Patent Grant
9017906
Reference is made to commonly owned and co-pending, U.S. patent application Ser. No. 13/940,177 entitled “Imaging Members Having A Cross-Linked Anti-Curl Back Coating” to Robert C.U. Yu et al., electronically filed on the same day herewith; and U.S. patent application Ser. No. 13/940,145 entitled “Flexible Imaging Members Having Externally Plasticized Imaging Layers” to Robert C.U. Yu et al., electronically filed on the same day herewith, the entire disclosures of which are incorporated herein by reference in their entirety.
The presently disclosed embodiments relate generally to a flexible electrophotographic imaging member having an anticurl back coating. The anticurl back coating of the flexible electrophotographic imaging member of the present disclosure not only provides wear/scratch resistance, it also gives the resulting imaging member flatness to meet the functional requirement of electrophotographic imaging apparatuses. While the present anticurl back coating (ACBC) can be used in all conventional electrophotographic imaging member designs, particular attention is focused on its application in a flexible multi-layered electrophotographic imaging member comprising a plasticized imaging layer.
In conventional prior art electrophotographic flexible imaging members, there may be included a photoconductive layer including a single layer or composite layers. One type of composite photoconductive layer used in xerography is illustrated in U.S. Pat. No. 4,265,990 which describes an imaging member having at least two electrically operative layers. One layer comprises a photoconductive layer or charge generating layer which is capable of photogenerating holes and injecting the photogenerated holes into a contiguous charge transport layer. Generally, where the two electrically operative layers are supported on a conductive layer, the charge genearting layer is sandwiched between a contiguous charge transport layer and the supporting conductive layer. Alternatively, the charge transport layer may be sandwiched between the supporting electrode and a charge generating layer.
In the case where the charge generating layer is sandwiched between the outermost exposed charge transport layer and the electrically conducting layer, the outer surface of the charge transport layer is charged negatively and the conductive layer is charged positively. The charge generating layer then should be capable of generating electron hole pair when exposed image wise and inject only the holes through the charge transport layer. In the alternate case when the charge transport layer is sandwiched between the charge generating layer and the conductive layer, the outer surface of the charge generating layer is charged positively while conductive layer is charged negatively and the holes are injected through from the charge generating layer to the charge transport layer. The charge transport layer should be able to transport the holes with as little trapping of charge as possible. In flexible imaging member belt such as photoreceptor, the charge conductive layer may be a thin coating of metal on a flexible substrate support layer.
Typical negatively charged imaging member belts, such as flexible photoreceptor belt designs, are made of multiple layers comprising a flexible supporting substrate, a conductive ground plane, a charge blocking layer, an optional adhesive layer, a charge generating layer, a charge transport layer. The charge transport layer is usually the last layer, or the outermost layer, to be coated and is applied by solution coating then followed by drying the wet applied coating at elevated temperatures of about 120° C., and finally cooling it down to ambient room temperature of about 25° C. When a production web stock of several thousand feet of coated multilayered imaging member material is obtained after finishing solution application of the charge transport layer coating and through drying/cooling process, upward curling of the multilayered photoreceptor is observed. This upward curling is a consequence of thermal contraction mismatch between the charge transport layer and the substrate support. Since the charge transport layer in a typical imaging member has a coefficient of thermal contraction approximately 3.7 times greater than that of the flexible substrate support, the charge transport layer does therefore have a larger dimensional shrinkage than that of the substrate support as the imaging member web stock cools down to ambient room temperature. Since the typical flexible electrophotographic imaging member, if unrestrained, exhibits undesirable upward imaging member curling, an anticurl back coating, applied to the backside, is required to balance the curl. Thus, the application of anticurl back coating is necessary to provide the appropriate imaging member belt with desirable flatness.
Flexible electrophotographic imaging members having these electrically operative layers, as disclosed above, provide excellent electrostatic latent images when charged in the dark with a uniform negative electrostatic charge, exposed to a light image and thereafter developed with finely divided electroscopic marking particles. The resulting toner image is usually transferred to a suitable receiving member such as paper or to an intermediate transfer member which thereafter transfers the image to a receiving member such as paper.
However, when a negatively charged imaging member (e.g., in belt configuration) is in dynamic cyclic motion under a normal machine operation condition in the field, the anticurl back coating of conventional imaging members (as the outermost exposed backing layer) is subject to high surface contact friction when it slides and flexes over the machine subsystems of the belt support module, such as rollers, stationary belt guiding components, and backer bars. The mechanical/frictional sliding interactions of ACBC against the belt support module components have been found to create numbers of issues; such as: (1) exacerbate ACBC wear/abrasion, causing loss of anti-curling control capability and resulting in imaging member belt curling-up problem because the thinning of the ACBC reduces its curl control effectiveness to result in premature curling up of the imaging member that impacts normal imaging belt machine functioning condition, such as non-uniform charging for proper latent image formation; (2) create debris/dirt of ACBC wear-off that scatters and deposits on critical machine components such as lenses; (3) wear/abrasion/scratch damage in the ACBC does also produce unbalanced forces between the charge transport layer and the ACBC to cause micro belt ripples formation during electrophotographic imaging processe; (4) cause the development of tribo-electrical charge built-up in the ACBC that increases belt drive torque and, in some instances, it has been found to result in belt stalling; (5) in other cases, the tribo-electrical charge build up can be so high as to cause sparking; and lastly (6) under extensively cycled condition in precision electrostatographic imaging machines, an audible squeaky sound generation due to high contact friction interaction between the ACBC and the backer bars has also been a problem. Therefore, pre-mature ACBC failure shortens the imaging member belt functional life and requires frequent costly belt replacement in the field. Moreover, inclusion of an ACBC to provide flatness also incurs additional material and labor cost.
To overcome the abovementioned shortcomings association with the conventional ACBC in the flexible imaging member belt, research activities devoted to ACBC elimination have been pursued and ACBC-free flexible imaging members have been designed. To achieve the purpose of ACBC elimination, these imaging members are re-designed so that they contain a plasticized charge transport layer (CTL) which minimizes the CTL/substrate dimensional contraction mismatch for effecting internal tension stress/strain build-up reduction in the CTL. Even though the ACBC-free imaging members provide valid curl reduction, they do not render the desirable member flatness and still exhibit about 16 inch to about 25 inch diameter of curl-up curvature. As used herein, the measurement of curvature is determined by the following: a 2 inch×10 inch sample was cut from an ACBC-free imaging member and left unrestrained and free standing on a table. The extent of sample upward curling was then measured and recorded as its diameter of curl-up curvature.
While the fabricated ACBC-free flexible imaging members having a plasticized CTL produce good photo-electrical functioning stability results, quality copy prints, and curl suppression, they are unable to provide the resulting imaging members with complete flat configuration to meet the high volume machines imaging member belt flatness requirement. Moreover, the unprotected bottom side of the substrate of these imaging members is highly susceptible to the development of pre-mature onset of wear/scratch failure against the machine belt module support rollers and backer bars sliding mechanical friction action under a normal dynamic belt cycling machine operation condition. This causes generation of large amount of debris and/or dust particles inside the machine cavity to adversely impede proper imaging member belt functional operation.
Thus, there exists a need to provide a flexible electrophotographic imaging member with an ACBC re-formulation that improves physical/mechanical function and does not suffer from the abovementioned issues while providing the imaging member flatness to meet machine functioning requirement.
According to the present embodiments illustrated herein, there is provided a flexible electrophotographic imaging member comprising: a substrate; a charge generating layer disposed on the substrate; a charge transport layer disposed on the charge generating layer; and an anticurl back coating layer disposed on the substrate on a side opposite to the charge transport layer, wherein the anticurl back coating layer comprises crosslinked melamine formaldehyde and an organic or inorganic particle dispersion distributed thorough out the matrix of the crosslinked melamine formaldehyde.
In particular, the present embodiments provide a flexible electrophotographic imaging member comprising: a substrate; a charge generating layer disposed on the substrate; a charge transport layer disposed on the charge generating layer, the charge transport layer comprising a plasticizer; and an anticurl back coating disposed on the substrate on a side opposite to the charge transport layer, wherein the anticurl back coating layer comprises crosslinked melamine formaldehyde and an organic or inorganic particle dispersion distributed thorough out the matrix of the crosslinked melamine formaldehyde and a weight ratio of the organic or inorganic particle dispersion to the crosslinked melamine formaldehyde is from about 1:99 to about 1:9 in the anticurl back coating layer.
In further embodiments, there is provided an image forming apparatus for forming images on a recording medium comprising: a) an electrophotographic imaging member having a charge retentive-surface for receiving an electrostatic latent image thereon, wherein the imaging member comprises: a substrate; a charge generating layer disposed on the substrate; a charge transport layer disposed on the charge generating layer; and an anticurl back coating layer disposed on the substrate on a side opposite to the charge transport layer, wherein the anticurl back coating layer comprises crosslinked melamine formaldehyde and an organic or inorganic particle dispersion distributed thorough out the matrix of the crosslinked melamine formaldehyde; b) a development component adjacent to the charge-retentive surface for applying a developer material to the charge-retentive surface to develop the electrostatic latent image to form a developed image on the charge-retentive surface; c) a transfer component adjacent to the charge-retentive surface for transferring the developed image from the charge-retentive surface to a copy substrate; and d) a fusing component adjacent to the copy substrate for fusing the developed image to the copy substrate.
For a better understanding of the present disclosure, reference may be made to the accompanying figures.
In the following description, reference is made to the accompanying drawings, which form a part hereof and which illustrate the exemplary embodiments of the present disclosure herein and not for the purpose of limiting the same. It is also understood that other embodiments may be utilized and structural and operational changes may be made without departure from the scope of the present disclosure.
Conventional negatively charged flexible electrophotographic imaging member belts, comprising a single or composite photoconductive layers, such as for example, the charge generation layer (CGL) and CTL, through subsequent coating application of CGL over a flexible substrate support and CTL onto the CGL, exhibit undesirable upward imaging member curling. To offset and control the curl, an ACBC is coated onto the back side (opposite to the photoconductive layer(s) side) of the substrate support to impart the imaging member with desirable flatness.
In the present embodiments, there is provided negatively charged flexible electrophotographic imaging members that have flatness that meets the high volume machine requirement as well as provide service life extension in the field. This is achieved by providing methodology that renders the resulting imaging member belt with tribo-electrical charge suppression, superior wear/scratch resistant ACBC formulation, and photo-electrical stability enhancement. In embodiments, the flexible negatively charged multiple layered electrophotographic imaging member belt of conventional prior art is modified to have two formulations: (1) one comprising the inventive ACBC of this disclosure, and (2) one comprising a plasticized CTL/CGL and the inventive ACBC of this disclosure, to provide curl control to render imaging member belt flatness. The flexible negatively charged multiple layered electrophotographic imaging member belts described in all the preceding may alternatively include an optional top outermost protective overcoat layer over the CTL.
The specific terms are used in the following description for clarity, selected for illustration in the drawings and not to define or limit the scope of the disclosure. The structures in the figures are not drawn according to their relative proportions and the drawings should not be interpreted as limiting the disclosure in size, relative size, or location. In addition, though the discussion will address negatively charged systems, the imaging member belts of the present disclosure may also include material compositions designed to be used in positively charged systems. The terms “photoreceptor” or “photoconductor” or “photosensitive member” are generally used interchangeably with the terms “imaging member.” The term “electrostatographic” includes “electrophotographic” and “xerographic.” The terms “charge transport molecule” are generally used interchangeably with the terms “hole transport molecule.”
According to aspects illustrated herein, there is provided a negatively charged flexible imaging member belt comprising a flexible substrate support; a charge generating layer disposed on the substrate; a charge transport layer (CTL) disposed on the charge generating layer (CGL); and an anticurl back coating (ACBC) of present disclosure disposed on the substrate support on a side opposite to the CGL/CTL. The disclosed ACBC in the present embodiments is prepared to comprise a cross-linked melamine formaldehyde layer and an organic or inorganic particle dispersion.
Referring back to
Although the CGL 18 and CTL 20 of the negatively charged imaging member described and shown in all four figures have two separate layers, it will also be appreciated that the functional components of these two layers may be combined and formulated into a single plasticized layer to give a structurally simplified imaging member. Alternatively, the CGL 18 may also be disposed on top of the plasticized CTL 20, so the imaging member as prepared is therefore converted into a positively charge imaging member.
The Substrate
The imaging member support substrate 10 is a flexible layer and may be opaque but preferably to be substantially transparent, and may comprise any suitable organic or inorganic material having the requisite mechanical properties. The entire substrate can comprise the same material as that in the electrically conductive surface, or the electrically conductive surface can be merely a coating on the substrate. Any suitable electrically conductive material can be employed, such as for example, metal or metal alloy. Electrically conductive materials include copper, brass, nickel, zinc, chromium, stainless steel, conductive plastics and rubbers, aluminum, semitransparent aluminum, steel, cadmium, silver, gold, zirconium, niobium, tantalum, vanadium, hafnium, titanium, nickel, niobium, stainless steel, chromium, tungsten, molybdenum, paper rendered conductive by the inclusion of a suitable material therein or through conditioning in a humid atmosphere to ensure the presence of sufficient water content to render the material conductive, indium, tin, metal oxides, including tin oxide and indium tin oxide, and the like. It could be single metallic compound or dual layers of different metals and/or oxides.
The substrate 10 can also be formulated entirely of an electrically conductive material, or it can be an insulating material including inorganic or organic polymeric materials, such as MYLAR, a commercially available biaxially oriented polyethylene terephthalate (PET) from DuPont, or polyethylene naphthalate (PEN) available as KALEDEX 2000, with a ground plane layer 12 comprising a conductive titanium or titanium/zirconium coating, otherwise a layer of an organic or inorganic material having a semiconductive surface layer, such as indium tin oxide, aluminum, titanium, and the like, or exclusively be made up of a conductive material such as, aluminum, chromium, nickel, brass, other metals and the like. The thickness of the support substrate depends on numerous factors, including mechanical performance and economic considerations.
The substrate 10 may have a number of different configurations, such as for example, a plate, a cylinder, a drum, a scroll, an endless flexible belt, and the like. In the case of the substrate being in the form of a belt, as shown in the figures, the belt can be seamed or seamless. In certain embodiments, the photoreceptor is rigid. In certain embodiments, the photoreceptor is in a drum configuration.
The thickness of the substrate 10 of a flexible belt depends on numerous factors, including flexibility, mechanical performance, and economic considerations. The thickness of the flexible support substrate 10 of the present embodiments may be from 1.0 to about 7.0 mils; or from about 2.0 to about 5.0 mils.
The substrate support 10 is not soluble in the solvents used in each of the coating layer solutions. The substrate support 10 is optically transparent or semi-transparent. The substrate support 10 remains physical/mechanical stable at temperature below about 170° C. Therefore, at or below 170° C. the substrate support 10, below which temperature, may have a thermal contraction coefficient ranging from about 1×10−5/° C. to about 3×10−5/° C. and a Young's Modulus of between about 5×105 psi (3.5×104 Kg/cm2) and about 7×105 psi (4.9×104 Kg/cm2).
The Ground Plane
The electrically conductive ground plane 12 may be an electrically conductive metal layer which may be formed, for example, on the substrate 10 by any suitable coating technique, such as a vacuum depositing technique. Metals include aluminum, zirconium, niobium, tantalum, vanadium, hafnium, titanium, nickel, stainless steel, chromium, tungsten, molybdenum, and other conductive substances, and mixtures thereof. The conductive layer may vary in thickness over substantially wide ranges depending on the optical transparency and flexibility desired for the electrophotoconductive member. Accordingly, for a flexible photoresponsive imaging device, the thickness of the conductive layer is from about 20 Angstroms to about 750 Angstroms, or from about 50 Angstroms to about 200 Angstroms, for an optimum combination of electrical conductivity, flexibility and light transmission.
Regardless of the technique employed to form the metal layer, a thin layer of metal oxide forms on the outer surface of most metals upon exposure to air. Thus, when other layers overlying the metal layer are characterized as “contiguous” layers, it is intended that these overlying contiguous layers may, in fact, contact a thin metal oxide layer that has formed on the outer surface of the oxidizable metal layer. Generally, for rear erase exposure, a conductive layer light transparency of at least about 15 percent is desirable. The conductive layer need not be limited to metals. Other examples of conductive layers may be combinations of materials such as conductive indium tin oxide as transparent layer for light having a wavelength between about 4000 Angstroms and about 9000 Angstroms or a conductive carbon black dispersed in a polymeric binder as an opaque conductive layer.
The Hole Blocking Layer
After deposition of the electrically conductive ground plane layer 12, the hole blocking layer 14 may be applied thereto. Electron blocking layers for positively charged photoreceptors allow holes from the imaging surface of the photoreceptor to migrate toward the conductive layer. For negatively charged photoreceptors, any suitable hole blocking layer capable of forming a barrier to prevent hole injection from the conductive layer to the opposite photoconductive layer may be utilized. The hole blocking layer may include polymers such as polyvinylbutryral, epoxy resins, polyesters, polysiloxanes, polyamides, polyurethanes and the like, or may be nitrogen containing siloxanes or nitrogen containing titanium compounds such as trimethoxysilyl propylene diamine, hydrolyzed trimethoxysilyl propyl ethylene diamine, N-beta-(aminoethyl) gamma-amino-propyl trimethoxy silane, isopropyl 4-aminobenzene sulfonyl, di(dodecylbenzene sulfonyl)titanate, isopropyl di(4-aminobenzoyl)isostearoyl titanate, isopropyl tri(N-ethylamino-ethylamino)titanate, isopropyl trianthranil titanate, isopropyl tri(N,N-dimethylethylamino)titanate, titanium-4-amino benzene sulfonate oxyacetate, titanium 4-aminobenzoate isostearate oxyacetate, [H2N(CH2)4]CH3Si(OCH3)2, (gamma-aminobutyl) methyl diethoxysilane, and [H2N(CH2)3]CH3Si(OCH3)2 (gamma-aminopropyl) methyl diethoxysilane, as disclosed in U.S. Pat. Nos. 4,338,387, 4,286,033 and 4,291,110.
The hole blocking layer should be continuous and have a thickness of less than about 0.5 micrometer because greater thicknesses may lead to undesirably high residual voltage. A hole blocking layer of between about 0.005 micrometer and about 0.3 micrometer is used because charge neutralization after the exposure step is facilitated and optimum electrical performance is achieved. A thickness of between about 0.03 micrometer and about 0.06 micrometer is used for hole blocking layers for optimum electrical behavior. 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, chemical treatment and the like. For convenience in obtaining thin layers, the blocking layer is 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, heating and the like. Generally, a weight ratio of hole blocking layer material and solvent of between about 0.05:100 to about 0.5:100 is satisfactory for spray coating.
The Adhesive Layer
An optional separate adhesive interface layer 16 may be provided in certain configurations, such as, for example, in flexible web configurations. In the embodiment illustrated in the figure, the interface layer 16 would be situated between the blocking layer 14 and the CGL 18. The interface layer may include a copolyester resin. Exemplary polyester resins which may be utilized for the interface layer include polyarylatepolyvinylbutyrals, such as ARDEL POLYARYLATE (U-100) commercially available from Toyota Hsutsu Inc., VITEL PE-100, VITEL PE-200, VITEL PE-200D, and VITEL PE-222, all from Bostik Inc., 49,000 polyester from Rohm Hass, polyvinyl butyral, and the like. The adhesive interface layer may be applied directly to the hole blocking layer 14. Thus, the adhesive interface layer in embodiments is in direct contiguous contact with both the underlying hole blocking layer 14 and the overlying CGL 18 to enhance adhesion bonding to provide linkage. In yet other embodiments, the adhesive interface layer is entirely omitted.
Any suitable solvent or solvent mixtures may be employed to form a coating solution of the polyester for the adhesive interface layer. Solvents may include tetrahydrofuran, toluene, monochlorobenzene, methylene chloride, cyclohexanone, and the like, and mixtures thereof. Any other suitable and conventional technique may be used to mix and thereafter apply the adhesive layer coating mixture to the hole blocking layer. Application techniques may include spraying, dip coating, roll coating, wire wound rod coating, and the like. Drying of the deposited wet coating may be effected by any suitable conventional process, such as oven drying, infrared radiation drying, air drying, and the like.
The adhesive interface layer 16 may have a thickness of at least about 0.01 micrometer, and no more than about 900 micrometers after drying. In certain embodiments, the dried thickness is from about 0.03 micrometer to about 1.00 micrometer, or from about 0.05 micrometer to about 0.50 micrometer.
The Ground Strip Layer
The ground strip layer 19 may comprise a film-forming polymer binder and electrically conductive particles. Typical film forming binder may include, for example, A-B diblock copolymer, polycarbonate, polystyrene, polyacrylate, polyarylate, and the like. Any suitable electrically conductive particles may be used in the electrically conductive ground strip layer 19. The ground strip 19 may comprise materials which include those enumerated in U.S. Pat. No. 4,664,995. Electrically conductive particles include carbon black, graphite, copper, silver, gold, nickel, tantalum, chromium, zirconium, vanadium, niobium, indium tin oxide and the like. The electrically conductive particles may have any suitable shape. Shapes may include irregular, granular, spherical, elliptical, cubic, flake, filament, and the like. The electrically conductive particles should have a particle size less than the thickness of the electrically conductive ground strip layer to avoid an electrically conductive ground strip layer having an excessively irregular outer surface. An average particle size of less than about 10 micrometers generally avoids excessive protrusion of the electrically conductive particles at the outer surface of the dried ground strip layer and ensures relatively uniform dispersion of the particles throughout the matrix of the dried ground strip layer. The concentration of the conductive particles to be used in the ground strip depends on factors such as the conductivity of the specific conductive particles utilized.
The ground strip layer 19 may have a thickness of from about 7 micrometers to about 42 micrometers, from about 14 micrometers to about 27 micrometers, or from about 17 micrometers to about 22 micrometers.
The Charge Generation Layer
The CGL 18 may thereafter be applied to the undercoat layer 14. Any suitable charge generation binder including a charge generating/photoconductive material, which may be in the form of particles and dispersed in a film-forming binder, such as an inactive resin, may be utilized. Examples of charge generating materials include, for example, inorganic photoconductive materials such as amorphous selenium, trigonal selenium, and selenium alloys selected from the group consisting of selenium-tellurium, selenium-tellurium-arsenic, selenium arsenide and mixtures thereof, and organic photoconductive materials including various phthalocyanine pigments such as the X-form of metal free phthalocyanine, metal phthalocyanines such as vanadyl phthalocyanine and copper phthalocyanine, hydroxy gallium phthalocyanines, chlorogallium phthalocyanines, titanyl phthalocyanines, quinacridones, dibromo anthanthrone pigments, benzimidazole perylene, substituted 2,4-diamino-triazines, polynuclear aromatic quinones, enzimidazole perylene, and the like, and mixtures thereof, dispersed in a film-forming polymeric binder. Selenium, selenium alloy, benzimidazole perylene, and the like and mixtures thereof may be formed as a continuous, homogeneous charge generation layer. Benzimidazole perylene compositions are well known and described, for example, in U.S. Pat. No. 4,587,189, the entire disclosure thereof being incorporated herein by reference. Multi-charge generation layer compositions may be used where a photoconductive layer enhances or reduces the properties of the charge generation layer. Other suitable charge generating materials known in the art may also be utilized, if desired. The charge generating materials selected should be sensitive to activating radiation having a wavelength between about 400 and about 900 nm during the imagewise radiation exposure step in an electrophotographic imaging process to form an electrostatic latent image. For example, hydroxygallium phthalocyanine absorbs light of a wavelength of from about 370 to about 950 nanometers, as disclosed, for example, in U.S. Pat. No. 5,756,245.
A number of titanyl phthalocyanines, or oxytitanium phthalocyanines for the photoconductors illustrated herein are photogenerating pigments known to absorb near infrared light around 800 nanometers, and may exhibit improved sensitivity compared to other pigments, such as, for example, hydroxygallium phthalocyanine. Generally, titanyl phthalocyanine is known to have five main crystal forms known as Types I, II, III, X, and IV. For example, U.S. Pat. Nos. 5,189,155 and 5,189,156, the disclosures of which are totally incorporated herein by reference, disclose a number of methods for obtaining various polymorphs of titanyl phthalocyanine. Additionally, U.S. Pat. Nos. 5,189,155 and 5,189,156 are directed to processes for obtaining Types I, X, and IV phthalocyanines. U.S. Pat. No. 5,153,094, the disclosure of which is totally incorporated herein by reference, relates to the preparation of titanyl phthalocyanine polymorphs including Types I, II, III, and IV polymorphs. U.S. Pat. No. 5,166,339, the disclosure of which is totally incorporated herein by reference, discloses processes for preparing Types I, IV, and X titanyl phthalocyanine polymorphs, as well as the preparation of two polymorphs designated as Type Z-1 and Type Z-2.
Any suitable inactive resin materials may be employed as a binder in the CGL 18, including those described, for example, in U.S. Pat. No. 3,121,006, the entire disclosure thereof being incorporated herein by reference. Organic resinous binders include thermoplastic and thermosetting resins such as one or more of polycarbonates, polyesters, polyamides, polyurethanes, polystyrenes, polyarylethers, polyarylsulfones, polybutadienes, polysulfones, polyethersulfones, polyethylenes, polypropylenes, polyimides, polymethylpentenes, polyphenylene sulfides, polyvinyl butyral, polyvinyl acetate, polysiloxanes, polyacrylates, polyvinyl acetals, polyamides, polyimides, amino resins, phenylene oxide resins, terephthalic acid resins, epoxy resins, phenolic resins, polystyrene and acrylonitrile copolymers, polyvinylchloride, vinylchloride and vinyl acetate copolymers, acrylate copolymers, alkyd resins, cellulosic film formers, poly(amideimide), styrene-butadiene copolymers, vinylidenechloride/vinylchloride copolymers, vinylacetate/vinylidene chloride copolymers, styrene-alkyd resins, and the like. Another film-forming polymer binder is PCZ-400 (poly(4,4′-dihydroxy-diphenyl-1-1-cyclohexane) which has a viscosity-molecular weight of 40,000 and is available from Mitsubishi Gas Chemical Corporation (Tokyo, Japan).
The charge generating material can be present in the resinous binder composition in various amounts. Generally, the charge generating material is dispersed in an amount of from about 5 percent to about 95 percent by volume, from about 20 percent to about 80 percent by volume, or from about 40 percent to about 60 percent by volume of the resinous binder composition.
The CGL 18 containing the charge generating material and the resinous binder material generally ranges in thickness of from about 0.1 micrometer to about 5 micrometers, or from about 0.2 micrometer to about 3 micrometers. In certain embodiments, the charge generating materials in CGL 18 may include chlorogallium phthalocyanine, hydroxygallium phthalocyanines, or mixture thereof.
The CGL thickness is generally related to binder content. Higher binder content compositions generally employ thicker layers for charge generation layers.
The Conventional Charge Transport Layer
Although the CTL is discussed specifically in terms of a single layer 20, the details apply to embodiments having dual or multiple charge transport layers. The CTL 20 of conventional design is typically applied by solution coating over the CGL 18. In the coating process, the CTL along the adjacent ground strip layer is disposed on the CGL by co-coating application. The conventional CTL 20 may include a film forming transparent organic polymer or a non-polymeric material. Such transparent organic polymers and non-polymeric materials are capable of supporting the injection of photogenerated holes or electrons from the CGL 18 to allow the transport of these holes/electrons through the conventional CTL 20 to selectively discharge the surface charge on the imaging member surface. During the electrophotgraphic imaging process, the conventional CTL 20 supports holes transporting, and protects the CGL 18 from abrasion or chemical attack, thereby extends the service life of the imaging member. Interestingly, the conventional CTL 20 may be a substantially non-photoconductive material, yet it supports the injection of photogenerated holes from the CGL 18 below.
The conventional CTL 20 is typically transparent in a wavelength region in which the electrophotographic imaging member is to be used when exposure is affected there to ensure that most of the incident radiation is utilized by the underlying charge generation layer 18. The conventional CTL 20 should exhibit excellent optical transparency with negligible light absorption and no charge generation when exposed to a wavelength of light useful in xerography, e.g., 400 to 900 nanometers. In the case when the imaging member is prepared with the use of a transparent support substrate 10 and also a transparent conductive ground plane 12, image wise exposure or erase may alternatively (or optionally) be accomplished through the substrate 10 with all light passing through the back side of the support substrate 10. In this particular case, the materials of the conventional CTL 20 need not have to be able to transmit light in the wavelength region of use for electrophotographic imaging processes if the charge generating layer 18 is sandwiched between the support substrate 10 and the conventional CTL 20. In all events, the top conventional CTL 20 in conjunction with the charge generating layer 18 is an insulator to the extent that an electrostatic charge deposited/placed over the conventional CTL 20 is not conducted in the absence of radiant illumination. Importantly, the conventional CTL 20 should trap minimal or no charges as the charge pass through it during the image copying/printing process.
Typically, the conventional CTL 20 disclosed in all prior arts is a binary solid solution comprising a film forming polymer and charge transport compound or activating compound useful as an additive dissolved or molecularly dispersed in an electrically inactive polymeric material, such as a polycarbonate binder, to form a solid solution and thereby making this material electrically active. “Dissolved” refers, for example, to forming a solid solution in which the small molecule is dissolved in the polymer to form a homogeneous phase; and molecularly dispersed in all descriptions refers, for example, to charge transporting molecules dispersed in the polymer, the small molecules being dispersed in the polymer on a molecular scale.
The charge transport component may be added to a plasticized film-forming polymeric material which is otherwise incapable of supporting the injection of photogenerated holes from the charge generation material and incapable of allowing the transport of these holes through. This addition converts the electrically inactive polymeric material to a material capable of supporting the injection of photogenerated holes from the CGL 18 and capable of allowing the transport of these holes through the conventional CTL 20 in order to discharge the surface charge on the conventional CTL 20. The high mobility charge transport component may comprise small molecules of an organic compound which cooperate to transport charge between molecules and ultimately to the surface of the conventional CTL 20.
A number of charge transport compounds can be included in the conventional CTL 20. Examples of charge transport components are aryl amines of the following formulas:
wherein each X is independently alkyl, alkoxy, aryl, and derivatives thereof, or a halogen, or mixtures thereof. In certain embodiments, each X is independently Cl or methyl. Additional examples of charge transport components are aryl amines of the following formulas:
wherein X, Y and Z are independently alkyl, alkoxy, aryl, halogen, or mixtures thereof, and wherein at least one of Y and Z are present.
Alkyl and alkoxy may be substituted or unsubstituted, containing from 1 to about 25 carbon atoms, and more specifically, from 1 to about 12 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, and the corresponding alkoxides. Aryl may be substituted or unsubstituted, containing from 6 to about 36 carbon atoms, such as phenyl, and the like. Halogen includes chloride, bromide, iodide, and fluoride.
Exemplary charge transport components include aryl amines such as N,N′-diphenyl-N,N′-bis(methyl)phenyl)-1,1-biphenyl-4,4′-diamine, N,N,N′,N′-tetra-p-tolyl-1,1′-biphenyl-4,4′-diamine, N,N′-diphenyl-N,N′-bis(chlorophenyl)-1,1′-biphenyl-4,4′-diamine, N,N′-bis(4-butylphenyl)-N,N′-di-p-tolyl-[p-terphenyl]-4,4′-diamine, N,N′-bis(4-butylphenyl)-N,N′-di-m-tolyl-[p-terphenyl]-4,4′-diamine, N,N′-bis(4-butylphenyl)-N,N′-di-o-tolyl-[p-terphenyl]-4,4′-diamine, N,N′-bis(4-butylphenyl)-N,N′-bis-(4-isopropylphenyl)-[p-terphenyl]-4,4′-diamine, N,N′-bis(4-butylphenyl)-N,N′-bis-(2-ethyl-6-methylphenyl)-[p-terphenyl]-4,4′-diamine, N,N′-bis(4-butylphenyl)-N,N′-bis-(2,5-dimethylphenyl)-[p-terphenyl]-4,4′-diamine, N,N′-diphenyl-N,N′-bis(3-chlorophenyl)-[p-terphenyl]-4,4′-diamine, In one embodiment, the charge transport component is N,N′-diphenyl-N,N′-bis(3-methyl phenyl)-1,1′-biphenyl-4,4′-diamine (TPD) and N,N,N′,N′-tetra-p-tolyl-1,1′-biphenyl-4,4′-diamine (TM-TPD), and the like. Other known charge transport layer components may be selected in embodiments, reference for example, U.S. Pat. Nos. 4,921,773 and 4,464,450, the disclosures of which are totally incorporated herein by reference.
In one embodiment, the charge transport component is N,N′-diphenyl-N,N-bis(3-methyl phenyl)-1,1′-biphenyl-4,4′-diamine (TPD). In another embodiment, the charge transport component is N,N,N′,N′-tetra-p-tolyl-1,1′-biphenyl-4,4′-diamine (TM-TPD).
Examples of the binder materials selected for the CTL 20 include components, such as those described in U.S. Pat. No. 3,121,006, the disclosure of which is totally incorporated herein by reference. Specific examples of polymer binder materials include polycarbonates, polyarylates, acrylate polymers, vinyl polymers, cellulose polymers, polyesters, polysiloxanes, polyamides, polyurethanes, poly(cyclo olefins), epoxies, and random or alternating copolymers thereof. In one embodiment, the charge transport layer includes polycarbonates.
Typically, the formulation of the conventional CTL 20 is a solid solution which includes a charge transport compound molecularly dispersed or dissolved in a film forming polycarbonate binder, such as poly(4,4′-isopropylidene diphenyl carbonate) (i.e., bisphenol A polycarbonate), or poly(4,4′-diphenyl-1,1′-cyclohexane carbonate) (i.e., bisphenol Z polycarbonate).
Bisphenol A polycarbonate used for the conventional CTL 20 formulation is available commercially: MAKROLON (from Farbensabricken Bayer A.G) or FPC 0170 (from Mitsubishi Chemicals). Bisphenol A polycarbonate, poly(4,4′-isopropylidene diphenyl carbonate), has a weight average molecular weight of from about 80,000 to about 250,000, and a molecular structure of Formula X below:
wherein m is the degree of polymerization, from about 310 to about 990. Bisphenol Z polycarbonate, poly(4,4′-diphenyl-1,1′-cyclohexane carbonate), has a weight average molecular weight of from about 80,000 to about 250,000, and a molecular structure of Formula Y below:
wherein n is the degree of polymerization, from about 270 to about 850.
The conventional CTL 20 is an insulator to the extent that the electrostatic charge placed on the conventional CTL 20 surface is not conducted in the absence of illumination at a rate sufficient to prevent formation and retention of an electrostatic latent image thereon. The conventional CTL 20 is substantially non-absorbing to visible light or radiation in the region of intended use. The conventional CTL 20 is yet electrically “active,” as it allows the injection of photogenerated holes from the charge generation layer 18 to be transported through itself to selectively discharge a surface charge presence on the surface of the conventional CTL 20.
Any suitable and conventional technique may be utilized to form and thereafter apply the conventional CTL 20 coating solution to the supporting substrate layer. The conventional CTL 20 may be formed in a single coating step to give single conventional CTL 20 or in multiple coating steps to produce dual layered or multiple layered CTLs. Dip coating, ring coating, spray, gravure or any other coating methods may be used. For dual layered design, the CTL 20 includes a top CTL and a bottom CTL in contiguous contact with the CGL 18. The top CTL may contain less charge transport compound than the bottom CTL for impacting mechanically robust function. The top and bottom CTLs may have different thickness, or the same thickness. Drying of the applied wet coating layer(s) may be effected by any suitable conventional technique such as oven drying, infrared radiation drying, air drying and the like.
During the manufacturing process of a conventional negatively charged flexible imaging member, the conventional CTL 20 is coated over the CGL 18 by applying a CTL solution coating on top of the CGL 18, then subsequently drying the wet applied CTL coating at elevated temperatures of about 120° C., and finally cooling down the coated imaging member web to the ambient room temperature of about 25° C. Due to the thermal contraction mismatch between the conventional CTL 20 and the substrate support 10, the processed imaging member web (after finishing CTL drying/cooling process), if unrestrained, does exhibit spontaneous upward curling as a result of greater dimensional contraction of conventional CTL 20 than that of substrate support 10.
Without being bounded by theory, the development of this upward imaging member curling may be explained by the following mechanisms: (1) while the imaging member web after application of wet CTL coating (typically comprising equal parts of a polycarbonate binder and a specific diamine charge transport compound dissolved in an organic solvent) over a 3½ mil polyethylene naphthalate substrate (or a polyethylene terephthalate) is dried at elevated temperature (120° C.), the solvent(s) of the CTL coating solution evaporates leaving a viscous free flowing CTL liquid where the CTL releases internal stress, and maintains its lateral dimension stability without causing the occurrence of dimensional contraction; (2) during the cool down period, the temperature falls and reaches the glass transition temperature (Tg) of the CTL at 85° C., the CTL instantaneously solidifies and adheres to the underneath CGL as it transforms from being a viscous liquid into a solid layer; and (3) as the CTL temperature subsequently drops from its Tg of 85° C. down to the 25° C. room ambient, the solid CTL in the imaging member web laterally contracts more than the flexible substrate support due to significantly higher thermal coefficient of dimensional contraction than that of the substrate support. Such differential in dimensional contraction between these two layers results in internal tension strain built-up in the CTL and compression the substrate support layer, which therefore pulls the imaging member web upwardly to exhibit curling. That means the processed imaging member web (with the finished CTL coating obtained through drying/cooling process) does spontaneously curl upwardly into a roll.
The internal tension pulling strain built-up in the dried CTL 20 (caused by differential dimensional contraction between CTL 20 and substrate 10 to result in spontaneous upward imaging member curling) can be calculated according to the expression of equation (1) below:
ε=(αCTL−αsub)(TgCTL−25° C.) (1)
wherein ε is the internal strain build-in in the charge transport layer, αCTL and αsub are coefficient of thermal contraction of conventional CTL 20 and substrate 10 respectively, and TgCTL is the glass transition temperature of the conventional CTL 20.
The thickness of the conventional CTL 20 (being a single, dual, or multiple layered CTLs), after drying and cooling steps, is about 29 micrometers for optimum photoelectrical and mechanical results. Note that the conventional CTL 20 typically has a Young's Modulus of about 3.5×105 psi and a thermal contraction coefficient of about 6.6×10−5/° C. compared to the Young's Modulus of about 5.4×105 psi and the thermal contraction coefficient of about 1.8×10−5/° C. for the conventional polyethylene terephthalate substrate support.
In essence, if the completed imaging member web having a 29-micrometer thickness of dried conventional CTL 20 (comprising equal parts of a polycarbonate binder and a specific diamine charge transport compound), is coated over a 3½ mil polyethylene terephthalate (or a polyethylene naphthalate) substrate support 10 and being unrestrained, it will spontaneously curl-up into a 1½-inch roll. So to balance the curl and render desirable imaging member web flatness, a standard ACBC 1 having a conventional composition is generally included in prior imaging member web.
The Conventional Anti-Curl Back Coating Layer
As the imaging member web exhibits spontaneous upward curling after the completion of the conventional CTL 20 coating/drying and cooling processes, a conventional ACBC 1 is applied to the back side of the substrate 10 to counteract the curl and render flatness. Typically, a conventional ACBC for effective curl control is formulated to comprised of a film forming polymer and a small amount of an adhesion promoter. Although the film forming polymer employed in the conventional ACBC 1 formulation may be different from the polymer binder used in the conventional CTL 20, but it is preferred to be the exact same one as that in the conventional CTL. It is also important to mention that that the polymer(s) used in the conventional ACBC formulation and that in the conventional CTL has about equivalent thermal contraction coefficient to effect best imaging member curl control outcome. For imaging member having a typical 29 micrometers CTL 20 thickness, a conventional 17 micrometers polycarbonate ACBC 1 is need to balance/control the curl and render flatness.
The applied conventional ACBC 1 is, however, required to have suitable optically transmittance (e.g., transparency), so that the residual voltage remaining after completion of a photoelectrical imaging process on the imaging member surface can conveniently be erased by radiation illumination directed from the back side of the imaging member through the ACBC thickness of the imaging member during electrophotographic imaging processes. In addition, since the imaging member in flexible belt configuration is mounted over to encircle around a machine belt module and be supported by a number of belt module rollers and backer bars, so it is necessary that the ACBC 1 (under a dynamic imaging member belt cyclic machine functioning condition in the field) should also have adequate mechanical robustness of good wear resistance to withstand the frictional action against these belt module support components.
The Optional Overcoat Layer
Referring to
Disclosure Imaging Member I
The flexible imaging member web, shown in
Since the conventional prior art imaging members have a typical CTL 20 thickness in the range of from about 10 to about 35 micrometers, the disclosed cross-linked melamine formaldehyde ACBC 2 is required to have a thickness of between about 8 and about 32 micrometers to effect imaging member flatness control.
For a first exemplary embodiment of the present disclosure, the particle dispersed melamine-formaldehyde ACBC is formulated to have a binary material compositions by first reacting the melamine with formaldehyde to give methylolated melamines which are then subsequently cross-linked, among themselves, into a three-dimensional cross-linked network by condensation reaction activated at an elevated temperature or an elevated temperature and a catalyst. The term “methylolated melamine” means that the melamine is already reacted or combined with the formaldehyde. In embodiments, the elevated temperature is in a range of from about 120 to about 130° C. The mole ratio of melamine to formaldehyde is from about 1:2 to about 1:6. The chemical reactions leading to the formation of a cross-linked melamine-formaldehyde ACBC layer of the present disclosure are described and represented by the following two reaction steps:
The condensation reaction between two —OH terminal of different molecules may spontaneously occur at an elevated temperature to give a crosslinked network. In embodiments, the elevated temperature is in a range of from about 120 to about 130° C. Otherwise, the condensation reaction may alternatively be carried out in the present of a catalyst. Typical catalysts suitable for use to activate the cross-linking reaction or condensation reaction include dibutyltin dilaurate, zinc octoate, para-toluene sulfonic acid, and mixtures thereof. The mole ratio of melamine to formaldehyde may be from about 1:1 to about 1:3.
For a second exemplary embodiment, the particle dispersed melamine-formaldehyde ACBC layer may alternatively be re-formulated to have a triple material composition including melamine, formaldehyde, and a binder. The binder suitable for use in the creation of a triple composition cross-linked polyacrylate/melamine-formaldehyde ACBC of this disclosure is a polyhydroxyalkyl arcrylate or hydroxyl functional acrylic polyol which may be selected from the groups consisting of polyhydroxymethyl acrylate, polyhydroxyethyl acrylate, polyhydroxyproyl acrylate, polyhydroxybutyl acrylate, polyhydroxypentyl acrylate, polyhydroxyhexyl acrylate, and mixtures thereof. The mole ratio of melamine to formaldehyde is from about 1:1 to about 1:3. The polyhydroxyalkyl arcrylate may be present in an amount of from about 20 to about 50 weight percent, or from about 30 to about 40 weight percent, based on the total weight of the prepared dried cross-linked polyacrylate/melamine-formaldehyde ACBC.
The weight average molecular weight of polyhydroxyalkyl arcrylate is in a range of from about 5,000 to about 50,000, or from about 10,000 to about 30,000.
One specific example of a hydroxyl functional acrylic polyol binder is Joncryl 587 (a polyhydroxymethyl acrylate commercially available from BASF) having a weight average molecular weight of about 14,000 and contains hydroxyl groups at the polymer side chains readily for effective cross-linking reaction in the presence of methylolated melamine-formaldehyde to form a 3-dimensional network.
In essence, the particle dispersed melamine-formaldehyde ACBC of this disclosure can be prepared by adding a hydroxyl functional acrylic polyol to a methylolated melamine resin, such as, Cymel 303LF, commercially available from Cytec, with an optional catalyst, in a solvent to form a coating solution. The coating solution can be applied over substrate support opposite to the site of the CTL/CGL layers. The applied wet coating is then dried under an elevated temperature to evaporate away the solvent while the methylolated melamine-formaldehyde acts as a cross-linker to link with the hydroxyl side groups of the acrylic polyol molecules into a 3-dimensional cross-linked network ACBC of this disclosure.
The resulting melamine-formaldehyde ACBC layer of the present disclosure, obtained as either a binary material composition or a triple material composition described in the above embodiments, contains of from about 1 to about 10, or from about 2 to about 6 weight percent of an organic or inorganic particle dispersion in it material matrix based on the total weight of the prepared ACBC. To achieve a proper homogeneous dispersion, the particle size in all dimensions of the organic or inorganic particles used for the ACBC dispersion is required to be less than ⅓ the thickness of the prepared ACBC. The melamine-formaldehyde ACBC as prepared is an optically clear, substantially continuous, and uniform melamine-formaldehyde cross-linked coating layer.
Preparation of ACBC Free Imaging Member Containing Plasticized Charge Transport Layer, Charge Generation layer, and Ground Strip Layer
From imaging member manufacturing point of view, the addition of an ACBC in the conventional prior art flexible imaging member incurs material cost, adds labor involvement, and also reduces daily imaging member product throughput too, so efforts devoted to the elimination of ACBC 1 from the imaging member of
To minimize the dimensional thermal contraction mismatched magnitude between the CTL 20 and the support substrate 10 of the conventional imaging member in
In a specific embodiment, an 8% wt diethyl phthalate plasticizer incorporation is used in these layers to provide internal stress/strain reduction and render curl suppression, so the resulting ACBC-free imaging member as prepared has a substantially curl-free or nearly flat configuration. The thickness of the 8% wt diethyl phthalate plasticized CTL 20P (being a single, dual, or multiple layered CTLs with every layer plasticized) after drying is typically about 29 micrometers. However, a substantially curl-free or nearly flat configuration of this ACBC free imaging member does mean that it (a 2 inch by 10 inch cut piece of this member under unstrained/free standing condition) is not completely flatness since it still exhibits about 16 inch diameter of curl-up curvature.
Plasticized CTL and plasticized ground strip are described in U.S. patent application Ser. Nos. 12/762,257; 12/782,671; and 12/216,151, the entire disclosures of which are hereby incorporated by reference.
Disclosure Imaging Member II
The plasticizer incorporation into the CTL 20P, CGL 18P, and the ground strip layer 19P of an ACBC free imaging member of
Thus, to capture and maintain all the benefits offered by utilizing plasticized CTL 20P, CGL 18P, and ground strip 19P in the imaging member web of
Referring to
In one specific embodiment, the CTL 20P, CGL 18P, and ground strip 19P may be plasticized with 8% wt diethyl phthalate, based on the total weight of each respective plasticized layer. A 4-micrometer thick melamine formaldehyde ACBC 3F is employed to counteract a 29-micrometer thick and 8% diethyl phthalate plasticized CTL 20P to achieve complete imaging member curl control. The CTL 20P may be prepared to have a single, dual, or multiple layered design with every layer being plasticized. In still another specific embodiment, the plasticized CGL 18P and the CTL 20P may alternatively be combined and reformulated into a functional single plasticized layer to give a further structurally simplified imaging member from that shown in
The superior wear/scratch resistant and optically clear cross-linked melamine formaldehyde ACBC 3F in
In summary, the novel cross-linked melamine-formaldehyde ACBC layer, thus prepared according to each of the descriptions of this disclosure above, is a substantially continuous and uniform melamine-formaldehyde cross-linked coating layer having excellent optical clarity so that the residual voltage remaining after completion of a photoelectrical imaging process on the imaging member surface can conveniently be erased by radiation illumination directed from the back side of the imaging member belt through the entire ACBC thickness of the imaging member belt during electrophotographic imaging processes. For imaging member having a conventional CTL 20 of between about 10 and 35 micrometer thickness shown in
Typical solvent(s) used for the melamine-formaldehyde ACBC layer coating solution preparation may include 1-methoxy-2-propanol, methyl n-amy ketone, methyl ethyl ketone, n-butyl Acetate, xylene, toluene, glycol ether acetates, and mixtures thereof. Typical catalyst(s) used to activate the cross-linking reaction are selected from the group consisting of dibutyltin dilaurate, zinc octoate, p-touene sulfonic acid, and mixtures thereof. Generally, the weight ratio of the solid content of the coating solution to solvent is from about 0.2:10 to about 2:10, or from about 0.4:8 to about 4:8. Such weight ratio range of solid content to solvent content is satisfactory for use to give the variances of ACBC thickness. After application of the coating solution, the solvent in the wet coating ACBC may be removed by conventional techniques, such as, by vacuum in combination of heating, and the like.
The disclosed melamine-formaldehyde ACBC layer may be solution applied by any suitable conventional technique, such as, spraying, extrusion coating, dip coating, draw bar coating, gravure coating, silk screening, air knife coating, reverse roll coating, and the like with the solvent being removed after deposition of the coating layer by conventional techniques, such as, by vacuum in combination of heating, and the like. For the convenience of obtaining a thin ACBC coating layer of between about 2 and about 8 micrometers in thickness, the coating solution may be applied in the form of a dilute solution.
In electrophotographic reproducing or digital printing apparatuses using a flexible imaging member belt prepared to comprise a conventional CTL 20 or a plasticized CTL 20P (utilizing a melamine formaldehyde ACBC 2F or 3F of present disclosure), a light image is recorded in the form of an electrostatic latent image upon a photosensitive member and the latent image is subsequently rendered visible by the application of a developer mixture. The developer, having toner particles contained therein, is brought into contact with the electrostatic latent image to develop the image on the imaging member belt which has a charge-retentive surface. The developed toner image can then be transferred to a copy out-put substrate, such as paper, that receives the image via a transfer member.
Various exemplary embodiments encompassed herein include a method of imaging which includes generating an electrostatic latent image on an imaging member, developing a latent image, and transferring the developed electrostatic image to a suitable substrate.
While the description above refers to particular embodiments, it will be understood that many modifications may be made without departing from the spirit thereof. The accompanying claims are intended to cover such modifications as would fall within the true scope and spirit of embodiments herein.
The development of the presently disclosed embodiments will further be demonstrated in the non-limited Working Examples below. They are, therefore in all respects, to be considered as illustrative and not restrictive nor limited to the materials, conditions, process parameters, and the like recited herein. The scope of embodiments is being indicated by the appended claims rather than the foregoing description. All changes that come within the meaning of and range of equivalency of the claims are intended to be embraced therein. All proportions are by weight unless otherwise indicated.
Conventional Anticurl Back Coating Example
A conventional anti-curl back coating (ACBC) was prepared by combining 88.2 grams of poly(4,4′-isopropylidene diphenyl carbonate) (i.e., bisphenol A polycarbonate) resin (having weight average molecular weight, Mw, of 120,000 and available as FPC170 from Mitsubishi Chemicals), 7.12 grams VITEL PE-200 copolyester (available from Bostik, Inc. Middleton, Mass.) and 1,071 grams of methylene chloride in a carboy container to form a coating solution containing 8.2 percent solids. The container was covered tightly and placed on a roll mill for about 24 hours until the polycarbonate and polyester were dissolved in the methylene chloride to form the ACBC solution. The ACBC solution was then applied onto a 3.5 mils (89 micrometers) thickness biaxially oriented polyethylene naphthalate substrate (PEN, KADALEX, available from DuPont Teijin Films) by following the standard hand coating procedures and dried to a maximum temperature of 125° C. in a forced air oven for two minutes to produce a dried ACBC with a thickness of 17 micrometers. The dried ACBC of the conventional design had good optical clarity and gave a 99.9% light transmittance in the visible light wavelength.
The bisphenol A polycarbonate used has a molecular formula shown below:
where z is about 470.
(a) Binary Material Composition Melamine Formaldehyde ACBC Formulation:
The formulation of the disclosed melamine-formaldehyde ACBC, containing an organic or inorganic dispersion binary material compositions, was CYMEL 303LF a commercially available resin from Cytec CYMEL 303LF, as supplied from Cytec, was a methylolated melamine resin obtained by reacting melamine with formaldehyde to give methylolated melamines as described below:
The methylolated melamine resin as commercially available was dissolved in Dowanol (from Dow Chemicals) along with 0.2 percent weight catalyst para-toluene sulfonic acid (NACURE XP357 from King Industries), based on the combined weight of the resin and catalyst, and plus a predetermined amount of particles to give the ACBC coating solution of this disclosure. The ACBC solution was applied over a 3.5 mils (89 micrometers) polyethylene naphthalate substrate by hand coating process and then dried at 130° C. for three minute in a forced air oven to initiate the chemical reaction among the methylolated melamine molecules and give a 3-dimensional crosslinked melamine formaldehyde ACBC network according to the following condensation/cross-linking reaction:
The dried ACBC that was obtained had optical clarity equivalent to that of the control ACBC.
(b) Triple Material Composition Melamine Formaldehyde ACBC Formulation
The formulation of another melamine-formaldehyde ACBC made according to the present embodiments was alternatively modified by the inclusion of a film forming hydroxyl functional acrylic polyol binder to give a cross-linked polyacrylate/melamine-formaldehyde layer variance of triple material composition comprising melamine, formaldehyde, and an acrylic polyol binder.
The formulation of the triple material ACBC was carried out as follows:
An ACBC pre-coating solution was first prepared to contain the composition shown in Table 1.
It is noted that CYMEL 303LF (from Cytec) is a methylolated melamine (a reaction product of melamine and formaldehyde) to serve as cross-linking agent; JONCRYL 587 (a hydroxyl functional acrylic polyol from BASF) is the binder resin; and catalyst NACURE XP357 (from King Industries) is an ionic salt of p-toluene sulfonic acid compounded with a liquid organic amine in methanol. The NACURE XP357, as received from King Industries, contains 20 weight percent solid p-toluene sulfonic acid/amine ionic salts in 80 weight percent methanol solvent. All these components plus a predetermined amount of particles were mixed and dissolved with agitation in DOWANOL (a propylene glycol monomethyl ether solvent also known as 1-methoxy-2-propanol, available form Dow Chemicals) to give the pre-coating solution. The concentration of this pre-coating solution (20.68% wt solid) as prepared was further adjusted by adding it with DOWANOL to give a 16.7% wt solid final charge undercoat layer coating solution for application. The prepared ACBC coating solution was likewise applied onto a 3.5 mils (89 micrometers) thickness polyethylene naphthalate substrate by following the standard hand coating procedures and dried to a maximum temperature of 130° C. in the forced air oven for three minutes to produce 20 micrometers dried disclosed ACBC thickness. Both of the resulting ACBCs as prepared had reasonable optical transmission about equivalent to that of the conventional ACBC control.
In recapitulation, the resulting melamine-formaldehyde ACBC layer of the present disclosure, obtained as either a binary material composition or a triple material composition described in the above embodiments, contains of from about 1 to about 10, or from about 2 to about 6 weight percent of an organic or inorganic particle dispersion in it material matrix based on the total weight of the prepared ACBC. In addition, the particle size of the organic or inorganic particles used for ACBC dispersion is required to be less than 1/3 the thickness of the prepared ACBC for a proper dispersion. The melamine-formaldehyde ACBC as prepared is an optically clear, substantially continuous, and uniform melamine-formaldehyde cross-linked coating layer.
For charge transport without incorporation of a plasticizer, the ACBC has a thickness of from about 3 to about 32 micrometers to render imaging member flatness control. However, ACBC thickness was required to be from about 2 to about 8 micrometers when the imaging member employed a plasticized charge transport layer.
Control Imaging Member Preparation Example I
A conventional prior art negatively charged flexible electrophotographic imaging member web (as that illustrated in
An adhesive interface layer 16 was then applied by extrusion coating to the blocking layer with a coating solution containing 0.16 percent by weight of ARDEL polyarylate, having a weight average molecular weight of about 54,000, available from Toyota Hsushu, Inc., based on the total weight of the solution in an 8:1:1 weight ratio of tetrahydrofuran/monochloro-benzene/methylene chloride solvent mixture. The adhesive interface layer was allowed to dry for 1 minute at 125° C. in a forced air oven. The resulting adhesive interface layer had a dry thickness of about 0.02 micrometer.
The adhesive interface layer was thereafter coated over with a charge generating layer. The charge generating layer (CGL 18) dispersion was prepared as described below.
To a 4 ounce glass bottle was added IUPILON 200, a polycarbonate of poly(4,4′-diphenyl)-1,1′-cyclohexane carbonate (PC-z 200, available from Mitsubishi Gas Chemical Corporation) (0.45 grams), and tetrahydrofuran (50 milliliters), followed by hydroxygallium phthalocyanine Type V (2.4 grams) and ⅛ inch (3.2 millimeters) diameter stainless steel shot (300 grams). The resulting mixture was placed on a ball mill for about 20 to about 24 hours to obtain a slurry. Subsequently, a solution of poly(4,4′-diphenyl-1,1′-cyclohexane carbonate) (2.25 grams) having a weight average molecular weight of 20,000 (PC-z 200) dissolved in tetrahydrofuran (46.1 grams) was added to the hydroxygallium phthalocyanine slurry. The resulting slurry was placed on a shaker for 10 minutes and thereafter coated onto the adhesive interface 16 by extrusion application process to form a layer having a wet thickness of 0.25 mil. A strip of about 10 millimeters wide along one edge of the substrate web stock bearing the blocking layer 14 and the adhesive layer 16 was deliberately left uncoated by the CGL 18 to facilitate adequate electrical contact by a ground strip layer to be applied later. The resulting CGL 18 containing poly(4,4′-diphenyl)-1,1′-cyclohexane carbonate, tetrahydrofuran and hydroxygallium phthalocyanine was dried at 125° C. for 2 minutes in a forced air oven to form a dry charge generating layer having a thickness of 0.4 micrometers.
This coated web stock was simultaneously coated over with a charge transport layer (CTL 20) and a ground strip layer 19 by co-extrusion of the coating materials. The CTL was prepared as described below.
To an amber glass bottle was added bisphenol A polycarbonate thermoplastic having an average molecular weight of about 120,000 (FPC 0170, commercially available from Mitsubishi Chemicals) and a charge transport compound of N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine. The weight ratio of the bisphenol A polycarbonate thermoplastic and N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine was 1:1. The resulting mixture was dissolved in methylene chloride such that the solid weight percent in methylene chloride was 15 percent by weight. Such mixture was applied on the CGL 18 by extrusion to form a coating which upon drying in a forced air oven gave a dry CTL 20 of 29 micrometers thick. The strip, about 10 millimeters wide, of the adhesive layer 16 left uncoated by the CGL 18, was coated with a ground strip layer 19 during the co-extrusion process. The ground strip layer coating mixture was prepared as described below:
To a carboy container was added 23.8 grams of bisphenol A polycarbonate resin (FPC 0170) and 332 grams methylene chloride. The container was covered tightly and placed on a roll mill for about 24 hours until the polycarbonate was dissolved and gave a 7.9 percent by weight solution. The prepared solution was mixed for 15-30 minutes with about 94 grams of graphite dispersion solution (available as RW22790, from Acheson Colloids Company) to give ground strip layer coating solution. (Note: The graphite dispersion solution, RW22790 as commercially obtained, contained a 12.3 percent by weight solids including 9.41 parts by weight of graphite, 2.87 parts by weight of ethyl cellulose, and 87.7 parts by weight of solvent).
To provide a homogeneous graphite dispersion, the resulting ground strip layer coating solution was then mixed with the aid of a high shear blade dispersed in a water cooled, jacketed container to prevent the dispersion from overheating and losing solvent. The resulting dispersion was then filtered and the viscosity was adjusted with the aid of methylene chloride. This ground strip layer coating mixture was then applied, by co-extrusion with the CTL solution, to the electrophotographic imaging member web to form an electrically conductive ground strip layer 19 having a dried thickness of about 19 micrometers.
The imaging member web stock containing all of the above layers was then passed through 125° C. in a forced air oven for 3 minutes to simultaneously dry both the CTL 20 and the ground strip 19. Since the CTL has a Young's Modulus of 3.5×105 psi (2.4×104 Kg/cm2) and a thermal contraction coefficient of 6.5×10−5/° C. compared to the Young's Modulus of 5.5×105 psi (3.8×104 Kg/cm2) and thermal contraction coefficient of 1.8×10−5/° C. for the PEN substrate support 10, the CTL 20 was about 3.6 times greater in dimensional shrinkage than that of PEN substrate support. Therefore, the imaging member web if unrestrained at this point would curl upwardly into a 1½-inch tube.
To achieve imaging member curl control, a conventional ACBC 1 was prepared by combining 88.2 grams of FPC 0170 bisphenol A polycarbonate resin, 7.12 grams VITEL PE-2200 copolyester (available from Bostik, Inc. Middleton, Mass.), and 1,071 grams of methylene chloride in a carboy container to form a coating solution containing 8.2 percent solids. The container was covered tightly and placed on a roll mill for about 24 hours until the polycarbonate and polyester were dissolved in methylene chloride to form an anti-curl back coating solution. The ACBC coating solution as prepared was then applied to the rear surface (side opposite to the charge generating layer and CTL) of the electrophotographic imaging member web by extrusion coating and dried to a maximum temperature of 125° C. in a forced air oven for about 3 minutes to produce a dried ACBC 1 of conventional design which having a thickness of 17 micrometers and flattening the imaging member.
Disclosure Imaging Member Preparation Example I
A negatively charged flexible electrophotographic imaging member web of
Control Acbc-Free Imaging Member Preparation Example II
A control negatively charged flexible electrophotographic imaging member web (not shown) was prepared by using the exact same materials, compositions, and following identical procedures as described in the preceding EXAMPLE I CONTROL IMAGING MEMBER PREPARATION, but without the application of ACBC 1 while the CTL 20, CGL 18P, and the ground strip layer 19P were each plasticized by incorporation of 8% wt diethyl phthalate (DEP) in respective layer. The resulting ACBC-free imaging member web, having a plasticized CTL 20P, as obtained, is shown
It is important to emphasize that even though the nearly flat imaging member configuration refers in particular to an ACBC-free flexible negatively charge imaging member prepared to have the CTL/CGL/ground strip incorporated with a plasticizer in its material matrix to effect reduction of internal stress/strain build-up in the layers to minimize/suppress the extent of imaging member curling-up, plasticizing the CTL/CGL/ground strip layer by 8 weight percent DEP incorporation did only impact partial decrease in the thermal dimensional contraction differential between the CTL and PEN (or PET) substrate, without totally eliminating the curl. Therefore, the prepared imaging member web (though having a nearly flat configuration of exhibiting about 16 inch diameter of curl-up curvature) was still not giving total belt flatness to meet the stringent requirement for high volume machines.
The resulting nearly flat ACBC-free imaging member as prepared was also used to serve as another imaging member Control.
Disclosure Imaging Member Preparation Example II
Although the CONTROL ACBC-FREE IMAGING MEMBER PREPARATION EXAMPLE II described above (to contain 8% wt DEP plasticized CTL/ground strip) was able to give the benefits of producing: a nearly flat imaging member web configuration, with CTL fatigue cracking life extension, excellent long term photo-electrical cyclic stability, and copy print out quality improvement results in actual machine belt print test run, the plasticization of CTL/CGL/ground strip was still unable to totally eliminate imaging member curling to meet the stringent flatness requirement in high volume machines. Moreover, since the bottom PEN substrate support (without the protection of an ACBC) was exposed to numbers of belt module support rollers and backer bars mechanical friction interactions under a normal imaging member belt function in the high volume machine, pre-mature onset of PEN substrate wear/scratch failure had become a serious problem to outweigh and negate the benefits of the ACBC-free imaging member's practical application value.
To resolve these short comings and issues while preserving/maintaining the photo-electrical stability and copy print quality improvement benefits, the same negatively charged flexible ACBC-free electrophotographic imaging member web of the CONTROL ACBC-FREE IMAGING MEMBER PREPARATION EXAMPLE II, described above, was again prepared to have 8% wt DEP plasticized CTL 20P/CGL 18P/ground strip layer 19P, but with the inclusion of a thin cross-linked melamine formaldehyde ACBC 3F prepared according to the described ACBC 2 in the preceding DISCLOSURE IMAGING MEMBER PREPARATION EXAMPLE I except by using a diluted coating solution. The resulting ACBC 3F coated over the PEN substrate support 10 was a thin coating layer of 4 micrometer thick 5 weight percent PTFE dispersed crosslinked polyacrylate/melamine-formaldehyde ACBC layer that gave imaging member flatness control of curl-free configuration as that shown in
Adhesion and Wear/Scratch Assessments
The imagine member webs of Disclosure Imaging Member Preparation Example I (having ACBC 2F) and Disclosure Imaging Member Preparation Example II (having ACBC 3F), prepared according to these two preceding Disclosure Working Examples, were first tested for the adhesion bond strength to the PEN substrate 10 by 180° peel strength measurement. They were found to not separable from the PEN substrate, since melamine formaldehyde is by itself an excellent adhesive.
The ACBC 2F and 3F of the present embodiments was subsequently evaluated for coefficient of sliding friction against rubber and wear resistance against sliding glass surface along the convention prior art ACBC control to determine and compare each respective mechanical function.
For ACBC wear resistance assessment, the imaging member web of the Disclosure Examples I and II and the conventional imaging member control of Example I were each again cut to give a size of 1 inch (2.54 cm) by 12 inches (30.48 cm) sample and then determined for its respective resistance to wear. Testing was conducted by means of a dynamic mechanical cycling device in which glass tubes were skidded across and on the test surface on each sample. More specifically, one end of each test sample was clamped to a stationary post and the sample was looped upwardly over three equally spaced horizontal glass tubes and then downwardly over a stationary guide tube through a generally inverted “U” shaped path with the free end of the sample secured to a weight which provided one pound per inch width tension on the sample. The surface of the test sample bearing the ACBC was faced downwardly so that it would periodically be brought into sliding mechanical contact with the glass tubes. The glass tubes had a diameter of one inch.
Each tube was secured at each end to an adjacent vertical surface of a pair of disks that were rotatable about a shaft connecting the centers of the disks. The glass tubes were parallel to and equidistant from each other and equidistant from the shaft connecting the centers of the disks. Although the disks were rotated about the shaft, each glass tube was rigidly secured to the disk to prevent rotation of the tubes around each individual tube axis. Thus, as the disk rotated about the shaft, two glass tubes were maintained at all times in sliding contact with the surface of the ACBC. The axis of each glass tube was positioned about 4 cm from the shaft. The direction of movement of the glass tubes along the charge transport layer surface was away from the weighted end of the sample toward the end clamped to the stationary post. Since there were three glass tubes in the test device, each complete rotation of the disk was equivalent to three wear cycles in which the surface of the test sample was in sliding mechanical contact with a single stationary support tube during the testing. The rotation of the spinning disk was adjusted to provide the equivalent of 11.3 inches (28.7 cm) per second tangential speed. The extent of the ACBC wear-off by the sliding contact friction against the glass tubes was measured using a permascope at the end of a 330,000 wear cycles test.
The ACBCs of these imaging member webs were evaluated further for each propensity to scratch damage by scratch resistant test. Scratch resistance was conducted out by sliding a 6 grams load phonographic stylus over the ACBC surface at a rate of one centimeter per second. The depth of scratch damage of each ACBC caused by the stylus sliding mechanical action was then measured with a surface probe.
The results obtained for ACBC 180° peel-off strength, coefficient of sliding friction against rubber, and wear/scratch resistance are listed in Table 2 below:
Table 2 showed that the electrophotographic imaging member containing the disclosed ACBC formulated to comprise PTFE dispersed cross-linked polyacrylate/melamine-formaldehyde gave very good adhesion bonding strength to the PEN substrate (being not separable), because melamine formaldehyde is by itself a super adhesive. Very importantly, the wear and scratch resistance of the two ACBCs of Disclosure Imaging Member Preparation Examples I and II were much better than the conventional prior art ACBC of the imaging member control. The reasonable coefficient of friction against rubber of the disclosed ACBCs indicates proper belt drive capacity by the belt support module drive-roll for motion quality assurance and control. It is noted that the ACBCs of the imaging member of the Disclosure Examples caused nil or little tribo-electrical charging-up in contrast to that seen for the conventional imaging member ACBC control counterpart as each ACBC of these imaging members was sliding over belt module backer bars.
In summary, the present embodiments provide a physically/mechanically robust PTFE dispersed cross-linked polyacrylate/melamine-formaldehyde ACBC formulation, prepared according to the present embodiments, for practical application in flexible imaging members designed to contain either a conventional CTL or a plasticized CTL. The resulting ACBC formulation, as prepared, had uniform coating thickness and also provided enhanced physical and mechanical properties such as: scratch/wear resistance; excellent adhesion bonding to the support substrate; good optical clarity/transparency to allow the convenient of imaging member belt back erase by radiant light; and very importantly, excellent curling control to meet the imaging member belt flatness requirement for all the high volume machines.
Therefore, the experimental results obtained and demonstrated in all the above embodiments indicated that conventional prior art flexible imaging member belt prepared to include a PTFE dispersed cross-linked polyacrylate/melamine-formaldehyde ACBC of this disclosure for STD ACBC replacement could provide effective imaging member curl control and improve physical/mechanical function for achieving imaging member belt service extension in the field.
The foregoing demonstrates that imaging members employing a plasticized CTL for curl suppression did still require the inclusion of a PTFE dispersed cross-linked polyacrylate/melamine-formaldehyde ACBC formulation of the present disclosure to provide: (a) protection of the substrate support against pre-mature onset of back side of the belt wear failure under dynamic machine imaging member belt cycling condition in the field, (b) preservation/maintain the photo-electrical stability and copy print-out quality improvement benefits offered by the plasticized CTL, and very importantly (c) render imaging member flatness to meet stringent machine belt flatness requirement.
All the patents and applications referred to herein are hereby specifically, and totally incorporated herein by reference in their entirety in the instant specification.
It will be appreciated that several of the above-disclosed and other features and functions, or alternatives thereof, may be desirably combined into many other different systems or applications. Also that various presently unforeseen or unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompassed by the following claims. Unless specifically recited in a claim, steps or components of claims should not be implied or imported from the specification or any other claims as to any particular order, number, position, size, shape, angle, color, or material.
While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents as would fall within the true scope and spirit of embodiments herein.
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