CN1303491A - Methods of making charge generation layers containing charge transport compounds, and photoconductors containing same - Google Patents
Methods of making charge generation layers containing charge transport compounds, and photoconductors containing same Download PDFInfo
- Publication number
- CN1303491A CN1303491A CN 99806629 CN99806629A CN1303491A CN 1303491 A CN1303491 A CN 1303491A CN 99806629 CN99806629 CN 99806629 CN 99806629 A CN99806629 A CN 99806629A CN 1303491 A CN1303491 A CN 1303491A
- Authority
- CN
- China
- Prior art keywords
- compound
- charge
- charge transport
- optical conductor
- generating layers
- 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.)
- Pending
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
- G03G5/02—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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photoreceptors In Electrophotography (AREA)
Abstract
Methods of making a charge generation layer comprise premixing a charge generation compound, a charge transport compound and solvent to form a premix essentially free of polymeric binder, mixing the premix with at least one polymeric binder to form a dispersion, and coating the dispersion on a substrate. Photoconductors comprising a substrate, a charge transport layer and a charge generation layer formed by such a method exhibit improved electrical sensitivity.
Description
Field of the present invention
The present invention relates to prepare the method for the charge generating layers that comprises the charge transport compound and contain the optical conductor of this charge generating layers.
Background technology
In electronic photography, on image forming such as optical conductor material surface,, the surf zone selectivity is exposed to light forms potential image then by at first making surperficial uniform charged.It is poor to form electrostatic charge density between those surf zones that are exposed to light and those surf zones of not being exposed to light.Potential electrostatic image develops by electrostatic toner and is visual picture.Toner is optionally attracted by the exposure on optical conductor surface or unexposed portion, depends on the relative static charge on optical conductor surface, development electrode and the toner.
Usually, double-deck electronic photography optical conductor comprises that one is coated with the base material of charge generating layers (CGL) and charge transport layer (CTL) thereon, as the metal bottom plane.Charge transport layer comprises charge transport material, and this charge transport material comprises hole transporting material or electron transport materials.For the sake of simplicity, following discussion relates to using and comprises the charge transport layer of hole transporting material as the charge transport compound.Those skilled in the art will know, if charge transport layer comprises electron transport materials but not hole transporting material, then be positioned at the lip-deep electric charge of optical conductor with described herein opposite.
Usually, when formation contained the charge transport layer of hole transporting material on charge generating layers, negative charge generally was on the optical conductor surface.On the contrary, when forming charge generating layers on charge transport layer, positive charge generally is on the optical conductor surface.Usually, charge generating layers comprises the polymer adhesive that contains electric charge generation compound or molecule, and charge transport layer comprises the polymer adhesive that contains charge transport compound or molecule.Electric charge generation compound in CGL forms radiosensitive to image, and owing to absorbs this radiation photic generation electron-hole pair in CGL.CTL is generally the non-absorbent that image forms radiation, and the charge transport compound plays the lip-deep effect of cavity conveying to electronegative optical conductor.This optical conductor is disclosed in people's such as Adley US5, in 130,215 and people's such as Balthis US5,545,499.
Usually, by increasing the content of the charge transport compound in the charge transport layer, can obtain image taking speed and low residual voltage faster.Yet, be higher than approximately 40 to 50wt% the time when the amount of charge transport compound in the charge transport layer increases by the weight of charge transport layer, the mechanical property of optical conductor begins sustain damage usually, and causes rate of depreciation to raise and the physical strength reduction.Several pieces of documents disclose the specific charge of using the amount of determining in charge generating layers and have carried compound or charge transport polymkeric substance, and the example of these documents is US4 of people such as Champ, and 490,452, people's such as Kato US4,882,253 and people's such as Umeda US5,677,094.Yet, owing to need to improve photosensitivity and permanance day by day and at the optical conductor of the improvement performance of the optical conductor life period that prolongs, therefore particularly lower-cost optical conductor still needs to develop new material and method to satisfy these requirements.
Summary of the invention
Therefore, an object of the present invention is to provide a kind of optical conductor that shows improved performance and/or request for utilization.More specifically, an object of the present invention is to provide the improved electrical property of a kind of demonstration, comprise the bilayer light conductor of improved photosensitivity.
These and other objects of the present invention and advantage can be by preparing charge generating layers of the present invention method and provide by optical conductor of the present invention.The method for preparing optical conductor of the present invention comprises: electric charge is generated the pre-composition that compound, charge transport compound and solvent premix form essentially no polymer adhesive, the pre-composition that this electric charge is generated compound, charge transport compound and solvent mixes the formation dispersion with at least a polymer adhesive, and this dispersion is applied on the base material.This premix preferably includes the solvent of solubilized charge transport compound.The gained charge generating layers offers the optical conductor that wherein uses this charge generating layers improved electrical property, particularly better photosensitivity.Usually, this optical conductor is bilayer light conductor and comprises base material, charge generating layers and charge transport layer.Charge transport layer comprises bonding agent and first kind of charge transport compound, and charge generating layers comprises that bonding agent, electric charge generate compound and second kind of charge transport compound.Wherein charge generating layers passes through method for preparing, this method comprises: electric charge is generated the pre-composition that compound, charge transport compound and solvent premix form essentially no polymer adhesive, this pre-composition is mixed the formation dispersion with at least a polymer adhesive, and this dispersion is applied on the base material.
Form charge generating layers according to the inventive method, when this charge generating layers is used for optical conductor, provide to have good electrical properties, comprise the optical conductor of good photosensitivity.
These and other purpose and advantage of the present invention will be apparent in the following detailed description.
Brief description of the drawings
Be described in detail in conjunction with the drawings, can more fully understand the present invention.
Fig. 1 provide charge generating layers wherein comprise the charge transport compound and by the electrical property of the optical conductor A of the present invention of the inventive method preparation and wherein charge generating layers do not have the electrical property of the conventional optical conductor B of charge transport compound, as description among the embodiment 1;
Fig. 2 provides that charge generating layers wherein comprises the charge transport compound and by the electrical properties of the electrical property of the optical conductor C of the present invention of the inventive method preparation and three contrast optical conductor D, E and F, as describing among the embodiment 2;
Fig. 3 provides that charge generating layers wherein comprises the charge transport compound and by the electrical property of the optical conductor G of the present invention of the inventive method preparation and the electrical property of contrast optical conductor H and I, as describing among the embodiment 3;
Fig. 4 A and 4B provide the electrical property by the optical conductor J of the inventive method preparation and contrast optical conductor K, as describing among the embodiment 4.
The present invention describes in detail
In first embodiment, the present invention relates to a kind of preparation and comprise that simultaneously electric charge generates the charge generating layers of compound and charge transport compound.This charge generating layers and the bilayer light conductor that contains this charge generating layers are disclosed in people's such as Levin US patented claim 09/066,284, and (in 24 days April in 1998 of the applying date, the disclosed full content of this patented claim is here as with reference to introducing.This favourable part that contains the charge generating layers of electric charge generation compound and charge transport compound is, use the optical conductor of this charge generating layers to show good electrical properties, comprise good photosensitivity and/or good residual voltage, and/or they are compared with the conventional optical conductor that charge generating layers does not wherein contain the charge transport compound and show that significantly dark decay reduces.Generating premix that compound and charge transport compound form essentially no polymer adhesive by the premix electric charge therein prepares and comprises that simultaneously electric charge generates in the embodiment of the present invention of charge generating layers of compound and charge transport compound, can obtain the further improvement to optical conductor electricity photosensitivity.
Usually, charge generating layers generates the dispersion preparation by the electric charge that electric charge generates compound, polymer adhesive and solvent, wherein dispersion is ground, and so grinds electric charge and generate compound in the presence of bonding agent and solvent.According to the inventive method, at first electric charge is generated compound and charge transport compound and solvent premix, the essentially no polymer adhesive of this pre-composition.With electric charge generate compound with charge transport compound premix before or after grind.If with electric charge generate compound with charge transport compound premix before grind, then preferably electric charge is generated premix elementary mixing before adding polymer adhesive of compound and charge transport compound, add the bonding agent prerequisite for even premix to guarantee thoroughly to mix to be incorporated in.
The premix that electric charge generates compound and charge transport compound preferably includes a kind of solvent that wherein can disperse electric charge to generate compound and solubilized charge transport compound.Suitable solvent is that those skilled in the art are conspicuous, depends on use therein specific charge conveying compound especially.Suitable solvent includes but not limited to ketone, ether and its potpourri.
The essentially no polymer adhesive of this premix.Within the scope of the present invention, essentially no polymer adhesive is meant that premix only contains the polymer adhesive that its amount does not stop charge transport compound molecule local concentration around electric charge generates compound molecule in premix.This premix contains the polymer adhesive that preferably is lower than 10wt%, more preferably less than the polymer adhesive of 5wt%, further more preferably less than the polymer adhesive of about 1wt%.In a further preferred embodiment, premix does not contain polymer adhesive.
Although the inventor does not wish to be subjected to any theory constraint, but it is believed that this formation electric charge generates the step of compound and charge transport compound and essentially no polymer adhesive, the optical excitation electric charge that can make the electronics self charge carry compound more effectively to inject the gained optical conductor generates material.It is believed that, the electric charge that relates in implantation step shifts the distance sensitive (short distance is preferred) between electric charge generation molecule and the charge transport molecule, and to the local concentration sensitivity (higher concentration be preferred) of charge transport molecule around electric charge generates molecule.By in the presence of the charge transport molecule in the presence of adhesive-free the premix electric charge generate crystal, it is believed that can improve the charge transport molecule generates on the crystal or concentration on every side and can reduce electric charge and generate distance between molecule and the charge transport molecule at electric charge, and can the charge transport molecule be absorbed directly in the electric charge generation plane of crystal under shifting the electric charge of bonding agent in the charge generating layers of optical conductor not generated plane of crystal.
Premix of the present invention comprises that electric charge generates compound and charge transport compound, and its relative quantity will provide electric charge to generate compound and the required ratio of charge transport compound in final charge generating layers.In one embodiment, premix comprises that about electric charge of 5 to about 90wt% generates the charge transport compound of compound and about 10 to 90wt%, generates the total content of compound and charge transport compound by electric charge.This premix comprises that more preferably about electric charge of 25 to about 75wt% generates the charge transport compound of compound and about 25 to 75wt%, generates the total content of compound and charge transport compound by electric charge.In another embodiment preferred, this premix comprises about 1 to about 50, more preferably from about 5 to about 20wt% electric charge generates compound, about 1 to about 50,5 to about 20wt% charge transport compound more preferably from about, with about 5 to about 98,60 to about 90wt% solvent more preferably from about is by the general assembly (TW) of premix.
After electric charge generated compound and the charge transport compound fully mixes in premix, bonding agent added form electric charge in the premix and generate dispersion.Other solvent can be added in the dispersion, and when beginning, all add or in a period of time, divide adding for several times, wherein an intermediate section prose style free from parallelism be ground, stirred or handles during bonding agent adds bonding agent.Gained generates dispersion with the compound doped electric charge of charge transport and can be used for forming the optical conductor charge generating layers that shows the improvement photosensitivity.
Final dispersion comprises that the electric charge of the charge generating layers composition that its content is adapted at providing required after the solvent evaporation generates compound, charge transport compound and polymer adhesive, and comprises that its content is enough to make dispersion preferably to be applied to solvent on the base material suitably by dip-coating or similar common process.In one embodiment, the final dispersion that is used to be coated with comprises that about 5 to about 60wt% electric charge generates compound, about 5 to about 60wt% charge transport compound and about polymer adhesive of 10 to about 90wt%, by the total content of electric charge generation compound, charge transport compound and polymer adhesive.This dispersion comprises that more preferably about 20 to about 50wt% electric charge generates compound, about 20 to about 50wt% charge transport compound and about polymer adhesive of 20 to about 75wt%, by the total content of electric charge generation compound, charge transport compound and polymer adhesive.In another preferred embodiment, this dispersion comprises that about 0.1 to about 30wt%, more preferably from about 1 to about 10wt% electric charge generates compound, 0.1 to about 30wt%, 1 to about 10wt% charge transport compound more preferably from about, about 0.1 to about 30wt%, more preferably from about 1 to about 10wt% polymer adhesive and about 10 to about 99,75 to about 98wt% solvent more preferably from about is by the general assembly (TW) of dispersion.
Various electric charge known in the art generates compound and is applicable among the preparation method of optical conductor of the present invention and charge generating layers.Organic charge generates compound and is suitable in the optical conductor of the present invention, its example includes but not limited to azo-compound, US4 as people such as Ishikawa, 413, Unit three known in the art and four blocking compounds, phthalocyanine dye are described in 045, the phthalocyanine that comprises no metallic forms such as X-form metal-free phthalocyanine dyestuff and metallic phthalocyanine such as titaniferous is (as US4,664,997,4,725,519 and 4, disclosed in 777,251), its polymorphic material and derivant, with squaric acid derivative dye, for example hydroxyl-squaraine electric charge generates compound.In preferred embodiments, charge generating layers comprises phthalocyanine compound.The phthalocyanine of no metallic forms and containing metal form all is preferred.The particularly preferred electric charge that is used for charge generating layers of the present invention generates compound and comprises metallic phthalocyanine, and particularly wherein metal is the containing metal phthalocyanine of transition metal or III A family metal.Generate in the compound at these containing metal phthalocyanine electric charges, preferably those contain transition metal such as copper, titanium or manganese or contain the phthalocyanine electric charge generation compound of aluminium as III A family metal.Metallic phthalocyanine electric charge generates compound and is further preferably replaced by oxygen base, mercaptan or dihalo-.Especially preferred oxygen generation-titanyl phthalocyanine comprises its various polymorphs such as IV type polycrystalline and its derivant such as halogen substitutive derivative such as chlorine titanyl phthalocyanine.
Electric charge generates compound and is contained in the final charge generating layers with the convention amount that is fit to provide electric charge to generate effect.Charge generating layers comprises suitably that at least about 5wt% preferably the electric charge at least about 10wt% generates compound, by the weight of charge generating layers.In another preferred embodiment, charge generating layers comprises that the electric charge at least about 15wt% generates compound, and preferred about electric charge of 15 to about 50wt% generates compound, by the weight of charge generating layers.
The charge transport compound that comprises in the charge generating layers can be identical or different with the charge transport compound that comprises in the charge transport layer.In optical conductor of the present invention, in charge generating layers, be added with the charge transport compound, improved the electrical property of optical conductor, for example photosensitivity and/or residual voltage, and unlikely because the high load capacity of charge transport layer causes the optical conductor rate of wear to strengthen or physical strength reduces.And being added with the charge transport compound in charge generating layers can provide optical conductor of the present invention to reduce with tangible dark decay.Usually the effect of adulterant in the charge transport compound aliquation in the charge generating layers is in order to reach these improvement.
Electric charges contained conveying compound can comprise the conventional known any charge transport compound in this area in the charge generating layers, includes but not limited to hereinafter described to be used for those of charge transport layer.In a preferred embodiment, the charge transport compound that is contained in the charge generating layers comprises hydrazone compound, aromatic amine (comprising aromatic diamine and triamine) or replaces aromatic amine (comprise and replace aromatic diamine and triamine) or their potpourri.
The charge transport compound is preferably to be enough to the providing amount of doping effect to be included in the charge generating layers.This charge transport compound more preferably to be enough to provide one or more electrical performance characteristics of optical conductor, for example provides better photosensitivity and/or improved residual voltage, and/or the amount of the dark decay loss of charge of reduction optical conductor is included in the charge generating layers.In preferred embodiments, the amount of the charge transport compound that comprises is about 10 to about 50wt%, by the weight of charge generating layers.In another embodiment, the weight ratio that contained electric charge generates compound and charge transport compound in the charge generating layers was not less than about 1: 3, more preferably was not less than about 1: 2.To generate the weight ratio of compound and charge transport compound be about 10: 1 to about 1: 3 suitably for contained electric charge in the charge generating layers.
The polymer adhesive of charge generating layers can be any polymer adhesive that is used for charge generating layers known in the art.The bonding agent of charge generating layers is preferably inactive, do not show that promptly electric charge generates or the charge transport performance, can include but not limited to the multipolymer of polyvinyl such as Polyvinylchloride, polyvinyl butyral, polyvinyl acetate, styrene polymer and these polyvinyls, acrylic acid and acrylate polymer and multipolymer, carbonate polymer and multipolymer (comprising polyestercarbonate), polyester, alkyd resin, polyamide, polyurethane, epoxy resin etc.Charge generating layers preferably includes about 10 to about 90wt%, and 20 to about 75wt% bonding agent more preferably from about is by the weight of charge generating layers.
Charge generating layers prepared according to the methods of the invention is suitable for optical conductor, particularly bilayer light conductor.Bilayer light conductor of the present invention comprises base material, charge transport layer and the charge generating layers that forms by said method.
The base material of optical conductor can be flexible, for example is pliability net or band forms; Or can right and wrong flexible, as be cylinder (drum) form.Usually, the optical conductor base material evenly is coated with skim metal (preferred aluminium), this thin metal layer plays the effect of electric baseplane.In another embodiment preferred, aluminium is carried out anodizing make the aluminium surface become alumina surface.In addition, bottom planar member can comprise sheet metal, as aluminium or nickel, and metallic cylinder or paper tinsel, or the plastic sheeting of vacuum evaporation aluminium, tin oxide or indium oxide etc. on it.
In preferred embodiments, can form charge generating layers on the optical conductor base material, then form the charge transport layer that contains the cavity conveying compound, so negative charge can be in the optical conductor surface.On the contrary, can form the charge transport layer that contains the cavity conveying compound on the optical conductor base material, then form charge generating layers on charge transport layer, so positive charge can be on the optical conductor surface.On the other hand, know as those skilled in the art, if charge transport layer contains the electron transport material, then because the arrangement of charge transport and charge generating layers, be in the lip-deep electric charge of optical conductor can be opposite.
The charge transport layer that is included in the bilayer light conductor of the present invention contains bonding agent and charge transport compound.This charge transport layer is that this area is habitual, therefore can comprise any bonding agent and the charge transport compound that is used for charge transport layer well known in the art.Usually, bonding agent is a polymkeric substance, can comprise any bonding agent that is used for above-mentioned charge generating layers.The polymer adhesive of charge transport layer is preferably inactive, and promptly it does not show the charge transport performance.
The conventional charge transport compound that is applicable to optical conductor charge transport layer of the present invention should be able to support self charge to generate photic generation hole or electronics that layer injects, and these holes or electronics are carried optionally to make the surface charge discharge by charge transport layer.The appropriate charge that is applicable to charge transport layer carries compound to include but not limited to:
1. be described in US4, two amine delivery of molecules in 306,008,4,304,829,4,233,384,4,115,116,4,299,897,4,265,990 and/or 4,081,274
2. pyrazoline delivery of molecules as US4, is described in 315,982,4,278,746 and 3,837,851.
3. substituted fluorene charge transport molecule as US4, is described in 245,021.
4. the oxadiazole delivery of molecules is as 2, two (the 4-lignocaine phenyl)-1,3 of 5-, and 4-oxadiazole, imidazoles, triazole etc. as Deutsche Bundespatent 1,058, are described in 836,1,060,260 and 1,120,875 and US3,895,944.
5. hydrazone delivery of molecules as US4, is described in 150,987 or 4,385,106,4,338,388,4,387,147,4,399,208,4,399,207,4,256,821 and 4,297,426.
The charge transport compound that is included in the charge transport layer preferably includes hydrazone, arylamine (comprising aromatic diamine or triamine), substituted aromatic amines (comprise and replace aromatic diamine and triamine) or its potpourri.Preferred hydrazone delivery of molecules comprises derivant, cinnamate or the hydroxylated benzaldehyde of aminobenzaldehyde.The example of the hydrazone that aminobenzaldehyde is derived comprises people's such as Anderson US4,150,987 and 4,362, those that enumerate in 798, and the hydrazone of hydrazone that cinnamate is derived and hydroxylation of benzene formaldehyde-derived is recited in people's such as Levin common unsettled US application serial no 08/988,600 and 08/988 respectively, in 791, these patents and patented claim are all introduced as reference here.
When the charge transport compound of the charge transport compound of charge transport layer and charge generating layers not simultaneously, the oxidation potential (being commonly referred to redox-potential Eredox) of the charge transport compound of preferred charge transport layer is lower than the oxidation potential of the charge transport compound of charge generating layers, or is not higher than the about 0.2V of oxidation potential of the charge transport compound of charge generating layers.Can make like this hole by the active parts requirement from the charge transport compound of the charge transport compound iunjected charge transfer layer of charge generating layers.When the charge transport compound of the charge transport compound of charge transport layer and charge generating layers not simultaneously, the charge transport compound of charge transport layer more preferably has the oxidation potential that oxidation potential is lower than the charge transport compound of charge generating layers.
Usually, when two or more charge transport compounds mix,, then present tangible trap in charge transport layer if the charge transport compound has visibly different oxidation potential (usually greater than about 0.2V).Therefore, as known in the art, for the potpourri of the charge transport compound that is used for single charge transport layer, the compound of choosing should make its oxidation potential difference be no more than about 0.2V, preferably is no more than about 0.1V.Owing to be expected at optical conductor charge generating layers of the present invention and occur a certain amount of the mixing at the interface, expect that then to need the oxidation potential of the corresponding charge transport compound of charge transport layer of the present invention and charge generating layers substantially similar with charge transport layer.Surprisingly, definite, even when the oxidation potential of the charge transport compound in the charge generating layers during obviously greater than the oxidation potential of the charge transport compound in the charge transport layer, in charge transport layer and charge generating layers, use different charge transport compounds respectively, the optical conductor that can obtain to have good electrical properties.Even when the oxidation potential of the charge transport compound in the charge generating layers than the about 0.1V of oxidation potential of the charge transport compound in the charge transport layer or approximately during 0.2V, also can in charge transport layer and charge generating layers, use different charge transport compounds respectively, obtain optical conductor with good electrical properties.
Charge transport layer generally includes about 5 to about 60wt%, 15 to about 40wt% charge transport compound more preferably from about, and by the general assembly (TW) of charge transport layer, the surplus materials of charge transport layer comprises bonding agent and any conventional additives.
Optical conductor image-forming component described herein can prepare according to routine techniques, and condition is charge generating layers is generated compound and charge transport compound by above-mentioned electric charge premix preparation.The thickness of optical conductor matrix should be suitable for providing desired mechanical stability usually.Charge generating layers has about 0.05 to the 5.0 μ m of thickness usually, and charge transport layer will have thickness about 10 to about 40 μ m.According to the known technology of this area, can between baseplane and charge generating layers, be provided with and have thickness about 0.05 one or more restraining barriers usually to about 20 μ m.By the charge transport compound being disperseed and/or is dissolved in polymer adhesive and the solvent, then with this dispersion and/or solution is applied in the corresponding lower floor and with this coating drying, form charge transport layer.
The various embodiments of optical conductor of the present invention illustrate in the following embodiments.Except as otherwise noted, umber in these embodiment and whole instructions and number percent are all by weight.
In the present embodiment, prepare optical conductor A of the present invention and conventional optical conductor B.In each optical conductor, with the charge generating layers dip-coating on the aluminium base that carries out anodizing and with the charge transport layer dip-coating on charge generating layers.The charge transport layer of each optical conductor comprises the polymer adhesive of about 70wt% and the N that comprises following formula of about 30wt%, N '-two-(3-tolyl)-N, and the charge transport compound of N '-two phenyl benzidines (TPD):
The charge generating layers of optical conductor A of the present invention comprises that the TPD of the bonding agent of oxo-titanyl phthalocyanine (TiOpc) type I pigment of about 40wt%, about 27wt% and about 33wt% is as the charge transport compound.The charge generating layers of conventional optical conductor (optical conductor B) does not have the charge transport compound, and comprises oxo-titanyl phthalocyanine pigment type I pigment and the about 60wt% bonding agent of about 40wt%.
The charge generating layers of the optical conductor A of present embodiment uses premix preparation of the present invention.Particularly, with TiOpc type I pigment 20: the 80 mixed solvent slurryization (12wt% solid) that comprise methyl ethyl ketone (MEK) and cyclohexanone.This slurry was ground about 1 hour, add TPD then, then the gained slurry was stirred 2 hours.After this grinding and stirring, add the binder solution that is included in the about 12wt% polyvinyl butyral (PVB) among the MEK, obtain comprising that 16.8% contains the component and the 83.2% solvent (MEK: millbase cyclohexanone ratio 52: 48) of pigment, TPD and bonding agent (40.4%TiOpc pigment, 32.7%TPD and 26.9%PVB, percentage by weight).And then ground about 2 hours.By millbase is diluted with the extremely dilute solution of PVB bonding agent in MEK, prepare last dispersion.This final dispersion composition is included in 95.6% solvent (MEK: the component that contains pigment, TPD and bonding agent (40%TiOpc pigment, 33%TPD and 27% bonding agent, percentage by weight) of 4.4% cyclohexanone ratio 90: 10).Optical conductor A forms the charge generating layers preparation with this final dispersion.Conventional dispersion by 40%TiOpc pigment in solvent and 60% bonding agent prepares optical conductor B, does not comprise TPD in this dispersion.
Measure the photosensitivity value of the optical conductor of present embodiment with the sensitometer that electrostatic probe is housed, to measure as the voltage swing that shines the lip-deep luminous energy of optical conductor.This sensitometer comprises that design charges to optical conductor in the charging source of pact-700V.Sensitometric curve is by measuring at a certain luminous energy (the μ J/cm of unit
2) the interior exposure of the scope residual voltage generation of optical conductor afterwards.The result of these measurements provides in Fig. 1.Compare with optical conductor B (curve B among Fig. 1), optical conductor A (curve A among Fig. 1) has shown improved photosensitivity curve and residual voltage surprisingly.The improvement photosensitivity curve negotiating of optical conductor A proves in the low-yield district curve A gradient sharper than curve B.
Embodiment 2
In the present embodiment, prepare optical conductor C of the present invention and contrast optical conductor D, E and F.In each optical conductor, with the charge generating layers dip-coating on the aluminium base that carries out anodizing and with the charge transport layer dip-coating on charge generating layers.The charge transport layer of each optical conductor comprises the polymer adhesive of about 70wt% and the charge transport compound that comprises TPD of about 30wt%.
The charge generating layers of optical conductor C of the present invention and contrast optical conductor D comprises that separately the TPD of the bonding agent of the TiOpc Type IV pigment of about 30wt%, about 37wt% and about 33wt% is as the charge transport compound.The charge generating layers of contrast optical conductor E and F does not have the charge transport compound, and comprises TiOpc Type IV pigment and the about 55wt% bonding agent of about 45wt%.
The charge generating layers of the optical conductor C of present embodiment uses the inventive method to be prepared by premix.Particularly, with the solvent slurryization (12wt% solid) of TiOpc Type IV pigment with 20: 80 potpourris that comprise MEK and cyclohexanone.This slurry was ground about 15 minutes, add TPD then, then the gained slurry was stirred 2 hours.After this grinding and stirring, the binder solution that adds the about 12wt%PVB in the potpourri that is included in MEK and cyclohexanone (62: 38 ratios), obtain comprising that 16.8% contains the component and the 83.2% solvent (MEK: millbase cyclohexanone ratio 1: 2) of pigment, TPD and bonding agent (39%TiOpc pigment, 43%TPD and 18%PVB, percentage by weight).And then ground about 2 hours.By millbase is diluted with the extremely dilute solution of PVB bonding agent in MEK, prepare last dispersion.This final dispersion composition is included in MEK: the component that contains pigment, TPD and bonding agent (30%TiOpc pigment, 33%TPD and 37% bonding agent, percentage by weight) of 4.4% in 90: 10 solvents of cyclohexanone ratio.Form charge generating layers with this final dispersion and prepare optical conductor C.
With the charge generating layers of the step preparation contrast optical conductor D identical with the charge generating layers of preparation optical conductor C, different is TPD not to be added in the TiOpc Type IV pigment when forming premix.In addition, TPD is added in the TiOpc Type IV pigment with the PVB bonding agent.With TiOpc Type IV pigment slurryization and carry out grinding steps in solvent, with research in charge transport compound and bonding agent effect of grinding down not.With the charge generating layers of technology (comprise grinding steps) the preparation contrast optical conductor E identical with preparation optical conductor C, different is not comprise TPD in premix or in the charge generating layers dispersion.The conventional dispersion preparation in solvent by TiOpc pigment and bonding agent of contrast optical conductor does not comprise TPD in dispersion.
According to embodiment 1 described technology the optical conductor of present embodiment being carried out photosensitivity measures.The result provides in Fig. 2.Result among Fig. 2 proves, compares with F with contrast optical conductor D, E, and optical conductor C of the present invention shows improved photosensitivity.
Embodiment 3
In the present embodiment, prepare optical conductor G of the present invention and two kinds contrast optical conductor H and I.In each optical conductor, with the charge generating layers dip-coating on the aluminium base that carries out anodizing and with the charge transport layer dip-coating on charge generating layers.The charge transport layer of each optical conductor comprises the polymer adhesive of about 60wt% and the charge transport compound 4-N that comprises following general formula of about 40wt%, N-diphenyl amino benzaldehyde-N ＇, and N ＇-diphenyl hydrazone (TPH):
The charge generating layers of optical conductor G of the present invention comprises the TiOpc type I pigment of about 30wt%, the bonding agent of about 37wt% and the TPH of about 33wt%.This charge generating layers forms adhesive-free in this premix according to the general technology of embodiment 1 by the dispersion that electric charge generates the premix preparation of compound, TPH charge transport compound and solvent.The charge generating layers of contrast optical conductor H does not have the charge transport compound, comprises the TiOpc type I pigment of about 34wt% and the bonding agent of about 66wt%, and the conventional dispersion preparation in solvent by pigment and bonding agent.The charge generating layers of contrast optical conductor I comprises the TiOpc type I pigment of about 30wt%, the bonding agent of about 37wt% and the TPH of about 33wt%.Different with the charge generating layers of optical conductor G, the charge generating layers of contrast optical conductor I is prepared by a kind of like this dispersion, promptly wherein electric charge generation compound and charge transport compound do not mix with the premix of essentially no bonding agent, but charge transport compound and bonding agent are being mixed approximately simultaneously with electric charge generation compound.
According to the technology of embodiment 1 general remark the optical conductor of present embodiment being carried out photosensitivity measures.The result of these measurements provides in Fig. 3.H compares with I with the contrast optical conductor, and optical conductor G of the present invention shows tangible better photosensitivity.
Embodiment 4
Further proof prepared according to the methods of the invention and wherein improvement of the contained charge transport compound of the charge generating layers optical conductor demonstration different of present embodiment by charge generating layers wherein with the charge transport compound of charge transport layer.In each optical conductor, with the charge generating layers dip-coating on the aluminium base that carries out anodizing and with the charge transport layer dip-coating on charge generating layers.The charge transport layer of each optical conductor comprises the polymer adhesive of about 60wt% and the 4-N that comprises following formula of about 40wt%, N-lignocaine benzaldehyde-N ＇, and the charge transport compound of N ＇-diphenyl hydrazone (DEH):
The dispersion that is equipped with forms, and wherein dispersion comprises 33wt%TPD, 30wt%TiOpc and 37wt% polymer adhesive.For comparing, preparation contrast optical conductor K, this optical conductor comprise the charge generating layers that contains 30%TiOpc pigment and 70% polymer adhesive and do not have TPD.
Optical conductor J and K are carried out photosensitivity measure by embodiment 1 is described, at first use the exposure duration 76ms that develops, its result provides in Fig. 4 A, secondly uses the exposure duration 257ms that develops, and its result provides in Fig. 4 B.In Fig. 4 A and 4B, curve J and K represent the performance of optical conductor J and K respectively.The presentation of results that Fig. 4 A and 4B provide when using different charge transport compounds respectively in charge transport layer and charge generating layers, obtains further improved optical conductor photosensitivity.
Do not wish to be subjected under any one theory the inventor, it is believed that when being coated with charge transport layer on the charge generating layers in optical conductor such as optical conductor J of the present invention, part TPD charge transport compound contained in the charge generating layers diffuses in the charge transport layer, and some contained in opposite charges transfer layer DEH charge transport compounds diffuse in the charge generating layers.Therefore it is shocking, this charge generating layers and charge transport layer take place at the interface mix and can not cause trap and the reduction of optical conductor photosensitivity.In addition, as what prove above, when particularly contained charge transport compound and electric charge generate compound and grind in advance according to the inventive method in the presence of no polymer adhesive in charge generating layers, the photosensitivity rising of optical conductor.With TPD as the charge transport compound in the charge generating layers with combine as the charge transport compound in the charge transport layer with DEH, provide cost advantage and improved wearability (with comprise it on scribble the charge transport layer that contains TPD the standard charge conventional optical conductor that generates layer compare), and show improved photosensitivity (with comprise it on scribble the charge transport layer that contains DEH the standard charge conventional optical conductor that generates layer compare).
Embodiments of the invention that provide above and various preferred embodiment only are used for illustration purpose and are not used in the scope of the invention that the restriction claim defines.Other embodiments of the present invention and its advantage be conspicuous for those skilled in the art and the scope of the invention of below claim definition in.
Claims (22)
1. method for preparing charge generating layers, comprise electric charge is generated the pre-composition that compound, charge transport compound and solvent premix form essentially no polymer adhesive, the pre-composition that this electric charge is generated compound, charge transport compound and solvent mixes the formation dispersion with at least a polymer adhesive, and this dispersion is applied on the base material.
2. according to the process of claim 1 wherein that the charge transport compound dissolves in the solvent.
3. according to the method for claim 2, wherein solvent comprises ketone, ether or its potpourri.
4. according to the method for claim 2, the slurry that wherein electric charge is generated compound and solvent ground before adding charge transport compound formation premix.
5. according to the process of claim 1 wherein that premix do not have polymer adhesive.
6. according to the process of claim 1 wherein that electric charge generates compound and comprises phthalocyanine compound.
7. according to the process of claim 1 wherein that electric charge generates compound and comprises the titanyl phthalocyanine compound.
8. according to the process of claim 1 wherein that the charge transport compound comprises hydrazone, arylamine, substituted aromatic amines or its potpourri.
9. according to the process of claim 1 wherein that premix comprises that about 25 to about 75wt% charge transport compound and about electric charge of 75 to about 25wt% generate compound, generate the total content of compound and charge transport compound by the electric charge in the premix.
10. according to the process of claim 1 wherein that premix comprises that about 1 to about 50wt% electric charge generates compound, about 1 to about 50wt% charge transport compound and about solvent of 5 to about 98wt%.
11. method according to claim 1, wherein premix comprises that about 5 to about 60wt% electric charge generates compound, about 5 to about 60wt% charge transport compound and about polymer adhesive of 10 to about 90wt%, by the total content of electric charge generation compound, charge transport compound and polymer adhesive.
12. according to the process of claim 1 wherein that dispersion comprises that about electric charge of 1 to about 30wt% generates compound, about 1 to about 30wt% charge transport compound, about polymer adhesive of 1 to about 30wt% and about solvent of 5 to about 99wt%.
13. charge generating layers that forms according to the method for claim 1.
14. optical conductor, comprise base material, charge transport layer and charge generating layers, wherein charge transport layer comprises bonding agent and first kind of charge transport compound, charge generating layers comprises bonding agent, electric charge generates compound and second kind of charge transport compound, wherein first kind and second kind of charge transport compound can be identical or different, wherein charge generating layers prepares by the following method: electric charge is generated compound, second kind of charge transport compound and solvent premix form the pre-composition of essentially no polymer adhesive, this electric charge is generated compound, the pre-composition of second kind of charge transport compound and solvent mixes with at least a polymer adhesive and forms dispersion, and this dispersion is applied on the base material.
15. according to the optical conductor of claim 14, wherein the weight ratio of the generation compound of the electric charge in the charge generating layers and second kind of charge transport compound was not less than about 1: 3.
16. according to the optical conductor of claim 14, wherein electric charge generation compound comprises phthalocyanine.
17. according to the optical conductor of claim 14, wherein charge generating layers comprises that the electric charge at least about 10wt% generates compound, by the weight of charge generating layers.
18. according to the optical conductor of claim 14, wherein first kind different with second kind of charge transport compound.
19. according to the optical conductor of claim 14, wherein first kind identical with second kind of charge transport compound.
20. according to the optical conductor of claim 14, wherein first kind and second kind of charge transport compound comprise hydrazone, arylamine or substituted aromatic amines or its potpourri separately.
21. according to the optical conductor of claim 14, wherein electric charge generates compound and comprises metal phthalocyanine, first kind and second kind of charge transport compound comprise hydrazone, arylamine or substituted aromatic amines or its potpourri separately.
22. according to the optical conductor of claim 14, wherein charge generating layers comprises that about 5 to about 60wt% electric charge generates compound, about 5 to about 60wt% second kind of charge transport compound and about bonding agent of 20 to about 80wt%
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/066,284 US5994013A (en) | 1998-04-24 | 1998-04-24 | Dual layer photoconductors with charge generation layer containing charge transport compound |
| US09/066,284 | 1998-04-24 | ||
| US09/219,331 US6022657A (en) | 1998-12-22 | 1998-12-22 | Methods of making charge generation layers containing charge transport compound, and photoconductors containing the same |
| US09/219,331 | 1998-12-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1303491A true CN1303491A (en) | 2001-07-11 |
Family
ID=26746568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99806629 Pending CN1303491A (en) | 1998-04-24 | 1999-04-23 | Methods of making charge generation layers containing charge transport compounds, and photoconductors containing same |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1073936B1 (en) |
| CN (1) | CN1303491A (en) |
| AU (1) | AU3866299A (en) |
| DE (1) | DE69933864T2 (en) |
| WO (1) | WO1999056180A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6245471B1 (en) * | 2000-04-12 | 2001-06-12 | Lexmark International, Inc. | Charge generation layers comprising at least one titanate and photoconductors including the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE68919071T2 (en) * | 1989-03-20 | 1995-04-13 | Agfa Gevaert Nv | Recording material suitable for electrophotographic purposes. |
| JPH04275557A (en) * | 1990-12-17 | 1992-10-01 | Eastman Kodak Co | Inverse multiple active electronic-photograph element |
| US5437950A (en) * | 1994-04-05 | 1995-08-01 | Xerox Corporation | Electrophotographic imagimg member with enhanced photo-electric sensitivity |
-
1999
- 1999-04-23 WO PCT/US1999/008917 patent/WO1999056180A1/en active IP Right Grant
- 1999-04-23 CN CN 99806629 patent/CN1303491A/en active Pending
- 1999-04-23 EP EP99921456A patent/EP1073936B1/en not_active Expired - Lifetime
- 1999-04-23 DE DE69933864T patent/DE69933864T2/en not_active Expired - Fee Related
- 1999-04-23 AU AU38662/99A patent/AU3866299A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| DE69933864D1 (en) | 2006-12-14 |
| WO1999056180A1 (en) | 1999-11-04 |
| EP1073936A1 (en) | 2001-02-07 |
| AU3866299A (en) | 1999-11-16 |
| EP1073936A4 (en) | 2004-10-27 |
| EP1073936B1 (en) | 2006-11-02 |
| DE69933864T2 (en) | 2007-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1469177A (en) | Method and composition for improving performance of cataphoresis display | |
| JPS5858550A (en) | Electrophotographic receptor | |
| CN1351722A (en) | Electrophotographic photoconductor containing fluorenyl-azine derivatives as charge transport additives | |
| CN1605944A (en) | Electrophotographic photoconductor and methods therefor | |
| CN1881092A (en) | Electrophotographic photoreceptor and electrophotographic imaging apparatus using the photoreceptor | |
| CN1218223C (en) | Electrophotographic photoconductor containing simple quinones to improve electrical properties | |
| DE2635887A1 (en) | ELECTROPHOTOGRAPHIC ELEMENT FOR THE GENERATION OF IMAGES AND THE PROCESS FOR ITS MANUFACTURING | |
| CN1158576C (en) | Photoconductor with charge generation binder blend | |
| CN1303491A (en) | Methods of making charge generation layers containing charge transport compounds, and photoconductors containing same | |
| CN1655067A (en) | Electrophotographic photoreceptor and electrophotographic imaging apparatus using the same | |
| CN1303490A (en) | Dual layer photo conductors with charge generation layer containing charge transport compound | |
| JPH11174707A (en) | Organic semiconductor film | |
| DE4000085A1 (en) | ELECTROSTATOGRAPHIC IMAGE GENERATION PART | |
| CN1326948C (en) | Charge generating layers comprising type I polymorph of titanyl phthalocyanine | |
| CN1301444C (en) | Charge generation layers comprising at least one titanate and photoconductors including same | |
| DE2355075A1 (en) | CONDENSATION PRODUCTS MADE FROM O-PHENYLENEDIAMINE OR 1,8-DIAMINONAPHTHALIN AND 4,10-BENZTHIOXANTHEN-3,1'-DICARBONIC ANHYDRIDE, THE PREPARATION AND USE OF THEREOF | |
| US6022657A (en) | Methods of making charge generation layers containing charge transport compound, and photoconductors containing the same | |
| JPS581155A (en) | Electrophotographic receptor | |
| CN1514308A (en) | Wet deleloping electronic photographic light sensor | |
| JP2511467B2 (en) | Method for manufacturing positively chargeable organic laminated photoreceptor | |
| JPH1031318A (en) | Electrophotographic photoreceptor | |
| JP2833192B2 (en) | Electrophotographic photoreceptor | |
| CN1461978A (en) | Photoconductor and quinolmethane compound for electronic photograph | |
| JP2001066802A (en) | Apparatus for production of electrophotographic photoreceptor, and production of electrophotographic photoreceptor | |
| JP2806399B2 (en) | Electrophotographic photoreceptor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |