Electrophotographic imaging member with improved charge generation layer

Abstract: An electrophotographic imaging member comprising a support substrate having a two layered electrically conductive outer surface, a hole blocking layer, an adhesive layer comprising a copolyester resin, a charge generation layer comprising photoconductive perylene or phthalocyanine particles dispersed in a film forming resin binder blend comprising polyvinyl butryal copolymer and a copolyester selected from the group consisting of a first copolyester, a second copolyester and mixtures thereof, and a charge transport layer.

Description: This invention relates in general to electrophotography and more specifically, to an improved electrophotographic imaging member having improved charge generation layers. Electrophotographic imaging members are usually multilayered photoreceptors that comprise a substrate support, an electrically conductive layer, an optional hole blocking layer, an adhesive layer, a charge generating layer, and a charge transport layer in either a flexible belt form or a rigid drum configuration. One type of multilayered photoreceptor comprises a layer of finely divided particles of a photoconductive inorganic compound dispersed in an electrically insulating organic resin binder. Inorganic or organic photoconductive material may be formed as a continuous, homogeneous photogenerating layer. As more advanced, higher speed electrophotographic copiers, duplicators and printers were developed, degradation of image quality was encountered during extended cycling. Moreover, complex, highly sophisticated, duplicating and printing systems employed flexible photoreceptor belts, operating at very high speeds, have also placed stringent mechanical requirements and narrow operating limits as well on photoreceptors. For example, the layers of many modern multilayered photoreceptor belt must be highly flexible, adhere well to each other, and exhibit predictable electrical characteristics within narrow operating limits to provide excellent toner images over many thousands of cycles. A typical prior art multilayered flexible photoreceptor configuration comprises an adhesive interface layer between the hole blocking layer and the adjacent photogenerating layer to improve adhesion or to act as an electrical barrier layer. Typical adhesive interface layers include film-forming polymers such as polyester, polyvinylbutyral, polyvinylpyrolidone, polyurethane, polycarbonates, polymethylmethacrylate or mixtures thereof. Specific polyester adhesive materials include, for example linear saturated copolyesters consisting of alternating monomer units of ethylene glycol and four randomly sequenced diacids and copolyesters of diacids and diols where the diacid is selected from the group consisting of terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and mixtures thereof and the diol is selected from the group consisting of ethylene glycol, 2,2-dimethyl propane diol and mixtures thereof. An encouraging advance in electrophotographic imaging which has emerged in recent years is the successful fabrication of a flexible imaging member which exhibits excellent capacitive charging characteristic, outstanding photosensitivity, low electrical potential dark decay, and long term electrical cyclic stability. This imaging member employed in belt form usually comprises a substrate, a conductive layer, a solution coated hole blocking layer, a solution coated adhesive layer, a thin charge generating layer comprising a sublimation deposited perylene or phthalocyanine organic pigment or a dispersion of one of these pigments in a selected binder resin, a solution coated charge transport layer, a solution coated anti-curl layer, and an optional overcoating layer. Multi-layered photoreceptors containing charge generating layers, comprising either vacuum sublimation deposited pure organic pigment or an organic pigment dispersion of perylene or phthalocyanine in a resin binder, have frequently been found to have undesirable characteristics such as forming charge deficient spots which are visible in the final hard copy print. Photoreceptors containing perylene pigments in the charge generating layers, particularly benzimidazole perylene dispersion charge generating layers, have a spectral sensitivity of up to 720 nanometers, are highly compatible with exposure systems utilizing visible laser diodes, exhibit low dark decay electrical characteristic and reduced background/residual voltages. These characteristics are superior to photoreceptor counterparts containing a trigonal selenium dispersion in the charge generating layer. Unfortunately, these multi-layered benzimidazole perylene photoreceptors have also been found to develop a serious charge deficient spots problem, particularly the dispersion of perylene pigment in the matrix of a bisphenol Z type polycarbonate film forming binder. The expression "charge deficient spots" as employed herein is defined as localized areas of dark decay that appear as toner deficient spots when using charged area development, e.g. appearance of small white spots having an average size of between 0.2 and 0.3 millimeter on a black toner background on an imaged hard copy. In discharged area development systems, the charge deficient spots appear in the output copies as small black toner spots on a white background. Moreover, multi-layered benzimidazole perylene photoreceptors have also been noted to yield low adhesion bond strength at the contacting surfaces between the charge generating layer and the adhesive interface layer, causing undesirable premature photoreceptor layer delamination during photoreceptor image cycling in copiers, duplicators and printers. In a customer service environment, premature photoreceptor layer delamination requires costly and frequent photoreceptor belt replacement by skilled technical representatives. Typically, flexible photoreceptor belts are fabricated by depositing the various layers of photoactive coatings onto long webs which are thereafter cut into sheets. The opposite ends of each photoreceptor sheet are overlapped and ultrasonically welded together to form an imaging belt. In order to increase throughput during the web coating operation, the webs to be coated have a width of twice the width of a final belt. After coating, the web is slit lengthwise and thereafter transversely cut into predetermined length to form photoreceptor sheets of precise dimensions that are eventually welded into belts. When multi-layered photoreceptors containing perylene pigment dispersion in the charge generating layer are slit lengthwise during the belt fabrication process, it has been found that some of the photoreceptor delaminates and becomes unusable. In the fabricated belt form, photoreceptor layer delamination at the welded seam, due to stress concentration development at the double thickness overlap area during dynamic fatigue photoreceptor belt bending/flexing over the machine belt support rollers, diminishes the practical application value of the belt. All of the above deficiencies, implicated by the low layer adhesion bond strength, hinder slitting of a photoreceptor web through the charge generating layer without encountering edge delamination. Slitting is used to transversely cut webs into sheets for welding into belts and also to longitudinally slice double wide coated photoreceptor webs into multiple narrower charge generating layers. In general, photoconductive pigment loadings of 80 percent by volume in a binder resin or a mixed resins binder are highly desirable in the photogenerating layer to provide excellent photosensitivity. However, these dispersions are highly unstable to extrusion coating conditions, resulting in numerous coating defects that generate a large number of unacceptable material that must be scrapped when using extrusion coating of a dispersion of pigment in organic solution of polymeric binder. More stable dispersions can be obtained by reducing the pigment loading to 30-40 percent by volume, but in most cases the resulting "diluted" photogenerating layer could not provide adequate photosensitivity. Also, the dispersions of higher pigment loadings generally provided a generator layer with poor to adequate adhesion to either the underlying ground plane or adhesive layer, or the overlying transport layer when polyvinylbutyral binders are utilized in the charge generating layer. Many of these organic dispersions are quite unstable with respect to pigment agglomeration, resulting in dispersion settling and the formation of dark streaks and spots of pigment during the coating process. Normally, the polymeric binders which produce the best (most stable, therefore most manufacturable) dispersion suffer from deficiencies either in xerographic or mechanical properties, while the least stable dispersions provided the best possible mechanical and xerographic properties. The best compromise of manufacturability and xerographic/mechanical performance is obtained by use of a photogenerating layer containing benzimidazole perylene pigment dispersed in a bisphenol Z type polycarbonate film forming binder. However, when a polyester adhesive layer is employed in a photoreceptor in combination with a photogenerating layer containing benzimidazole perylene pigment dispersed in a bisphenol A type or a bisphenol Z type polycarbonate film forming binder, poor adhesion between the charge generator layer and the adhesive layer can cause spontaneous photoreceptor delaminate during certain slitting operations, during fabrication, or during extensive photoreceptor belt cycling over small diameter machine belt support rollers. In addition, when a multilayered belt imaging member containing benzimidazole perylene pigment dispersed in the bisphenol Z polycarbonate film forming binder in the charge generating layer is fabricated by ultrasonic welding the opposite ends of an imaging sheet together, delamination is encountered when attempts are made to grind away some of the weld splash material. Removal of the weld splash material is of particular importance, because it allows the elimination of seams which form flaps during electrophotographic imaging and cleaning processes of belt function that causes the initiation of toner particles trapping and thereafter release them as unwanted dirts over the imaging belt surface to result in copy black spot print defects. Also, the inability to grind, buff, or polish a welded seam causes reduced cleaning blade life as well as seam interference with toner image ultrasonic transfer assist subsystems. In US-A 5,322,755 a layered photoconductive imaging member is disclosed comprising a supporting substrate, a photogenerator layer comprising perylene photoconductive pigments dispersed in a resin binder mixture comprising at least two polymers, and a charge transport layer. The resin binder can be, for example, a mixture of polyvinylcarbazole and polycarbonate homopolymer or a mixture of polyvinylcarbazole, polyvinylbutyral and polycarbonate homopolymer or a mixture of polyvinylcarbazole and polyvinylbutyral or a mixture of polyvinylcarbazole and a polyester. Although improvement in photosensitivity and adhesion are achieved, charge deficient spots print defects can still be a problem. Thus, there is a continuing need for improved photoreceptors that exhibit freedom from charge deficient spots and are more resistant to layer delamination during slitting, grinding, buffing, polishing, and dynamic belt image cycling. It is, therefore, the object of the present invention to provide an improved photoreceptor member which overcomes the above-noted disadvantages. In accordance with the present invention there is provided an electrophotographic imaging member comprising a support substrate the surface of which being covered with at least two electrically conductive metal layers comprising zirconium and/or titanium with the outermost metal layer containing at least 50 percent by weight of zirconium, a hole blocking layer, an adhesive layer comprising a copolyester resin, a charge generation layer comprising photoconductive perylene or phthalocyanine particles dispersed in a film forming resin binder blend, said resin binder blend comprising polyvinyl butyral copolymer represented by the following general formula: wherein: x is a number such that the polyvinyl butyral content is between 50 and 75 mol percent, y is a number such that the polyvinyl alcohol content is between 12 and 50 mol percent, and z is a number such that the polyvinyl acetate content is between 0 and 15 mol percent, and a copolyester represented by the following general formula: wherein said diacid is selected from the group consisting of terephthalic acid, isophthalic acid, and mixtures thereof, said diol comprises ethylene glycol and 2,2-dimethyl propane diol, said mole ratio of diacid to diol is 1:1, said mole ratio of terephthalic acid to isophthalic acid is 1.2:1, said mole ratio of ethylene glycol to 2,2-dimethyl propane diol is 1.33:1, n is a number between 160 and 330, and the T g of said copolyester resin is between 50°C and 80°C, and a charge transport layer, said charge transport layer being non-absorbing in the spectral region at which the charge generation layer generates and injects photogenerated holes but being capable of supporting the injection of photogenerated holes from said charge generation layer and transporting said holes through said charge transport layer. This photoreceptor is utilized in an electrophotographic imaging process. Preferred embodiments of the present invention are set forth in the claims. The substrate may be opaque or transparent and may comprise numerous suitable materials having the required mechanical properties. Accordingly, this substrate may comprise a layer of an electrically non-conductive or conductive material such as an inorganic or an organic composition. As electrically non-conducting materials there may be employed various thermoplastic and thermoset resins known for this purpose including polyesters, polycarbonates, polyamides and polyurethanes, or metals such as aluminum, nickel, steel, stainless steel, titanium, chromium, copper, brass or tin. The substrate may have any suitable shape such as, for example, a flexible web, rigid cylinder or sheet. Preferably, the substrate support is in the form of an endless flexible belt. The thickness of a flexible substrate support depends on numerous factors, including economical considerations, and thus this layer for a flexible belt may be of substantial thickness, for example, over 200 micrometers, or of minimum thickness less than 50 micrometers, provided there are no adverse affects on the final photoconductive device. In one flexible belt embodiment, the thickness of this layer ranges from 65 micrometers to 150 micrometers, and preferably from 75 micrometers to 125 micrometers for optimum flexibility and minimum stretch when cycled around small diameter rollers, e.g. 12 millimeter diameter rollers. The zirconium and/or titanium layer may be formed by any suitable coating technique, such as vacuum deposition. Typical vacuum depositing techniques include sputtering, magnetron sputtering and RF sputtering. Magnetron sputtering of zirconium or titanium onto a metallized substrate can be effected by a conventional type sputtering module under vacuum conditions in an inert atmosphere such as argon, neon, or nitrogen using a high purity zirconium or titanium target. The vacuum conditions are not particularly critical. In general, a continuous zirconium or titanium film can be attained on a suitable substrate, e.g. a polyester web substrate such as Mylar available from E.I. du Pont de Nemours & Co. with magnetron sputtering. It should be understood that vacuum deposition conditions may all be varied in order to obtain the desired zirconium or titanium thickness. The conductive layer comprises at least two metal layers with the outermost metal layer (i.e. the layer closest to the charge blocking layer) comprising at least 50 percent by weight of zirconium. At least 70 percent by weight of zirconium is preferred in the outermost metal layer for even better results. The multiple layers may, for example, all be vacuum deposited or a thin layer can be vacuum deposited over a thick layer prepared by a different techniques such as by casting. Thus, as an illustration, a zirconium metal layer may be formed in a separate apparatus than that used for previously depositing a titanium metal layer or multiple layers can be deposited in the same apparatus with suitable partitions between the chamber utilized for depositing the titanium layer and the chamber utilized for depositing zirconium layer. The titanium layer may be deposited immediately prior to the deposition of the zirconium metal layer. Generally, for rear erase exposure, a conductive layer light transparency of at least 15 percent is desirable. The combined thickness of the two layered conductive layer should be between 12 and 30 nanometers. A typical zirconium/titanium dual conductive layer has a total combined thickness of about 20 nanometers. Although thicker layers may be utilized, economic and transparency considerations may affect the thickness selected. Regardless of the technique employed to form the zirconium and/or titanium layer, a thin layer of zirconium or titanium oxide forms on the outer surface of the metal upon exposure to air. Thus, when other layers overlying the zirconium layer are characterized as "contiguous" layers, it is intended that these overlying contiguous layers may, in fact, contact a thin zirconium or titanium oxide layer that has formed on the outer surface of the metal layer. If the zirconium and/or titanium layer is sufficiently thick to be self supporting, no additional underlying member is needed and the zirconium and/or titanium layer may function as both a substrate and a conductive ground plane layer. Ground planes comprising zirconium tend to continuously oxidize during xerographic cycling due to anodizing caused by the passage of electric currents, and the presence of this oxide layer tends to decrease the level of charge deficient spots with xerographic cycling. Generally, a zirconium layer thickness of at least 10 nanometers is desirable to maintain optimum resistance to charge deficient spots during xerographic cycling. After deposition of the zirconium an/or titanium metal layer, a hole blocking layer is applied thereto. Generally, electron blocking layers for positively charged photoreceptors allow the photogenerated holes in the charge generating layer at the top of the photoreceptor to migrate toward the charge (hole) transport layer below and reach the bottom conductive layer during the electrophotographic imaging processes. Thus, an electron blocking layer is normally not expected to block holes in positively charged photoreceptors such as photoreceptors coated with charge a generating layer over a charge (hole) transport layer. For negatively charged photoreceptors, any suitable hole blocking layer capable of forming an electronic barrier to holes between the adjacent photoconductive layer and the underlying zirconium and/or titanium layer may be utilized. A hole blocking layer may comprise any suitable material. Typical hole blocking layers utilized for the negatively charged photoreceptors may include, for example, Luckamide, hydroxy alkyl methacrylates, nylons, gelatin, hydroxyl alkyl cellulose, organopolyphosphazines, organosilanes, organotitanates, organozirconates, silicon oxides or zirconium oxides. Preferably, the hole blocking layer comprises nitrogen containing siloxanes. Typical nitrogen containing siloxanes are prepared from coating solutions containing a hydrolyzed silane. Typical hydrolyzable silanes include 3-aminopropyl triethoxy silane, (N,N'-dimethyl 3-amino) propyl triethoxysilane, N,N-dimethylamino phenyl triethoxy silane, N-phenyl aminopropyl trimethoxy silane, trimethoxy silylpropyldiethylene triamine and mixtures thereof. During hydrolysis of the amino silanes described above, the alkoxy groups are replaced with hydroxyl group. An especially preferred blocking layer comprises a reaction product between a hydrolyzed silane and the zirconium and/or titanium oxide layer which inherently forms on the surface of the metal layer when exposed to air after deposition. This combination reduces spots at time 0 and provides electrical stability at low RH. The imaging member is prepared by depositing on the zirconium and/or titanium oxide layer of a coating of an aqueous solution of the hydrolyzed silane at a pH between 4 and 10, drying the reaction product layer to form a siloxane film and applying electrically operative layers, such as a photogenerator layer and a hole transport layer, to the siloxane film. The blocking layer may be applied by any suitable conventional technique such as spraying, dip coating, draw bar coating, gravure coating, silk screening, air knife coating, reverse roll coating, vacuum deposition or chemical treatment. For convenience in obtaining thin layers, the blocking layers are preferably applied in the form of a dilute solution, with the solvent being removed after deposition of the coating by conventional techniques such as by vacuum or heating. After drying, the siloxane reaction product film formed from the hydrolyzed silane contains larger molecules. The reaction product of the hydrolyzed silane may be linear, partially crosslinked, a dimer or a trimer. The siloxane blocking layer should be continuous and have a thickness of less than 0.5 micrometer because greater thicknesses may lead to undesirably high residual voltage. A blocking layer of between 0.005 micrometer and 0.3 micrometer is preferred because charge neutralization after the exposure step is facilitated and optimum electrical performance is achieved. A thickness of between 0.03 micrometer and 0.06 micrometer is preferred for zirconium and/or titanium oxide layers for optimum electrical behavior and reduced charge deficient spot occurrence and growth. Any suitable adhesive interface layer may be applied to the charge blocking layer. Any suitable adhesive layer may be utilized. Adhesive layer materials are well known in the art. Typical adhesive layer materials include, for example, polyesters, polyarylates, polysulfones, and polyurethanes. Any suitable solvent or solvent mixtures may be employed to form a coating solution. Typical solvents include tetrahydrofuran, toluene, methylene chloride, cyclohexanone, and mixtures thereof. Satisfactory results may be achieved with a dry adhesive layer thickness between 0.05 micrometer and 0.3 micrometer. Conventional techniques for applying an adhesive layer coating mixture to the charge blocking layer include spraying, dip coating, roll coating, wire wound rod coating, gravure coating and Bird applicator coating. Drying of the deposited coating may be effected by any suitable conventional technique such as oven drying, infra red radiation drying or air drying. The charge generating layer of the photoreceptor of this invention comprises a perylene pigment or a phthalocyanine pigment applied as a solution coated layer containing the pigment dispersed in a film forming resin binder blend. The perylene pigment is preferably benzimidazole perylene which is also referred to as bis(benzimidazole). This pigment exists in the cis and trans forms. The cis form is also called bis-benzimidazo(2,1-a-1',1'-b) anthra (2,1,9-def:6.5,10-d'e'f') disoquinoline-6,11-dione. The trans form is also called bisbenzimidazo (2,1-a1',1'-b) anthra (2,1,9-def:6,5,10-d'e'f') disoquinoline-10,21-dione. This pigment may be prepared by reacting perylene 3,4,9,10-tetracarboxylic acid dianhydride with 1,2-phenylene as illustrated in the following equation: Benzimidazole perylene is ground into fine particles having an average particle size of less than 1 micrometer and dispersed in a film forming binder blend. Optimum results are achieved with a pigment particle size between 0.2 micrometer and 0.3 micrometer. Benzimidazole perylene is described in US-A 5,019,473 and US-A 4,587,189. Although photoreceptor embodiments prepared with a charge generating layer comprising benzimidazole perylene dispersed in various types of resin binders give reasonably good results, the electrical life of the photoreceptor is found to be dramatically improved, particularly, with the use of benzimidazole perylene dispersed in a resin blend of a polyvinyl butyral and a copolyester. The polyvinyl copolymer is represented by the following general formula: wherein: x is a number such that the polyvinyl butyral content is between 50 and 75 mol percent, y is a number such that the polyvinyl alcohol content is between 12 and 50 mol percent, and z is a number such that the polyvinyl acetate content is between 0 and 15 mol percent Preferably, the film forming polyvinyl butyral copolymer binder for the charge generating layer is the reaction product of a polyvinyl alcohol and butyraldehyde in the presence of a sulphuric acid catalyst. The hydroxyl groups of the polyvinyl alcohol react to give a random butyral structure which can be controlled by varying the reaction temperature and time. The acid catalyst is neutralized with potassium hydroxide. The polyvinyl alcohol is synthesized by hydrolyzing polyvinyl acetate. The resulting hydrolyzed polyvinyl alcohol may contain some polyvinyl acetate moieties. The partially or completely hydrolyzed polyvinyl alcohol is reacted with the butyraldehyde under conditions where some of the hydroxyl groups of the polyvinyl alcohol are reacted, but where some of the other hydroxyl groups of the polyvinyl alcohol remain unreacted. For utilization in the photoconductive layer the reaction product should have a polyvinyl butyral content of between 50 percent and 75 mol percent, a polyvinyl alcohol content of between 12 mol percent and 50 mol percent and a polyvinyl acetate content up to 15 mol percent. These film forming polyvinyl butyral copolymers are commercially available and include, for example, Butvar B-79 resin (available from Monsanto Chemical Co.) having a polyvinyl butyral content of about 88 percent by weight, a polyvinyl alcohol content of 12 percent by weight and a polyvinyl acetate content of less than 1.5 percent by weight, a weight average molecular weight of between 50,000 and 80,000; Butvar B-76 resin (available from Monsanto Chemical Co.) having a polyvinyl butyral content of about 80 percent by weight, a polyvinyl alcohol content of 19 percent by weight and a polyvinyl acetate content of less than 2.5 percent by weight, a weight average molecular weight of between 90,000 and 120,000; and BMS resin (available from Sekisui Chemical) having a polyvinyl butyral content of about 72 percent, a vinyl acetate group content of about 5 weight percent, no polyvinyl acetate component and a weight average molecular weight of about 93,000. Preferably, the weight average molecular weight of the polyvinyl butyral utilized in this invention is between 50,000 and 250,000. Satisfactory results may be obtained with a polyvinyl butyral copolymer having a weight average molecular weight between 20,000 and 400,000. The solvent for the film forming polyvinyl butyral copolymer includes, for example, cyclohexanone or other suitable ketones such as methyl ethyl ketone or methyl iso-amyl ketone or mixtures thereof having a boiling point between 75°C and 160°C. The copolyester resin component of the blend is a copolyester represented by the following general formula: wherein said diacid is selected from the group consisting of terephthalic acid, isophthalic acid, and mixtures thereof, said diol comprises ethylene glycol and 2,2-dimethyl propane diol, said mole ratio of diacid to diol is 1:1, said mole ratio of terephthalic acid to isophthalic acid is 1.2:1, said mole ratio of ethylene glycol to 2,2-dimethyl propane diol is 1.33:1, n is a number between 160 and 330, and the T g of said copolyester resin is between 50°C and 80°C. Preferably, the binder blend consists of between 10 percent and 50 percent by weight of said polyvinyl butyral copolymer and between 90 percent and 50 percent by weight of the copolyester. Satisfactory results may be achieved when the dried charge generating layer contains between 20 percent and 90 percent by volume benzimidazole perylene dispersed in the film forming resin blend based on the total volume of the dried charge generating layer. Preferably, the perylene pigment is present in an amount between 30 percent and 80 percent by volume. Optimum results are achieved with an amount between 35 percent and 45 percent by volume. The use of the polymer blend as the charge generating binder allows a reduction in perylene pigment loading without an extreme loss in photosensitivity. Any suitable organic solvent may be utilized to dissolve the film forming resin binder blend. Typical solvents include tetrahydrofuran, toluene and methylene chloride. Tetrahydrofuran is preferred because it has no discernible adverse effects on xerography and has an optimum boiling point to allow adequate drying of the generator layer during a typical slot coating process. Coating dispersions for the charge generating layer may be formed by any suitable technique using, for example, attritors, ball mills, Dynomills, paint shakers, homogenizers or microfluidizers. Any suitable coating technique may be used to apply coatings. Typical coating techniques include slot coating, gravure coating, roll coating, spray coating, spring wound bar coating, dip coating, draw bar coating and reverse roll coating. Any suitable drying technique may be utilized to solidify and dry the deposited coatings. Typical drying techniques include oven drying, forced air drying and infrared radiation drying. Satisfactory results may be achieved with a dry charge generating layer thickness between 0.3 micrometer and 3 micrometers. Preferably, the charge generating layer has a dried thickness of between 1.1 micrometers and 2 micrometers. The photogenerating layer thickness is related to binder content. Thicknesses outside these ranges can be selected providing the object of the present invention is achieved. Typical charge generating layer thicknesses have an optical density of between 1.7 and 2.1. Any suitable charge transport layer may be utilized. The active charge transport layer may comprise any suitable transparent organic polymer or non-polymeric material capable of supporting the injection of photo-generated holes and electrons from the charge generating layer and allowing the transport of these holes or electrons through the organic layer to selectively discharge the surface charge. The charge transport layer in conjunction with the generation layer in the instant invention is a material which is an insulator to the extent that an electrostatic charge placed on the transport layer is not conducted in the absence of illumination. Thus, the active charge transport layer is a substantially non-photoconductive material which supports the injection of photogenerated holes from the generation layer. An especially preferred transport layer employed in one of the two electrically operative layers in the multilayer photoconductor of this invention comprises from 25 to 75 percent by weight of at least one charge transporting aromatic amine compound, and 75 to 25 percent by weight of a polymeric film forming resin in which the aromatic amine is soluble. A dried charge transport layer containing between 40 percent and 50 percent by weight of the small molecule charge transport molecule based on the total weight of the dried charge transport layer is preferred. The charge transport layer forming mixture preferably comprises an aromatic amine compound. Typical aromatic amine compounds include triphenyl amines, bis and poly triarylamines, bis arylamine ethers and bis alkyl-arylamines. Examples of charge transporting aromatic amines for charge transport layers capable of supporting the injection of photogenerated holes of a charge generating layer and transporting the holes through the charge transport layer include, for example, triphenylmethane, bis(4-diethylamine-2-methylphenyl)phenylmethane, 4'-4"-bis(diethylamino)-2',2"-dimethyltriphenylmethane, N,N'-bis(alkylphenyl)-[1,1'-biphenyl]-4,4'-diamine wherein the alkyl is, for example, methyl, ethyl, propyl or n-butyl, N,N'-diphenyl-N,N'-bis(chlorophenyl)-[1,1'-biphenyl]-4,4'-diamine, and N,N'-diphenyl-N,N'-bis(3"-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine dispersed in an inactive resin binder. Any suitable inactive resin binder soluble in methylene chloride or other suitable solvent may be employed in this invention. Typical inactive resin binders soluble in methylene chloride include polycarbonate resin, polyvinylcarbazole, polyester, polyarylate, polyacrylate, polyether and polysulfone. Molecular weights can vary from 20,000 to 1,500,000. The preferred electrically inactive resin materials are polycarbonate resins having a molecular weight from 20,000 to 120,000, more preferably from 50,000 to 100,000. The materials most preferred as the electrically inactive resin material are poly(4,4'-dipropylidene-diphenylene carbonate) with a molecular weight of from 35,000 to 40,000, available as Lexan 145 from General Electric Company; poly(4,4'-isopropylidene-diphenylene carbonate) with a molecular weight of from 40,000 to 45,000, available as Lexan 141 from the General Electric Company; a polycarbonate resin having a molecular weight of from 50,000 to 100,000, available as Makrolon from Farbenfabricken Bayer A. G., and a polycarbonate resin having a molecular weight of from 20,000 to 50,000, available as Merlon from Mobay Chemical Company. Any suitable and conventional technique may be utilized to mix and thereafter apply the charge transport layer coating mixture to the charge generating layer. Typical application techniques include spraying, dip coating, roll coating and wire wound rod coating. Drying of the deposited coating may be effected by any suitable conventional technique such as oven drying, infra red radiation drying or air drying. Generally, the thickness of the transport layer is between 5 micrometers and 100 micrometers, but thicknesses outside this range can also be used. A dried thickness of between 18 micrometers and 35 micrometers is preferred with optimum results being achieved with a thickness between 24 micrometers and 29 micrometers. Preferably, the charge transport layer comprises an arylamine small molecule dissolved or molecularly dispersed in a polycarbonate. Other layers such as conventional ground strips comprising, for example, conductive particles disposed in a film forming binder may be applied to one edge of the photoreceptor in contact with the zirconium and/or titanium layer, blocking layer, adhesive layer or charge generating layer. Optionally, an overcoat layer may also be utilized to improve resistance to abrasion. In some cases a back coating may be applied to the side opposite the photoreceptor to provide flatness and/or abrasion resistance. These overcoating and backcoating layers may comprise organic polymers or inorganic polymers that are electrically insulating or slightly semi-conductive. COMPARATIVE EXAMPLE I A photoconductive imaging member was prepared by providing a web of. titanium and zirconium coated polyester (Melinex, available from ICI Americas Inc.) substrate having a thickness of 0.08 mm, and applying thereto, with a gravure applicator, a solution containing 50 grams 3-amino-propyltriethoxysilane, 15 grams acetic acid, 684.8 grams of 200 proof denatured alcohol and 200 grams heptane. This layer was then dried for about 5 minutes at 135°C in the forced air drier of the coater. The resulting blocking layer had a dry thickness of 50 nanometers. An adhesive interface layer was then prepared by applying a wet coating over the blocking layer, using a gravure applicator, containing 3.5 percent by weight based on the total weight of the solution of copolyester adhesive (49,000, available from Morton International Inc., previously available from E.I. du Pont de Nemours & Co.) in a 70:30 volume ratio mixture of tetrahydrofuran/cyclohexanone. The adhesive interface layer was then dried for about 5 minutes at 135°C in the forced air drier of the coater. The resulting adhesive interface layer had a dry thickness of 62 nanometers. A 23 x 30.5 cm sample was then cut from the web, and the adhesive interface layer was thereafter coated with a photogenerating layer (CGL) containing 40 percent by volume benzimidazole perylene and 60 percent by volume poly(4,4'-diphenyl-1,1'-cyclohexane carbonate). This photogenerating layer was prepared by introducing 0.3 grams of poly(4,4'-diphenyl-1,1'-cyclohexane carbonate) PCZ -200, available from Mitsubishi Gas Chem., and 48 ml of tetrahydrofuran into a 118 ml amber bottle. To this solution was added 1.6 gram of benzimidazole perylene and 300 grams of 3.18 mm (1/8 inch) diameter stainless steel shot. This mixture was then placed on a ball mill for 96 hours. 10 grams of the resulting dispersion was added to a solution containing 0.547 grams of poly(4,4'-diphenyl-1,1'-cyclohexane carbonate) PCZ-200 and 6.14 grams of tetrahydrofuran. The resulting slurry was thereafter applied to the adhesive interface with a 0.0127 mm (1/2- mil) gap Bird applicator to form a layer having a wet thickness of 0.0127 mm (0.5 mil). The layer was dried at 135°C for 5 minutes in a forced air oven to form a dry thickness photogenerating layer having a thickness of about 1.2 micrometers. This photogenerator layer was overcoated with a charge transport layer. The charge transport layer was prepared by introducing into an amber glass bottle in a weight ratio of a hole transporting molecule of 1:1 N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine and Makrolon 5705, a polycarbonate resin having a molecular weight of from 50,000 to 100,000 commercially available from Farbenfabriken Bayer A.G. The resulting mixture was dissolved in methylene chloride to form a solution containing 15 percent by weight solids. This solution was applied on the photogenerator layer using a 0.0762 mm (3-mil) gap Bird applicator to form a coating which upon drying had a thickness of 24 micrometers. During this coating process the humidity was equal to or less than 15 percent. The photoreceptor device containing all of the above layers was annealed at 135°C in a forced air oven for 5 minutes and thereafter cooled to ambient room temperature. After application of the charge transport layer coating, the imaging member spontaneous curled upwardly. An anti-curl coating was needed to impart the desired flatness to the imaging member. The anti-curl coating solution was prepared in a glass bottle by dissolving 8.82 grams polycarbonate (Makrolon 5705, available from Bayer AG) and 0.09 grams copolyester adhesion promoter (Vitel PE-100, available from Goodyear Tire and Rubber Company) in 90.07 grams methylene chloride. The glass bottle was then covered tightly and placed on a roll mill for about 24 hours until total dissolution of the polycarbonate and the copolyester was achieved. The anti-curl coating solution thus obtained was applied to the rear surface of the supporting substrate (the side opposite to the imaging layers) by hand coating using a 0.076 mm (3 mil) gap Bird applicator. The coated wet film was dried at 135°C in an air circulation oven for about 5 minutes to produce a dry. 14 micrometer thick anti-curl layer and provide the desired imaging member flatness. The resulting photoconductive imaging member was used to serve as a control. COMPARATIVE EXAMPLE II A photoconductive imaging member was prepared as described in Comparative Example I, except that the charge generating layer used was a reformulated charge generating layer containing 60 percent by volume benzimidazole perylene and 40 percent by volume polyvinyl butyral copolymer (B-79, available from Monsanto Chemical Co.). This charge generating layer was prepared by introducing 0.45 grams polyvinyl butyral copolymer B-79 and 50 ml of tetrahydrofuran solvent into a 118 ml amber bottle. To this solution was added 2.4 grams of benzimidazole perylene and 300 grams of 3.18 mm (1/8 inch) diameter stainless steel shot. This mixture was then placed on a ball mill for 96 hours. 30 grams of the resulting dispersion was then added to a solution containing 0.47 gram of polyvinyl butyral copolymer B-79 and 7.15 grams of tetrahydrofuran solvent. The resulting slurry was thereafter applied to the adhesive interface with a 0.0127 mm (1/2 mil) gap Bird applicator to form a layer having a wet thickness of 0.0127 mm (0.5 mil). The layer was dried at 135°C for 5 minutes in a forced air oven to form a dried thickness charge generating layer having a thickness of 1.2 micrometers. The fabricated imaging member was used to serve as a second control. EXAMPLE III A photoconductive imaging member was prepared as described in Comparative Example II, except that the charge generating layer was modified by bending a copolyester (Vitel PE-200, available from Goodyear Tire & Rubber Co.) with the polyvinyl butyral copolymer to form a mixed binder blend. This new charge generating layer contained 45 percent by volume of benzimidazole perylene and 55 percent by volume of a mixed binder blend, having a polyvinyl butyral copolymer B-79 to copolyester Vitel PE-200 volume ratio of 12/43 in the dried charge generating layer. This charge generating layer was prepared by introducing 0.45 gram polyvinyl butyral copolymer B-79, and 50 ml of tetrahydrofuran solvent into a 118 ml amber bottle. To this solution was added 2.4 grams of benzimidazole perylene and 300 grams of 3.18 mm (1/8 inch) diameter stainless steel shot. This mixture was then placed on a ball mill for 96 hours. 10 grams of the resulting dispersion was then added to a solution containing 0.366 gram of PE-200 and 5.67 grams of tetrahydrofuran solvent. The resulting slurry was thereafter applied onto the adhesive interface with a 0.0127 mm (1/2 mil) gap Bird applicator to form a layer having a wet thickness of 0.0127 mm (0.5 mil). The layer was dried at 135°C for 5 minutes in a forced air oven to form a dried thickness photo charge generating layer having a thickness of 1.2 micrometers. EXAMPLE IV A photoconductive imaging member was prepared as described in Example III, except that the polyvinyl butyral copolymer B-79 to copolyester Vitel PE-200 volume ratio in the mixed binder of the charge generating layer was 20 : 35. EXAMPLE V A photoconductive imaging member was prepared as described in Example III, except that the polyvinyl butyral copolymer B-79 to copolyester Vitel PE-200 volume ratio in the mixed binder of the charge generating layer was 27.5 : 27.5. EXAMPLE VI The electrical properties of photoconductive imaging members of Comparative Examples I and II as well as Examples III through V were investigated with a xerographic testing scanner comprising a cylindrical aluminum drum having a diameter of 24.26 cm (9.55 inches), to evaluate their respective photoelectrical integrity. The test samples were taped onto the drum. When rotated, the drum carrying the samples produced a constant surface speed of 76.3 cm (30 inches) per second. A direct current pin corotron, exposure light, erase light, and five electrometer probes were mounted around the periphery of the mounted photoreceptor samples. The sample charging time was 33 milliseconds. Both expose and erase lights were broad band white light (400-700 nm) outputs, each supplied by a 300 watt output Xenon arc lamp. The relative locations of the probes and lights are indicated in Table A below: ELEMENT ANGLE (Degrees) POSITION (mm) DISTANCE FROM PHOTORECEPTOR (mm) Charge 0.0 18 (Pins) 12 (Shield) Probe 1 22.50 47.9 3.17 Expose 56.25 118.8 N.A. Probe 2 78.75 166.8 3.17 Probe 3 168.75 356.0 3.17 Probe 4 236.25 489.0 3.17 Erase 258.75 548.0 125.00 Probe 5 303.75 642.9 3.17 The test samples were first rested in the dark for at least 60 minutes to ensure achievement of equilibrium with the testing conditions at 40 percent relative humidity and 21°C. Each sample was then negatively charged in the dark to a development potential of about 900 volts. The charge acceptance of each sample and its residual potential after discharge by front erase exposure to 4 x 10 -5 J/cm 2 (400 ergs/cm 2 ) were recorded. The test procedure was repeated to determine the photo induced discharge characteristic (PIDC) of each sample by different light energies of up to 2 x 10 -6 J/cm 2 (20 ergs/cm 2 ). The duplicate sets of photoconductive imaging members of Comparative Examples I and II and Examples III to V were again tested in a motionless scanner by Differential Increase In Dark Decay (DIDD) measurement technique for charge deficient spot (microdefect) levels. The test involved the following steps: (a) providing at least a first electrophotographic imaging member having a known differential increase in dark decay value, the imaging member comprising an electrically conductive layer and at least one photoconductive layer, (b) repeatedly subjecting the at least one electrophotographic imaging member to cycles comprising electrostatic charging and light discharging steps, (c) measuring dark decay of the at least one photoconductive layer during cycling until the amount of dark decay reaches a crest value, (d) establishing with the crest value a first reference datum for dark decay crest value at an initial applied field between 24 volts/micrometer and 40 volts/micrometer, (e) establishing with the crest value a second reference datum for dark decay crest value at a final applied field between 64 volts/micrometer and 80 volts/micrometer, (f) determining the differential increase in dark decay between the first reference datum and the second reference datum for the first electrophotographic imaging member to establish a known differential increase in dark decay value, (g) repeatedly subjecting a virgin electrophotographic imaging member to aforementioned cycles comprising electrostatic charging and light discharging steps until the amount of dark decay reaches a crest value for the virgin which remains substantially constant during further cycling, (h) establishing with the crest value for the virgin electrophotographic imaging member a third reference datum for dark decay crest value at the same initial applied field employed in step (d), (i) establishing with the crest value for the virgin electrophotographic imaging member a fourth reference datum for dark decay crest value at the same final applied field employed in step (e), (j) determining the differential increase in dark decay between the third reference datum and the fourth reference datum to establish a differential increase in dark decay value for the virgin electrophotographic imaging member, and (k) comparing the differential increase in dark decay value of the virgin electrophotographic imaging member with the known differential increase in dark decay value to ascertain the projected microdefect levels of the virgin electrophotographic imaging member. The motionless scanner is described in US-A 5,175,503. To conduct the DIDD and motionless scanner cycling tests described above, the photoreceptor sample was first coated with a gold electrode on the imaging surface. The sample was then connected to a DC power supply through a contact to the gold electrode. The sample was charged to a voltage by the DC power supply. A relay was connected in series with the sample and power supply. After 100 milliseconds of charging, the relay was opened to disconnect the power supply from the sample. The sample was dark rested for a predetermined time, then exposed to a light to discharge the surface voltage to the background level and thereafter exposed to more light to further discharge to the residual level. The same charge-dark and rest-erase cycle was repeated for a few cycles until a crest value of dark decay was reached. The sample surface voltage was measured with a non-contact voltage probe during this cycling period. Additional duplicate sets of photoconductive imaging members of all the above Examples were also evaluated for adhesive properties using a 180° (reverse) peel test technique. The 180° peel strength was determined by cutting a minimum of five 1.28 x 15.3 cm (0.5 inch x 6 inches) imaging member samples from each of these Examples. For each sample, the charge transport layer is partially stripped from the test imaging member sample with the aid of a razor blade and then hand peeled to about 8.9 cm (3.5 inches) from one end to expose part of the underlying charge generating layer. The test imaging member sample is secured with its charge transport layer surface toward a 2.54 x 15.3 x 1.28 cm (1 inch x 6 inches x 0.5 inch) aluminum backing plate with the aid of two sided adhesive tape, 1.3 cm (1/2 inch) width Scotch® Magic Tape #810, available from 3M Company. At this condition, the anti-curl layer/substrate of the stripped segment of the test sample can easily be peeled away 180° from the sample to cause the adhesive layer to separate from the charge generating layer. The end of the resulting assembly opposite to the end from which the charge transport layer is not stripped is inserted into the upper jaw of an Instron Tensile Tester. The free end of the partially peeled anti-curl/substrate strip is inserted into the lower jaw of the Instron Tensile Tester. The jaws are then activated at a 2.54 cm/min (1 inch/min) crosshead speed, a 2 inch chart speed and a load range of 200 grams to 180° peel the sample at least 5.08 cm (2 inches). The load monitored with a chart recorder is calculated to give the peel strength by dividing the average load required for stripping the anti-curl layer with the substrate by the width of the test sample. Although the electrical properties obtained for the photoconductive imaging members of the two Comparative Examples and all the remaining Examples exhibited about equivalent photoelectrical characteristics, the imaging members of Comparative Example II and Examples III, IV, and V employed a charge generating layer containing a polyvinyl butyral copolymer B-79 (PVB) binder or a polymer bend having a mixture of polyvinyl butyral copolymer B-79 (PVB) and copolyester Vitel PE-200, as shown in the following Table B, gave reduced Charge deficient spots, as reflected in the reduction of DIDD values compared to the result obtained for the control imaging member counterpart of Comparative Example I. EXAMPLE CGL BINDER D I D D (VOLTS) PEEL STRENGTH (GMS/CM) I PCZ 415 5.6 II PVB 162 1.3 III PVB/PE-200 203 20.1 IV PVB/PE-200 190 22.8 V PVB/PE-200 164 13.1 The data in the above table indicate that replacing the polymer binder poly(4,4'-diphenyl-1,1'-cyclohexane carbonate) PCZ -200 from the charge generating layer of the imaging member of Comparative Example I with polyvinyl butyral copolymer B-79, as described in Comparative Example II, though, could produce significant DIDD reduction, unfortunately the adhesion bond strength of the resulting imaging member was seen to drop from 5.6 grams/cm to a low value of only 1.3 grams/cm. This imaging member layer adhesion bond strength reduction had been implicated in spontaneous delamination of the imaging member belt during electrophotographic imaging cycling under machine service conditions. Moreover, the results listed in the table above also show that introduction of a compatible second polymer, such as copolyester Vitel PE-200 to blend with the polyvinyl butyral copolymer B-79 to form a mixed binder for the charge generating layer application, provides a robust mechanical effect to substantially improve the layer adhesion bond strength.

Claims: An electrophotographic imaging member comprising a support substrate the surface of which being covered with at least two electrically conductive metal layers comprising zirconium and/or titanium with the outermost metal layer containing at least 50 percent by weight of zirconium, a hole blocking layer, an adhesive layer comprising a copolyester resin, a charge generation layer comprising photoconductive perylene or phthalocyanine particles dispersed in a film forming resin binder blend, said resin binder blend comprising polyvinyl butyral copolymer represented by the following general formula: wherein: x is a number such that the polyvinyl butyral content is between 50 and 75 mol percent, y is a number such that the polyvinyl alcohol content is between 12 and 50 mol percent, and z is a number such that the polyvinyl acetate content is between 0 and 15 mol percent, and a copolyester represented by the following general formula: wherein said diacid is selected from the group consisting of terephthalic acid, isophthalic acid, and mixtures thereof, said diol comprises ethylene glycol and 2,2-dimethyl propane diol, said mole ratio of diacid to diol is 1:1, said mole ratio of terephthalic acid to isophthalic acid is 1.2:1, said mole ratio of ethylene glycol to 2,2-dimethyl propane diol is 1.33:1, n is a number between 160 and 330, and the T g of said copolyester resin is between 50°C and 80°C, and a charge transport layer, said charge transport layer being non-absorbing in the spectral region at which the charge generation layer generates and injects photogenerated holes but being capable of supporting the injection of photogenerated holes from said charge generation layer and transporting said holes through said charge transport layer. The electrophotographic imaging member according to claim 1 wherein said binder blend consists of between 10 percent and 50 percent by weight of said polyvinyl butyral copolymer and between 90 percent and 50 percent by weight of said copolyester. The electrophotographic imaging member according to claim 1 or 2 wherein said polyvinyl butyral copolymer has a weight average molecular weight between 20,000 and 400,000. The electrophotographic imaging member according to any of claims 1 to 3 wherein said charge generation layer comprises between 20 percent and 90 percent by volume of said perylene pigment particles, based on the total weight of said charge generation layer. The electrophotographic imaging member according to any of claims 1 to 4 wherein said electrically conductive metal layers comprise a zirconium layer overlying a titanium layer, said zirconium layer having an oxidized outer surface, and wherein the combined thickness of said zirconium layer and said titanium layer is between 12 and 30 nm (120 and 300 Angstrom units). The electrophotographic imaging member according to any of claims 1 to 5 wherein said blocking layer comprises an organoamino siloxane. The electrophotographic imaging member according to any of claims 1 to 6 wherein said support substrate comprises a flexible belt. The electrophotographic imaging member according to any of claims 1 to 6 wherein said support substrate is a rigid drum.

Inventors: CARMICHAEL KATHLEEN M, GRABOWSKI EDWARD F, HORGAN ANTHONY M, LIMBURG WILLIAM W, MISHRA SATCHIDANAND, NORMANDIN SHARON E, PAI DAMODAR M, POST RICHARD L, SULLIVAN DONALD P, VON HOENE DONALD C, YU ROBERT C U, CARMICHAEL, KATHLEEN M., GRABOWSKI, EDWARD F., HORGAN, ANTHONY M., LIMBURG, WILLIAM W., MISHRA, SATCHIDANAND, NORMANDIN, SHARON E., PAI, DAMODAR M., POST, RICHARD L., SULLIVAN, DONALD P., VON HOENE, DONALD C., YU, ROBERT C.U.
Applicants: XEROX CORP, XEROX CORPORATION
Application year: 1997
Main classification: G03G5
IPC codes: G03G5, C08L29, C08F16