain phytic acid as organic phosphoric acid and hydrofluorite titanium and ammonium fluoride titanium aqueous acid solution (trade name: PALCOAT3753 as slaine, can obtain from Nihon Parkerizing company limited, pH:3.8) remain on 40 ℃, above-mentioned aluminum barrel is immersed in the aqueous acid solution, make its chemical transformation 1 minute, with the pure water washing, air-dry then afterwards.The chemical transformation coating bed thickness of Xing Chenging is 200 like this.
Then with sand mill with the titanium dioxide phthalocyanine of 4 weight portions, the polyvinyl butyral resin (trade name: BX-1 of 2 weight portions, can obtain from Sekisui Chemical company limited) and the cyclohexanone of 34 weight portions disperseed 8 hours, the tetrahydrofuran that then adds 60 weight portions is made the charge generation layer coating dispersion liquid.
This dispersion liquid dip-coating is being lived through on the aluminum barrel of chemical transformation,, forming the charge generation layer of bed thickness 0.2 μ m with 95 ℃ of heating and dry aluminum barrel 10 minutes.
Then, the solution dip-coating that the bis-phenol-Z polycarbonate resin by the triarylamine compound of following formula representative and 50 weight portions by dissolving 50 weight portions in the chlorobenzene of 400 weight portions is prepared is on charge generation layer, then, form the charge transport layer of bed thickness 20 μ m with 110 ℃ of heat dryings 1 hour.
Estimate
Partly carrying out the ultimate analysis test, carry out the argon ion etching from the substrate upper space along depth direction simultaneously with scanning auger electron ray spectroscope through chemical transformation, flushing and dry substrate surface.Therefore aluminium, titanium and oxygen are detected main composition elements.Their curve is seen Fig. 2.In this embodiment, about SiO
2The degree of depth and the relation of sputtering time be 110 /min.This value can suitably change.
Substrate upper space and the element ratio of components that is deep to 50 from this upper space are shown in Table 1, and wherein the basic number percent of aluminium element is 100.
From The above results as can be seen, the chemical transformation coating of substrate surface comprises the aluminum oxide coating layer that is mixed with titanium.As the result who analyzes, nitrogen, fluorine, phosphorus etc. are detected as other contained element.When these elements can be considered to carry out chemical transformation in the used aqueous acid solution phosphoric acid and fluoride just contained originally and mixed element in the chemical transformation coating.
The electric photosensitive element that then will prepare is normal temperature/normal wetting (23 ℃, 60%RH), high temperature/high humidity is (32.5 ℃, 85%RH) or (15 ℃ of low temperature/low humidities, environment 10%RH) was placed 48 hours down, put into commercially available laser printer again, under every kind of environment, duplicate the solid white picture with discharged-area development system.
The background fog state of formed solid white picture is with the naked eyes evaluation.This results are shown in Table 2.
Simultaneously, dark space potential value and clear zone potential value under every kind of environment have been measured.This results are shown in Table 2.
Except with contain tannic acid, ammonium salt and zirconium fluoride and zirconium sulfate as the solution of slaine as the aqueous acid solution (trade name: PALCOAT3756 that is used for chemical transformation, can obtain from NihonParkerizing company limited, pH:3.2) outside, prepare electric photosensitive element according to the mode identical with embodiment 1.Do identical evaluation.This results are shown in Table 1 and 2.The bed thickness of this chemical transformation coating is 150 .
Except with contain phytic acid and contain the hydrofluorite zirconium and zirconium ammonium fluoride as the solution of slaine as the aqueous acid solution (trade (brand) name: PALCOAT3753T that is used for chemical transformation, can obtain from NihonParkerizing company limited, pH:3.2) outside, prepare electric photosensitive element according to the mode identical with embodiment 1.Do similar evaluation.This results are shown in Table 1 and 2.The bed thickness of this chemical transformation coating is 180 .
Except with contain phosphoric acid and contain zirconium fluoride and the sodium salt of hydrofluorite zirconium as the solution of slaine as the aqueous acid solution (trade name: ALUSURF 301N-1 that is used for chemical transformation, can obtain from NihonPaint company limited, pH:4.0) outside, prepare electric photosensitive element according to the mode identical with embodiment 1.Do similar assessment.This results are shown in Table 1 and 2.The bed thickness of this chemical transformation coating is 300 .
Reference examples 1
Except not carrying out the chemical transformation, prepare electric photosensitive element according to the mode identical with embodiment 1.Do similar evaluation.This results are shown in Table 2.
Reference examples 2
Preparation concentration is 0.3% ammoniacal liquor, and is heated 95 ℃.
Will be identical with embodiment 1, do not immerse in the ammoniacal liquor after the above-mentioned heating and carry out surface treatment as yet through the aluminum barrel of chemical transformation, then be dried, form the boehmite coating on the aluminum barrel surface.
Except using this aluminum barrel, use the mode identical to prepare electric photosensitive element with embodiment 1.Do similar evaluation.This results are shown in Table 2.
Reference examples 3
Need not aqueous acid solution of the present invention, and do not contain chromium phosphate type solution (trade name: the ALUCHROME 3701 of zirconium with titaniferous neither yet, can obtain from Nihon Parkerizing company limited) be used for chemical transformation, it is remained on 30 ℃, with aluminum barrel immersion wherein carrying out chemical transformation 1 minute, form chromate type chemical transformation coating on the aluminum barrel surface.
Except using this aluminum barrel, use the mode identical to prepare electric photosensitive element with embodiment 1.Do similar evaluation.This results are shown in Table 2.
Table 1
The number percent (atom %) of every kind of atoms of elements number and aluminium atomicity
Measuring position aluminium titanium zirconium oxygen nitrogen fluorine phosphorus carbon embodiment 1
The 50 degree of depth 100 64.2-389.6,634 67 134-embodiment 2
Uppermost surface 100-23.3 422.1-10.5 66.3 541.9
The 50 degree of depth 100-10 185-8.8 9.1-embodiment 3
Uppermost surface 100-29.3 356.6 53.5 6.1-453.5
The 50 degree of depth 100-51.6 320.7 43.1 4.8--embodiment 4
Uppermost surface 100-59 232.7 100 34 100 394.7
The 50 degree of depth 100-95 916.7 20.8 8.3 45.8-measurement mechanisms: the 670xi type scanning auger electron spectroscope that ULVAC-PHI company produces; The electron probe diameter: 0.1 μ m or littler, argon-ion gun is used for etching.
Table 2
Evaluation to mist is measured current potential (V)
Normal high low normal temp/high temperature/low temperature/
Temperature/temperature/temperature/normal temperature high humidity low humidity
Normal height is dark bright dark bright secretly bright
Wet wet trivial trivial embodiment 1 A A A 700 170 700 170 700 175 2 A A A 705 170 700 170 705 180 3 A A A 695 170 695 165 700 175 4 A A A 700 170 700 165 700 180 reference examples 1 C B C 700 170 690 150 700 220 2 C B C 700 170 695 165 700 180 3 B B C 700 170 695 160 705 180 estimate A: fabulous B: good C: bad
Claims (24)
1, a kind of electric photosensitive element comprises the substrate of aluminium matter and is positioned at the suprabasil photographic layer of aluminium matter;
Described substrate contains aluminium, oxygen and titanium at the surface portion of photographic layer one side, or aluminium, oxygen and zirconium.
2, according to the electric photosensitive element of claim 1, wherein titanium or the zirconium content at the surface portion of photographic layer one side is in the scope of 4-100 atom % based on aluminium content.
3, according to the electric photosensitive element of claim 1, wherein the surface portion of photographic layer one side also contains phosphorus.
4, according to the electric photosensitive element of claim 1 or 3, wherein the surface portion of photographic layer one side also contains fluorine.
5, according to the electric photosensitive element of claim 1, wherein the surface portion of photographic layer one side is the coating that forms by chemical transformation.
6, according to the electric photosensitive element of claim 5, wherein said coating bed thickness is 1 μ m or littler.
7, a kind of method for preparing electric photosensitive element comprises the steps:
Make the substrate of aluminium matter carry out chemical transformation with the aqueous acid solution that contains titanium salt or zirconates: and
Form one deck photographic layer.
8, according to the method for claim 7, wherein titanium salt and zirconates are fluorine compounds.
9, according to the method for claim 7, the pH value of wherein said aqueous acid solution is 10-5.5.
10, according to the method for claim 7, the temperature of wherein said aqueous acid solution is 30 ℃-90 ℃.
11, according to the method for claim 7, wherein said aqueous acid solution also contains at least a compound that is selected from phosphoric acid, phosphate, tannin and the tannic acid.
12, according to the method for claim 7, wherein said aqueous acid solution also contains at least a compound that is selected from hydrofluorite, fluoboric acid, silicofluoric acid and their salt.
13, a kind of handle box comprises an electric photosensitive element and at least one device that is selected from charging device, developing apparatus and the cleaning device;
Described electric photosensitive element and described at least one device are merged into a unit, and are removably mounted on the Electrophotographingapparatus apparatus main body; And
Described electric photosensitive element comprises that the substrate of an aluminium matter and one are positioned at the suprabasil photographic layer of this aluminium matter;
Described substrate contains aluminium, oxygen and titanium at the surface portion of photographic layer one side, or aluminium, oxygen and zirconium.
14, according to the handle box of claim 13, wherein the titanium of the surface portion of photographic layer one side or zirconium content based on the content of aluminium in the scope of 4-100 atom %.
15, according to the handle box of claim 13, wherein the surface portion of photographic layer one side also contains phosphorus.
16, according to the handle box of claim 13 or 15, wherein the surface portion of photographic layer one side also contains fluorine.
17, according to the handle box of claim 13, wherein the surface portion in photographic layer one side is the coating that one deck is formed by chemical transformation.
18, according to the handle box of claim 17, wherein said coating bed thickness is 1 μ m or littler.
19, a kind of Electrophotographingapparatus apparatus comprises an electric photosensitive element, a charging device, an exposure device, a developing apparatus and a transfer device;
Described electric photosensitive element comprises that the substrate of an aluminium matter and one are arranged in the suprabasil photographic layer of aluminium matter;
Described substrate contains aluminium, oxygen and titanium or aluminium, oxygen and zirconium at the surface portion of photographic layer one side.
20, according to the Electrophotographingapparatus apparatus of claim 19, wherein the content of the titanium of the surface portion of photographic layer one side or zirconium based on the content of aluminium in the scope of 4-100 atom %.
21, according to the Electrophotographingapparatus apparatus of claim 19, wherein the surface portion of photographic layer one side also contains phosphorus.
22, according to the Electrophotographingapparatus apparatus of claim 19 or 21, wherein the surface portion of photographic layer one side also contains fluorine.
23, according to the Electrophotographingapparatus apparatus of claim 19, wherein the surface portion of photographic layer one side is the coating that one deck is formed by chemical transformation.
24, according to the Electrophotographingapparatus apparatus of claim 23, wherein said coating bed thickness is 1 μ m or littler.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP330386/1997 | 1997-12-01 | ||
| JP33038697 | 1997-12-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1241730A true CN1241730A (en) | 2000-01-19 |
| CN1222833C CN1222833C (en) | 2005-10-12 |
Family
ID=18232029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB981116515A Expired - Fee Related CN1222833C (en) | 1997-12-01 | 1998-12-01 | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0919877B1 (en) |
| KR (1) | KR100312951B1 (en) |
| CN (1) | CN1222833C (en) |
| DE (1) | DE69821728T2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6432603B1 (en) * | 1998-11-27 | 2002-08-13 | Canon Kabushiki Kaisha | Process for producing electrophotographic photosensitive member |
| US6248490B1 (en) | 1998-12-01 | 2001-06-19 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
| KR100864316B1 (en) * | 2007-07-03 | 2008-10-20 | (주)켐스 | Method of chemical treatment for surface of aluminum pipe for organic photo conductor drum |
| CN104357822A (en) * | 2014-10-24 | 2015-02-18 | 无锡伊佩克科技有限公司 | Environment-friendly steel surface treating fluid |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5413979B2 (en) * | 1975-01-23 | 1979-06-04 | ||
| US4518669A (en) * | 1982-11-06 | 1985-05-21 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member |
| JPH0715589B2 (en) * | 1988-09-26 | 1995-02-22 | 富士ゼロックス株式会社 | ELECTROPHOTOGRAPHIC PHOTOSENSITIVE BODY, PROCESS FOR PROCESSING THE SUBSTRATE, AND METHOD FOR MANUFACTURING ELECTROPHOTOGRAPHIC PHOTOSENSITIVE BODY |
| JPH03140965A (en) * | 1989-10-27 | 1991-06-14 | Olympus Optical Co Ltd | Electrophotographic sensitive body |
| DE4412138A1 (en) * | 1994-04-08 | 1995-10-12 | Henkel Kgaa | Chromium-free process for no-rinse treatment of aluminum and its alloys as well as suitable aqueous bath solutions |
-
1998
- 1998-11-27 EP EP98309737A patent/EP0919877B1/en not_active Expired - Lifetime
- 1998-11-27 DE DE69821728T patent/DE69821728T2/en not_active Expired - Lifetime
- 1998-12-01 CN CNB981116515A patent/CN1222833C/en not_active Expired - Fee Related
- 1998-12-01 KR KR1019980052197A patent/KR100312951B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR100312951B1 (en) | 2001-12-12 |
| DE69821728T2 (en) | 2005-01-20 |
| EP0919877B1 (en) | 2004-02-18 |
| EP0919877A1 (en) | 1999-06-02 |
| KR19990062682A (en) | 1999-07-26 |
| CN1222833C (en) | 2005-10-12 |
| DE69821728D1 (en) | 2004-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1102759C (en) | Electrophotographic photosensitive member, electrophotographic apparatus including same and electrophotographic apparatus unit | |
| EP1006414B1 (en) | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus | |
| CN1075831C (en) | Hydroxygallium phthalocyanine compound, production process therefor and electrophotographic photosensitive member using the compound | |
| CN1085353C (en) | Electrophotographic photosensitive member, process cartridge including same and electrophotographic apparatus | |
| CN1129038C (en) | Electrophotographic photosensitive member, process cartridge including same and electrophotographic apparatus | |
| CN1064460C (en) | Image forming apparatus and process cartridge | |
| CN1132360A (en) | Electrophotographic photosensitive member, process cartridge including same and image forming apparatus | |
| CN1605944A (en) | Electrophotographic photoconductor and methods therefor | |
| CN1117149A (en) | Electrophotographic photosensitive member, electrophotographic apparatus including same and electrophotographic apparatus unit | |
| CN1222833C (en) | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus | |
| CN1183424A (en) | Polycarbonate resin and electrophotographic photoconductor using the same | |
| JP2009150958A (en) | Method of manufacturing support for electrophotographic photoreceptor | |
| JP4143238B2 (en) | Method for producing electrophotographic photosensitive member | |
| US6400916B1 (en) | Process cartridge and electrophotographic apparatus | |
| CN1815373A (en) | Bottom coating for photoelectric photoreceptor and its forming method and photoelectric photoreceptor | |
| CN1135439C (en) | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus | |
| JP3360559B2 (en) | Electrophotographic photoreceptor for reversal development | |
| US6953647B2 (en) | Electrophotographic photosensitive member, process for producing electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus | |
| JP2003345042A (en) | Electrophotographic photoreceptor and process cartridge and electrophotographic device having the electrophotographic photoreceptor | |
| CN1159613A (en) | Electric photography photoactive elements, processing-box and electric photography apparatus | |
| CN1186262A (en) | Electrophotographic photoconductor | |
| JP2004037641A (en) | Process cartridge, electrophotographic system, and electrophotographic photoreceptor used in them | |
| KR19980018991A (en) | Photoconductor for Internal Irradiation Electrophotography | |
| JP2004029428A (en) | Electrophotographic photoreceptor, process cartridge, and electrophotographic device | |
| JP2004101630A (en) | Electrophotographic photoreceptor and method for manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20051012 Termination date: 20131201 |