WO2001051995A1 - Electrophotographic photoconductors comprising polyaryl ethers - Google Patents
Electrophotographic photoconductors comprising polyaryl ethers Download PDFInfo
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- WO2001051995A1 WO2001051995A1 PCT/US2001/000612 US0100612W WO0151995A1 WO 2001051995 A1 WO2001051995 A1 WO 2001051995A1 US 0100612 W US0100612 W US 0100612W WO 0151995 A1 WO0151995 A1 WO 0151995A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/07—Polymeric photoconductive materials
- G03G5/075—Polymeric photoconductive materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
- G03G5/0542—Polyvinylalcohol, polyallylalcohol; Derivatives thereof, e.g. polyvinylesters, polyvinylethers, polyvinylamines
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
- G03G5/0564—Polycarbonates
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
- G03G5/0567—Other polycondensates comprising oxygen atoms in the main chain; Phenol resins
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
- G03G5/0575—Other polycondensates comprising nitrogen atoms with or without oxygen atoms in the main chain
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0601—Acyclic or carbocyclic compounds
- G03G5/0612—Acyclic or carbocyclic compounds containing nitrogen
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0601—Acyclic or carbocyclic compounds
- G03G5/0612—Acyclic or carbocyclic compounds containing nitrogen
- G03G5/0616—Hydrazines; Hydrazones
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/07—Polymeric photoconductive materials
- G03G5/075—Polymeric photoconductive materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G5/076—Polymeric photoconductive materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds having a photoconductive moiety in the polymer backbone
- G03G5/0763—Polymeric photoconductive materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds having a photoconductive moiety in the polymer backbone comprising arylamine moiety
- G03G5/0766—Polymeric photoconductive materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds having a photoconductive moiety in the polymer backbone comprising arylamine moiety benzidine
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/07—Polymeric photoconductive materials
- G03G5/078—Polymeric photoconductive materials comprising silicon atoms
Definitions
- the present invention is directed toward photoconductors and compositions used to form photoconductors. More particularly, the invention is directed toward photoconductors comprising a substrate and a layer selected from the group consisting of charge transfer layers comprising a charge transfer molecule, polycarbonate and a first polyaryl ether; charge generating layers comprising a pigment, polyvinylbutyral and a second polyaryl ether; and mixtures thereof.
- the invention is also directed toward methods of improving the electrical characteristics of photoconductors, methods of extending the pot-life of charge transport compositions, and compositions used to form charge transport layers and charge generation layers.
- a latent image is created on the surface of an imaging member such as a photoconducting material by first uniformly charging the surface and then selectively exposing areas of the surface to light. A difference in electrostatic charge density is created between those areas on the surface which are exposed to light and those areas on the surface which are not exposed to light.
- the latent electrostatic image is developed into a visible image by electrostatic toners. The toners are selectively attracted to either the exposed or unexposed portions of the photoconductor surface, depending on the relative electrostatic charges on the photoconductor surface, the development electrode and the toner.
- a dual layer electrophotographic photoconductor comprises a substrate such as a metal ground plane member on which a charge generation layer (CGL) and a charge transport layer (CTL) are coated.
- the charge transport layer contains a charge transport material which comprises a hole transport material or an electron transport material.
- a charge transport layer which comprises a hole transport material as the charge transport compound.
- the charge transport layer contains an electron transport material rather than a hole transport material, the charge placed on a photoconductor surface will be opposite that described herein.
- a negative charge is typically placed on the photoconductor surface.
- the charge generation layer comprises the charge generation compound or molecule, for example a squaraine pigment, a phthalocyanine, or an azo compound, alone or in combination with a binder.
- the charge transport layer typically comprises a polymeric binder containing the charge transport compound or molecule.
- the charge generation compounds within the charge generation layer are sensitive to image-forming radiation and photogenerate electron-hole pairs therein as a result of absorbing such radiation.
- the charge transport layer is usually non-absorbent of the image-forming radiation and the charge transport compounds serve to transport holes to the surface of a negatively charged photoconductor. Photoconductors of this type are disclosed in the
- the photogenerator layer comprises a binder mixture of two or more polymers such as polyvinylcarbazole, polycarbonates, polyvinylbutyral and polyesters.
- Nogami et al. U.S. Patent No. 5,725,982 teach photoconductors comprising a charge transport layer comprising an aromatic polycarbonate resin.
- Nogami et al. further teach the photoconductor may comprise a charge generating layer comprising resins such as polycarbonate resin, polyvinylbutyral, polyacrylic ester, polymethacrylic ester, vinyl- chloride based copolymer, polyvinylacetal, polyvinylpropional, phenoxy resin, epoxy resin, urethane resin, cellulose ester and cellulose ether.
- resins such as polycarbonate resin, polyvinylbutyral, polyacrylic ester, polymethacrylic ester, vinyl- chloride based copolymer, polyvinylacetal, polyvinylpropional, phenoxy resin, epoxy resin, urethane resin, cellulose ester and cellulose ether.
- Nakamura et al. U.S. Patent No. 5,837,410, teach a photoconductor comprising a conductive layer and an organic film.
- the organic film may comprise a charge-generating layer which comprises binders such as polyvinylbutyral resin, polyvinylchloride copolymer resin, acrylic resin, polyester resin and polycarbonate resin and a charge transport layer comprising resins such as polyester resin, polycarbonate resin, polymethacrylic resin and polystyrene resin.
- Polyarylether ketones can be synthesized in art recognized ways, such as the method taught by Kelsey, U.S. Patent No. 4,882,397, Rose, U.S. Patent No. 4,419,486, and Roovers et al., U.S. Patent No. 5,288,834.
- Kelsey teaches a process for preparing polyarylether ketones from a polyketal.
- Rose teaches sulfonation of polyarylether ketones. Roovers et al.
- bromomethyl derivatives of polyarylether ketones are useful intermediates for further functionalizing the aromatic polyether ketones, and further teach functionalized polyarylether ketones such as carbonyl fluoride poly (aryl ether ether ketone), cyan methylene poly(aryl ether ether ketone), diethylamine methylene poly(aryl ether ether ketone), and aldehyde polyaryl (aryl ether ether ketone).
- Nakamura et al. teach a photoconductor comprising a substrate and a photosensitive layer comprising a charge generating layer and a charge transporting layer.
- Nakamura et al. teach the charge generating layer contains an organic pigment and a polyarylether ketone binder resin.
- Japanese Patent Application JP 63239454 A teaches an electrophotographic sensitive body comprising a layer containing a polyetherketone binder resin
- Japanese Patent Application JP 632247754 A teaches an electrophotographic sensitive body comprising a charge transfer layer comprising a hydrazone compound charge transfer material and a polyetherketone resin
- Japanese Application JP 63070256 A teaches a photoconductive layer comprising a polyetherketone resin laminated on a conductive base.
- Kan et al. U.S. Patent No. 4,772,526, disclose a reusable electrophotographic imaging element having a photoconductive surface layer in which the binder resin comprises a block copolyester or copolycarbonate having a fluorinated polyether block.
- Kan et al. teach that the surface layer is either capable of generating an injecting charge carriers upon exposure, or capable of accepting and transporting injected charge carriers.
- U.S. Patent No. 5,006,443 discloses perfluoralkyl group-containing polymers which are useful in radiation-sensitive reproduction layers. Muller teaches the perfluoroalkyl group-containing polymers comprise polymers or polycondensates and have phenolic hydroxyl groups and perfluoroalkyl groups which are optionally attached through intermediate members.
- Ishikawa et al. U.S. Patent No. 5,073,466, disclose an electrophotographic member comprising a support, a photoconductive layer, and a surface layer comprising a lubricating agent and a fixing group. Ishikawa et al. teach the lubricating agent has a perfluoropolyoxyalkyl group or a perfluoropolyoxyalkylene group.
- Suzuki, et al. U.S. Patent No. 5,344,733, disclose an electrophotographic receptor having an overcoat layer on the surface of a photosensitive layer containing a charge generating substance.
- Suzuki et al. teach the overcoat layer comprises a fluororesin cured with a melamine compound or an isocyanate compound as a cross- linking agent, a charge generating substance, and a charge transport substance.
- the charge transport layer and charge generation layers of photoconductors generally comprise binders.
- the charge generation layer generally comprises pigments, however, since pigments do not adhere effectively to metal substrates, polymer binders are usually included. Unfortunately, the electrical sensitivity of the charge generation layer, drum wear, or composition pot-life can be affected by the polymer binder.
- polyvinylbutyral as a charge generation layer binder is advantageous in that it significantly improves adhesion of the charge generation layer to the substrate.
- polyvinylbutyral can disadvantageously affect electrical characteristics of the resulting photoconductor in causing, inter alia, high dark decay and residual voltage properties.
- Polycarbonates have been known to improve the mechanical properties of a photoconductor, particularly its impact resistance. Unfortunately, the use of polycarbonates can result in photoconductors which are susceptible to drum-end wear, which may result in print-quality defects or drum failure, and to scratches in the paper area, which may lead to print-quality defects.
- photoconductors comprising a substrate and at least one layer selected from the group consisting of: a) charge transfer layers comprising a charge transfer molecule, polycarbonate and a first polyaryl ether selected from the group consisting of polyaryletherketones, poly(aryl-perfluoroaryl ether)s, polyaryletherketone- hydrazones, polyaryletherketone-azines and mixtures and copolymers thereof; b) charge generation layers comprising a pigment, polyvinylbutyral and a second polyaryl ether selected from the group consisting of polyaryletherketones, polyarylethersulfones and mixtures and copolymers thereof; and c) mixtures thereof.
- the methods comprise the step of forming photoconductors comprising a substrate and at least one layer selected from the group consisting of: a) charge transfer layers comprising a charge transfer molecule, polycarbonate and a first polyaryl ether selected from the group consisting of polyaryletherketones, poly(aryl-perfluoroaryl ether)s, polyaryletherketone- hydrazones, polyaryletherketone-azines and mixtures thereof; b) charge generating layers comprising a pigment, a polyvinylbutyral and a second polyaryl ether selected from the group consisting of polyaryletherketones, polyarylethersulfones and mixtures thereof; and c) mixtures thereof.
- the photoconductor comprises a charge transfer layer comprising a polyarylether ketone
- the weight ratio of polycarbonate to polyarylether ketone is preferably from about
- the methods comprise the step of providing polyaryl ethers selected from the group consisting of polyaryletherketones, poly(aryl-perfluoroaryl ether)s, polyaryletherketone-hydrazones, polyaryletherketone- azines and mixtures thereof in combination with polycarbonate and a charge transport molecule.
- charge transfer compositions comprising a charge transfer molecule, solvent and a binder blend.
- the binder blend comprises polycarbonate and a polyaryl ether selected from the group consisting of polyaryletherketones, poly(aryl-perfluoroaryl ether)s, polyaryletherketone- hydrazones, polyaryletherketone-azines and mixtures thereof.
- charge generation compositions comprising pigment, solvent and a binder blend.
- the binder blend comprises polyvinylbutyral and a polyaryl ether selected from the group consisting of polyaryletherketones, polyarylethersulfones and mixtures thereof.
- photoconductors in accordance with the present invention have good electrical characteristics, low electrical fatigue and stable print-performance. Further, it has been found that charge transport compositions in accordance with the present invention have improved extended pot-life.
- the charge transport and charge generation layers according to the present invention are suitable for use in dual layer photoconductors.
- Such photoconductors generally comprise a substrate, a charge generation layer (CGL) and a charge transport layer (CTL).
- CGL charge generation layer
- CTL charge transport layer
- the photoconductors may also comprise a sub-layer to assist in the adhesion of the charge generation and charge transport layers, or a protective coating to reinforce the durability of the charge generation and charge transport layers.
- Some substrates, such as aluminum, may be anodized.
- charge generation layer as being formed on the substrate, with the charge transport layer formed on the charge generation layer, it is equally within the scope of the present invention for the charge transport layer to be formed on the substrate with the charge generation layer formed on the charge transport layer.
- the present invention is directed toward photoconductors, and more particularly to photoconductors comprising charge transport layers and/or charge generation layers comprising binder blends containing a polyaryl ether.
- Photoconductors comprising charge generation layers and/or charge transfer layers in accordance with the present invention exhibit improved electrical characteristics such as improved photosensitivity, reduced dark decay, and reduced fatigue.
- cardo groups refers to cyclic groups that tend to form a loop in the polymer chain. Cardo groups include cyclohexyl, fluorenyl and phthalidenyl groups.
- charge voltage refers to the voltage applied on a drum by a charge roll or corona.
- discharge voltage refers to the voltage on the drum after shining light on the drum. Discharge voltage may be measured at several different light energies. Whereas the streak voltage corresponds to the voltage measured at the lower laser light energy (about 0.2 microjoules/cm 2 ), the discharge voltage (also referred to as residual voltage) corresponds to voltage at the higher laser energy.
- Photoconductor drums may exhibit a loss of charge in the dark, i.e., may lose some charge before a light source discharges the charge.
- dark decay refers to the loss of charge from the surface of a photoconductor when it is maintained in the dark. Dark decay is an undesirable feature as it reduces the contrast potential between image and background areas, leading to washed out images and loss of gray scale. Dark decay also reduces the field that the photoconductive process will experience when light is brought back to the surface, thereby reducing the operational efficiency of the photoconductor.
- sensitivity refers to the ability of a photoconductor to discharge its voltage efficiently. The photosensitivity may be measured as the amount of light energy, in microjoules/cm 2 , required to reduce the photoconductor's voltage from its initial charge to a lower charge.
- the photoconductors may be subjected to sensitivity measurements using a sensitometer fitted with electrostatic probes to measure the voltage magnitude as a function of light energy shining on the photoconductor surface. It is undesirable for a photoconductor to have poor sensitivity for such a photoconductor would require a large amount of light energy to discharge its voltage.
- charge transport compositions in accordance with the present invention show improved pot-life.
- pot-life refers to the length of time a composition, particularly a charge transport composition used to prepare a charge transport layer, can be stored without the composition becoming too viscous to be easily applied to a substrate and without the resulting layer exhibiting any adverse effects.
- the earliest layer formed by the composition and the latest layer formed by the composition have substantially similar characteristics. If the characteristics of the earlier layers differ from the later layers, it may be necessary to dispose of and replace the composition even though it has not yet become so viscous that it is difficult to apply. It is advantageous for a composition to have a long pot-life in order to avoid frequent disposal and replacement of the composition.
- Photoconductors of the present invention comprise a substrate and at least one layer selected from the group consisting of: a) charge transfer layers comprising a charge transfer molecule, polycarbonate and a first polyaryl ether selected from the group consisting of polyaryletherketones, poly(aryl-perfluoroaryl ether)s, polyaryletherketone- hydrazones, polyaryletherketone-azines, and mixtures thereof; b) charge generating layers comprising a pigment, polyvinylbutyral and a second polyaryl ether selected from the group consisting of polyaryletherketones, polyarylethersulfones and mixtures thereof; and c) mixtures thereof.
- a) charge transfer layers comprising a charge transfer molecule, polycarbonate and a first polyaryl ether selected from the group consisting of polyaryletherketones, poly(aryl-perfluoroaryl ether)s, polyaryletherketone- hydrazones, polyaryl
- polyaryl ethers is intended to refer to polymers having a backbone comprising aromatic groups and ether linkages.
- the polyaryl ether polymers include both homopolymers and copolymers.
- the copolymers comprise at least two different monomer units, wherein at least one monomer unit has a backbone comprising aromatic groups and ether linkages.
- Preferred polyaryl ethers for use in forming compositions and photoconductors in accordance with the present invention include polyaryletherketones (PAEKs), polyarylethersulfones (PAESs), poly(aryl-perfluoroaryl ether)s (PAPFAEs), polyaryletherketones-hydrazones (PAEK-hydrazones), and polyaryletherketone-azines (PAEK-azines) and mixtures and copolymers thereof.
- PAEKs polyaryletherketones
- PAESs polyarylethersulfones
- PAPFAEs poly(aryl-perfluoroaryl ether)s
- PAEK-hydrazones polyaryletherketones-hydrazones
- PAEK-azines polyaryletherketone-azines
- polyaryletherketones is intended to refer to polymeric compounds having a polymeric backbone comprising aromatic rings, ether linkages and ketone linkages
- polyarylethersulfones is intended to refer to polymeric compounds having a polymeric backbone comprising aromatic rings, ether linkages and sulfone linkages
- Polyaryletherketone-azines is intended to refer to PAEK polymers wherein at least one of the ketones of the polymeric backbone has been replaced with an azine
- polyaryletherketones-hydrazones is intended to refer to polymers wherein at least one of the ketones of the polymer backbone has been replaced with a hydrazone.
- Poly(aryl-perfluoroaryl ether)s is intended to refer to polymeric compounds having a backbone comprising aromatic groups, at least one of which is perfluorinated, and ether linkages.
- the polymeric compounds may be homopolymers or copolymers.
- the molecular weights of the polymers are from about 2,000 to about 100,000, more preferably from about 10,000 to about 70,000.
- PAEKs and PAESs there are several ways of synthesizing PAEKs and PAESs, such as a Friedel-Crafts reaction of stoichiometric amounts of aromatic bisbenzoyl chlorides with arenes, a nucleophilic displacement reaction of stoichiometric quantities of bisphenolate salts with activated aromatic dihalides in polar aprotic solvents, and a phase transfer catalyzed nucleophilic displacement reaction of bisphenols with hexafluorobenzene.
- a Friedel-Crafts reaction of stoichiometric amounts of aromatic bisbenzoyl chlorides with arenes such as a Friedel-Crafts reaction of stoichiometric amounts of aromatic bisbenzoyl chlorides with arenes, a nucleophilic displacement reaction of stoichiometric quantities of bisphenolate salts with activated aromatic dihalides in polar aprotic solvents, and a phase transfer catalyzed nucleophilic displacement
- the PAEKs and PAESs may be synthesized by the polymerization reaction of stoichiometric amounts of one or more bisphenol compounds, such as bisphenols or bisphenolate salts, with a dihalobenzophenone or a dihalophenylsulfone in a polar aprotic solvent, such as N,N-dimethylacetamide (DMAc), and an azeotroping solvent, such as toluene, under refluxing conditions.
- a base preferably an inorganic base such as potassium carbonate (K 2 CO 3 ), potassium hydroxide (KOH) or cesium fluoride (CsF).
- the water formed in the reaction may be removed by any convenient means, such as by forming an azeotrope with toluene.
- the reaction mixture is stirred under refluxing temperature to increase the degree of polymerization.
- the polymerization may be quenched in water, and the resulting product may be chopped in a high speed blender.
- the polymer may be isolated by filtration, neutralized, stirred in boiling water, stirred in boiling methanol, and then dried.
- Preferred PAEKs and PAESs include those shown in Reaction Sequence 1.
- R, and R 3 may be identical or different, and R and R 2 may be identical or different. In one embodiment R and R 2 are different.
- PAEK polymers may be modified to replace at least one of the ketones of the polymeric backbone with an azine or a hydrazone.
- the modification of a PAEK to the corresponding PAEK-hydrazone may be accomplished by the condensation of the PAEK with a hydrazine, while the modification of a PAEK to the corresponding PAEK- azine may be accomplished by the condensation of the PAEK with a hydrazone.
- PAEK- hydrazones comprise a group having the general structure:
- PAEK-azines comprise a group having the general structure:
- the R' and R" groups may be identical or different, further the R' and R" groups may be linked to form a ring structure, such as a fluorene structure. As one of ordinary skill will appreciate, the exact structures of the R' and R" groups depend upon the hydrazines or hydrazones used.
- Suitable hydrazines include dialkylhydrazines, diarylhydrazines and aralkylhydrazines, such as 1,1-diphenylhydrazine hydrochloride, phenyl methylhydrazine and dimethylhydrazine, while suitable hydrazones include dialkylhydrazones and aralkylhydrazones, such as 9-fluorenone hydrazone, diarylhydrazone, dialkylhydrazone and aralkyl hydrazone.
- ketone groups of the PAEK are converted, and the resulting polymers are co-polymers of either a ketone and an azine pendant, or a ketone and a hydrazone pendant. While not being bound by theory, the formations of the pendant azines and the pendant hydrazones are believed to proceed as set forth below in Reaction Sequences 2 and 3, respectively. Reaction Sequence 2. Synthesis of PAEK-azines
- PAEK-azines and PAEK-hydrazones include those set forth in Reaction Sequences 2 and 3, respectively.
- PAPFAEs may be synthesized by, for example, the polymerization reaction of stoichiometric amounts of one or more bisphenol compounds, such as bisphenols or bisphenolate salts, with a perfluoro aromatic compound, such as decafluorobiphenyl, perfluorobenzophenone and perfluorophenylsulfone, in N,N-dimethylacetamide.
- a perfluoro aromatic compound such as decafluorobiphenyl, perfluorobenzophenone and perfluorophenylsulfone
- Reaction Sequence 4 Preparation of poly(aryl-perfluoroaryl ether )s
- Preferred PAPFAEs include those set forth in Reaction Sequence 4.
- the reaction is generally catalyzed by a base, preferably an inorganic base such as potassium carbonate (K 2 CO 3 ), or cesium fluoride (CsF). Generally two equivalents of the base are used with respect to the bisphenol.
- a base preferably an inorganic base such as potassium carbonate (K 2 CO 3 ), or cesium fluoride (CsF).
- K 2 CO 3 potassium carbonate
- CsF cesium fluoride
- the polymerization may be quenched in water, and the resulting product may be chopped in a high speed blender.
- the polymer may be isolated by filtration, neutralized, stirred in boiling water, stirred in boiling methanol, and then dried.
- the reaction temperature during the polymerization is generally less than the refluxing temperature.
- refluxing temperature refers to the temperature at which the solvent boils in the solution. If the reaction temperature is substantially close to the refluxing temperature (> 145°C), the polymerization mixtures become highly viscous and cross-linked. The reaction temperature is a temperature below which such cross-linking occurs. Generally, the reaction temperature is less than 145°C, preferably the reaction temperature is from about 50°C to about 140°C, more preferably the reaction temperature is about 120°C.
- Preferred PAPFAEs are soluble in organic solvents. Particularly preferred are
- PAPFAEs which are soluble in tetrahydrofuran (THF), chlorinated hydrocarbons (such as dichloromethane and chloroform), dioxane and polar aprotic solvents (such as dimethyl acetamide, dimethyl formamide, N-methyl-2-pyrrolidinone and methyl sulfoxide).
- chlorinated hydrocarbons such as dichloromethane and chloroform
- dioxane dioxane
- polar aprotic solvents such as dimethyl acetamide, dimethyl formamide, N-methyl-2-pyrrolidinone and methyl sulfoxide.
- the polyaryl ethers may be synthesized using any suitable bisphenol compound.
- Preferred bisphenol compounds are selected from the group consisting of bisphenol- A, cyclohexylidenebiphenol, fluorenylidenebisphenol, phenolphthalein, methylbisphenol-A, bisphenolate salts and mixtures thereof.
- the polyaryl ethers are synthesized from two different bisphenol compounds.
- Charge transport layers in accordance with the present invention comprise at least one charge transport molecule, polycarbonate and a polyaryl ether selected from the group consisting of polyaryletherketones, poly(arylperfluoro ' ethers)s, polyaryletherketones-hydrozones, polyaryletherketones-azines and mixtures thereof.
- the weight ratio of the polycarbonate to the polyaryl ether is generally in the range of from about 93:7 to about 75:25, preferably in the range of from about 93:7 to about 85:15.
- charge transport compounds suitable for use in the charge transport layer of the photoconductors of the present invention should be capable of supporting the injection of photo-generated holes or electrons from the charge generation layer and allowing the transport of these holes or electrons through the charge transport layer to selectively discharge the surface charge.
- Suitable charge transport compounds for use in the charge transport layer include, but are not limited to, the following:
- Diamine transport molecules of the types described in U.S. Patents Nos. 4,306,008, 4,304,829, 4,233,384, 4,115,116, 4,299,897, 4,265,990 and/or 4,081,274.
- Typical diamine transport molecules include benzidine compounds, including substituted benzidine compounds such as the N,N'-diphenyl-N,N'-bis(alkylphenyl)-[l, -biphenyl]- 4,4'-diamines wherein the alkyl is, for example, methyl, ethyl, propyl, n-butyl, or the like, or halogen substituted derivatives thereof, and the like.
- Pyrazoline transport molecules as disclosed in U.S. Patents Nos. 4,315,982,
- Typical pyrazoline transport molecules include l-[lepidyl-(2)]- 3-(p-diethylaminophenyl)-5-(p-diethylaminophenyl)pyrazoline, l-[quinolyl-(2)]-3-(p- diethylaminophenyl)-5-(p-diethylaminophenyl)pyrazoline, l-[pyridyl-(2)]-3-(p- diemylarninostyryl)-5-(p-diethylaminophenyl)pyrazoline, l-[6-methoxypyridyl-(2)]-3-(p- diethylaminostyryl)-5-(p-diethylaminophenyl) pyrazoline, l-phenyl-3-[p- diethylaminostyryl]-5-(p-dimethylaminostyryl)pyrazoline, l-phenyl-3-[p-phenyl-3-[p-diethy
- Typical fluorene charge transport molecules include 9-(4'- dimethylaminobenzylidene)fluorene, 9-(4'-methoxybenzylidene)fluorene, 9-(2,4'- dimethoxybenzylidene)fluorene, 2-nitro-9-benzylidene-fluorene, 2-nitro-9-(4'- diethylaminobenzylidene)fluorene and the like.
- Oxadiazole transport molecules such as 2,5-bis(4-diethylaminophenyl)- 1,3,4- oxadiazole, imidazole, triazole, and others as described in German Patents Nos. 1,058,836, 1,060,260 and 1,120,875 and U.S. Patent No. 3,895,944.
- Hydrazone transport molecules including p-diethylaminobenzaldehyde- (diphenylhydrazone), p-diphenylaminobenzaldehyde-(diphenylhydrazone), o-ethoxy-p- diethylaminobenzaldehyde-(diphenylhydrazone), o-methyl-p-diethylaminobenzaldehyde- (diphenylhydrazone), o-methyl-p-dimethylaminobenzaldehyde(diphenylhydrazone), p- dipropylaminobenzaldehyde-(diphenylhydrazone), p-diethylaminobenzaldehyde-
- hydrazone transport molecules include compounds such as 1 -naphthalenecarbaldehyde 1 -methyl- 1-phenylhydrazone, 1- naphthalenecarbaldehyde 1,1-phenylhydrazone, 4-methoxynaphthlene-l-carbaldehyde 1 -methyl- 1-phenylhydrazone and other hydrazone transport molecules described, for example, in U.S. Patents Nos. 4,385,106, 4,338,388, 4,387,147, 4,399,208 and 4,399,207.
- hydrazone charge transport molecules include carbazole phenyl hydrazones such as 9-methylcarbazole-3-carbaldehyde-l,l-diphenylhydrazone, 9-ethylcarbazole-3- carbaldehyde- 1 -methyl- 1 -phenylhydrazone, 9-ethylcarbazole-3 -carbaldehyde- 1 -ethyl- 1 - phenylhydrazone, 9-ethylcarbazole-3 -carbaldehyde- 1 -ethyl- 1 -benzyl- 1 -phenylhydrazone, 9-ethylcarbazole-3-carbaldehyde-l,l-diphenylhydrazone, and other suitable carbazole phenyl hydrazone transport molecules described, for example, in U.S. Patent No. 4,256,821. Similar hydrazone transport molecules are described, for example, in U.S. Patent No.
- the charge transport compound included in the charge transport layer comprises a hydrazone, an aromatic amine (including aromatic diamines such as benzidine), a substituted aromatic amine (including substituted aromatic diamines such as substituted benzidines), or a mixture thereof.
- Preferred hydrazone transport molecules include derivatives of aminobenzaldehydes, cinnamic esters or hydroxylated benzaldehydes.
- Exemplary aminobenzaldehyde-derived hydrazones include those set forth in the Anderson et al U.S. Patents Nos.
- the charge transport compound comprises a compound selected from the group consisting of poly(N-vinylcarbazole)s, poly(vinylanthracene)s, poly(9, 10-anthracenenylene-dodecanedicarboxylate)s, polysilanes, polygermanes, poly(p-phenylene-sulfide), hydrazone compounds, pyrazoline compounds, enamine compounds, styryl compounds, arylmethane compounds, arylamine compounds, butadiene compounds, azine compounds, and mixtures thereof.
- the charge transport compound comprises a compound selected from the group consisting of p-diethylaminobenzaldehyde- (diphenylhydrazone) (DEH), N,N'- bis-(3-methylphenyl)-N,N'-bis-phenyl-benzidine (TPD) and mixtures thereof.
- TPD has the formula:
- the charge transport layer typically comprises the charge transport compound in an amount of from about 5 to about 60 weight percent, more preferably in an amount of from about 15 to about 40 weight percent, based on the weight of the charge transport layer, with the remainder of the charge transport layer comprising the polycarbonate, the polyaryl ether and any conventional additives.
- Suitable polycarbonates include polycarbonate-A's, polycarbonate-Z's, and mixtures thereof.
- Preferred polycarbonates have a number average molecular weight of from about 10,000 to about 100,000, preferably from about 20,000 to about 80,000.
- a preferred polycarbonate includes a polycarbonate-A having the structure set forth below:
- Such a polycarbonate-A is available from Bayer Corporation as MAKROLON ® -5208 Polycarbonate, having a number average molecular weight of about 34,000.
- the polyaryl ethers used in the charge transport layer have a number average molecular weight of at least about 2,000, preferably at least about 5,000, more preferably at least about 10,000, and even more preferably at least about 20,000.
- the polyaryl ethers generally have a molecular weight no greater than about 100,000, preferably no greater than abut 70,000.
- the charge transport layer comprises a polymer selected from the group consisting of polyaryl ether sulfones and polyaryl etherketones having a molecular weight in the range of from about 2,000 to about 100,000, preferably from about 10,000 to about 40,000.
- the charge transport layer comprises a polyaryl-perfluoroaryl ether having a number average molecular weight in the range of from about 5,000 to about 100,000, preferably from about 20,000 to about 70,000.
- the charge transport layer comprises a polyaryletherketone-hydrazine and/or polyaryletherketone-azine having a number average molecular weight in the range of from about 20,000 to about 100,000, preferably from about 10,000 to about 60,000.
- the charge transport layer will typically have a thickness of from about 10 to about 40 microns and may be formed in accordance with conventional techniques known in the art. Conveniently, the charge transport layer may be formed by preparing a charge transport composition, coating the charge transport composition on the respective underlying layer and drying the coating.
- the polycarbonate, polyaryl ether and the charge transport compound are dispersed or dissolved in an organic liquid.
- the composition which forms the charge transport layer may be referred to as a solution
- the polycarbonate, polyaryl ether and charge transport compound may disperse rather than dissolve in the organic liquid, thus the composition may be in the form of a dispersion rather than a solution.
- the polycarbonate, polyaryl ether and charge transport compound may be added to the organic liquid simultaneously or consecutively, in any order of addition.
- Suitable organic liquids are preferably essentially free of amines and therefore avoid environmental hazards conventionally incurred with the use of amine solvents. Suitable organic liquids include, but are not limited to, tetrahydrofuran, 1,2-dioxane, 1,4-dioxane, and the like.
- the charge transport composition generally comprises, by weight, from about
- the polycarbonate and the polyaryl ether form a binder blend.
- the weight ratio of polycarbonate and the polyaryl ether in the binder blend is from about 93:7 to about 75:25, preferably from about 93:7 to about 85:15.
- Charge generation layers in accordance with the present invention comprise a charge generation molecule, polyvinylbutyral and a polyaryl ether selected from the group consisting of polyaryletherketones, polyaryl ether sulfones and mixtures thereof.
- the polyaryletherketones and polyarylether sulfones generally have a number average molecular weight from about 2,000 to about 100,000, preferably from about 10,000 to about 40,000.
- Polyvinylbutyral polymers are well known in the art and are commercially available from various sources. These polymers are typically made by condensing polyvinyl alcohol with butyraldehyde in the presence of an acid catalyst, for example sulfuric acid, and contain a repeating unit of formula:
- the polyvinylbutyral polymer will have a number average molecular weight of from about 20,000 to about 300,000.
- the weight ratio of the polyvinylbutyral to the polyaryl ether in the charge generation layer is generally in the range of from about 25:75 to about 90:10, preferably from about 25:75 to about 75:25.
- Various organic and inorganic charge generation compounds are known in the art, any of which are suitable for use in the charge generation layers of the present invention.
- One type of charge generation compound which is particularly suitable for use in the charge generation layers of the present invention comprises the squarylium-based pigments, including squaraines. Squarylium pigment may be prepared by an acid route such as that described in U.S. Patents Nos.
- Preferred squarylium pigments suitable for use in the present invention may be represented by the structural formula:
- R ] represents hydroxy, hydrogen or C,. 5 alkyl, preferably hydroxy, hydrogen or methyl, and each R 2 individually represents C,. 5 alkyl or hydrogen.
- the pigment comprises a hydroxy squaraine pigment wherein each R, in the formula set forth above comprises hydroxy.
- Suitable phthalocyanine compounds include both metal-free forms such as the X-form metal-free phthalocyanines and the metal-containing phthalocyanines.
- the phthalocyanine charge generation compound may comprise a metal-containing phthalocyanine wherein the metal is a transition metal or a group IIIA metal.
- metal-containing phthalocyanine charge generation compounds those containing a transition metal such as copper, titanium or manganese or containing aluminum or gallium as a group IIIA metal are preferred.
- These metal-containing phthalocyanine charge generation compounds may further include oxy, thiol or dihalo substitution.
- Titanium-containing phthalocyanines as disclosed in U.S. Patents Nos. 4,664,997, 4,725,519 and 4,777,251, including oxo-titanyl phthalocyanines, and various polymorphs thereof, for example type IV polymorphs, and derivatives thereof, for example halogen-substituted derivatives such as chlorotitanyl phthalocyanines, are suitable for use in the charge generation layers of the present invention.
- Additional conventional charge generation compounds known in the art including, but not limited to, disazo compounds, for example as disclosed in the Ishikawa et al U.S. Patent No. 4,413,045, and tris and tetrakis compounds as known in the art, are also suitable for use in the charge generation layers of the present invention. It is also within the scope of this invention to employ a mixture of charge generation pigments or compounds in the charge generation layer.
- the charge generation molecule is a pigment selected from the group consisting of azo pigments, anthraquinone pigments, polycyclic quinone pigments, indigo pigments, diphenylmethane pigments, azine pigments, cyanine pigments, quinoline pigments, benzoquinone pigments, napthoquinone pigments, naphthalkoxide pigments, perylene pigments, fluorenone pigments, squarylium pigments, azuleinum pigments, quinacridone pigments, phthalocyanine pigments, naphthaloxyanine pigments, porphyrin pigments and mixtures thereof.
- the charge generation molecule is a pigment selected from the group consisting of hydroxy squaraines, Type IV oxotitanium phthalocyanines, and mixtures thereof.
- the charge generation layers may comprise the charge generation compound in amounts conventionally used in the art.
- the charge generation layer may comprise from about 5 to about 80, preferably at least about 10, and more preferably from about 15 to about 60, weight percent of the charge generation compound, and may comprise from about 20 to about 95, preferably not more than about 90, and more preferably comprises from about 40 to about 85, weight percent of the total of the polyvinylbutryal and the polyaryl ether, all weight percentages being based on the charge generation layer.
- the charge generation layers may further contain any conventional additives known in the art for use in charge generation layers.
- the polyvinylbutryal, polyaryl ether and the charge generation compound are dissolved and dispersed, respectively, in an organic liquid.
- the organic liquid may generally be referred to as a solvent, and typically dissolves the polyvinylbutryal and the polyaryl ether, the liquid technically forms a dispersion of the pigment rather than a solution.
- the polyvinylbutryal, polyaryl ether and pigment may be added to the organic liquid simultaneously or consecutively, in any order of addition. Suitable organic liquids are preferably essentially free of amines and therefore avoid environmental hazards conventionally incurred with the use of amine solvents.
- Suitable organic liquids include, but are not limited to, tetrahydrofuran, cyclopentanone, 2-butanone and the like. Additional solvents suitable for dispersing the charge generation compound, polyvinylbutryal and polyaryl ether blend will be apparent to those skilled in the art.
- the charge generation composition generally comprises, by weight, from about 0.5% to 20%, preferably from about 1% to 7%, of the polyvinylbutyral and from about from about 0.5% to 20%, preferably from about 0.5% to 3%, of the polyaryl ether.
- the polyvinylbutyral and the polyaryl ether form a binder blend.
- the binder blend comprises, by weight, 0.5% to 3% polyvinylbutyral and 0.5% to 3% polyaryl ether.
- the weight ratio of polyvinylbutyral and the polyaryl ether in the binder blend is from about 95:5 to about 5:95, preferably from about 75:25 to about 25:75.
- the composition preferably contains not greater than about 10 weight percent solids comprising the polyvinylbutryal, the polyaryl ether and charge generation compound in combination.
- compositions may therefore be used to form a charge generation layer of desired thickness, typically not greater than about 5 microns, and more preferably not greater than about 1 micron, in thickness. Additionally, a homogeneous layer may be easily formed using conventional techniques, for example dip coating or the like. These compositions also reduce any wash or leach of the charge generation compound into a charge transport layer coating which is subsequently applied to the charge generation layer.
- the charge generation layers according to the present invention exhibit good adhesion to underlying layers.
- the charge generation layer will be applied to a photoconductor substrate, with a charge transport layer formed on the charge generation layer.
- one or more barrier layers may be provided between the substrate and the charge generation layer.
- barrier layers typically have a thickness of from about 0.05 to about 20 microns. It is equally within the scope of the present invention that the charge transport layer is first formed on the photoconductor substrate, followed by formation of the charge generation layer on the charge transport layer.
- the photoconductor substrate may be flexible, for example in the form of a flexible web or a belt, or inflexible, for example in the form of a drum.
- the photoconductor substrate is uniformly coated with a thin layer of a metal, preferably aluminum, which functions as an electrical ground plane.
- the aluminum is anodized to convert the aluminum surface into a thicker aluminum oxide surface.
- the ground plane member may comprise a metallic plate formed, for example, from aluminum or nickel, a metallic drum or foil, or a plastic film on which aluminum, tin oxide, indium oxide or the like is vacuum evaporated.
- the photoconductor substrate will have a thickness adequate to provide the required mechanical stability.
- flexible web substrates generally have a thickness of from about 0.01 to about 0.1 microns
- drum substrates generally have a thickness of from about 0.75 mm to about 1 mm.
- PAEKs and PAESs were synthesized by the aromatic nucleophilic displacement reaction of a difluorobenzophenone or a difluorophenylsulfone using various potassium bisphenolates. The reactions were performed in N,N-dimethylacetamide solvent.
- the potassium bisphenolates were typically generated in situ by the reaction of a bisphenol with potassium carbonate, and the water formed thereby was removed by azeotropic distillation using toluene. In most cases, following the azeotropic removal of water and toluene and refluxing in the dimethylacetamide solvent, which required about 2 hours, the reaction mixture became viscous.
- the polymers comprised the structure:
- the vicous polymer solution was precipitated in water, and a white fibrous polymer was isolated by filtration.
- the white polymer was stirred in boiling water for about 1 hour, filtered, stirred in boiling methanol for about 1 hour and filtered.
- the fibrous white polymer was then dried in an vacuum oven for about 16 hours at 100°C. The yield was about 9.93 g.
- the number average molecular weight of the polymer was about 11.0 K.
- Polv(bisphenol-Z-benzophenone') f Pf BPZ-BNZPH ⁇ In a three neck 500 mL round-bottom flask was weighed bisphenol-Z (35.0000 g, 130.42 mmol), potassium carbonate (36.0505 g, 260.45 mmol), 4,4'-difluorobenzophenone (28.4587 g, 130.42 mmol), toluene (115 g) and N,N-dimethylacetamide (233 g). The flask was fitted with a condenser and a thermometer. The light yellow mixture was stirred and heated to reflux. The water formed was azeotropically distilled with toluene.
- the solution was stirred at reflux for about 2 hours.
- the viscous polymer solution was precipitated in water, and a white fibrous polymer was isolated by filtration.
- the white polymer was stirred in boiling water for about 1 hour, filtered, and then stirred in boiling methanol for about 1 hour and filtered.
- the fibrous white polymer was then dried in an vacuum oven for about 16 hours at 100°C. The yield was about 54.35 g.
- the number average molecular weight of the polymer was about 11.5K.
- Polymerization was carried out similar to the P(BPZ-BNZPH) polymerization, except 9,9-fluorenylidenebisphenol (8.0000 g, 22.829 mmol), potassium carbonate (6.31 g, 45.658 mmol), 4,4'-difluorobenzophenone (4.9815 g, 22.829 mmol), toluene (40 g) and N,N-dimethylacetamide (60 g) were used. The yield was about 11.38 g. The number average molecular weight of the polymer was about 35.5K.
- Polv(phenolphthalein-benzophenone') fPfPHENOLPH-BNZPH Polymerization was carried out similar to the P(BPZ-BNZPH) polymerization, except phenolphthalein (15.0000 g, 47.12 mmol), potassium carbonate (13.02 g, 94.28 mmol), 4,4'-difluorobenzophenone (10.2819 g, 47.12 mmol), toluene (117 g) and N,N-dimethylacetamide 100 g) were used. The yield was about 21.87 g. The number average molecular weight of the polymer was about 40.4K.
- Polymerization was carried out similar to the P(BPZ-BNZPH) polymerization, except methylbisphenol-A (10.0000 g, 39.00 mmol), potassium carbonate (10.782 g, 78.00 mmol), 4,4'-difluorobenzophenone (8.5102 g, 39.00 mmol), toluene (50 g) and N,N-dimethylacetamide (85 g) were used.
- the yield was about 15.34 g.
- the number average molecular weight of the polymer was about 8.2K.
- Polymerization was carried out similar to the P(BPZ-BNZPH) polymerization, except 1,1-cyclohexylidenebisphenol (4.9194 g, 18.331 mmol), bisphenol-A (4.1849 g, 18.33 mmol), potassium carbonate (10.13 g, 73.32 mmol), 4,4'-difluorobenzophenone (8.0000 g, 36.66 mmol), toluene (50 g) and N,N-dimethylacetamide (80 g) were used. The yield was about 14.12 g. The number average molecular weight of the polymer was about 47.8K.
- Polv(cvclohexylidenebisphenol-co-benzophenone-co-phenolphthalein-50/50 Q > fBPZ-BNZPH-PHENOLPH Polymerization was carried out similar to the P(BPZ-BNZPH) polymerization, except 1,1-cyclohexylidenebisphenol (4.9194 g, 18.331 mmol), phenolphthalein (5.8354 g, 18.33 mmol), potassium carbonate (10.13 g, 73.32 mmol), 4,4'-difluorobenzophenone (8.0000 g, 36.66 mmol), toluene (50 g) and N,N-dimethylacetamide (86 g) were used. The yield was about 15.85 g. The number average molecular weight of the polymer was about 22.6K.
- Polymerization was carried out similar to the P(BPZ-BNZPH) polymerization, except 1,1-cyclohexylidenebisphenol (6.0000 g, 22.35 mmol), potassium carbonate (6.18 g, 44.70 mmol), 4-fluorophenylsulfone (5.6847 g, 22.35 mmol), toluene (40 g) and N,N-dimethylacetamide (54 g) were used. The yield was about 9.67 g. The number average molecular weight of the polymer was about 21.3K.
- N,N-dimethylacetamide 50 g were used.
- the yield was about 9.34 g.
- the number average molecular weight of the polymer was about 28.8K.
- Polymerization was carried out similar to the P(BPZ-BNZPH) polymerization, except 9,9-fluorenylidenebisphenol (4.1346 g, 11.79 mmol), cyclohexylidenebisphenol (3.1664 g, 13.74 mmol), potassium carbonate (6.52 g, 47.19 mmol), 4-fluorophenylsulfone (6.0000 g, 23.598 mmol), toluene (32 g) and N,N-dimethylacetamide (64 g) were used. The yield was about 11.66 g. The number average molecular weight of the polymer was about 53.8K.
- Polymerization was carried out similar to the P(BPZ-BNZPH) polymerization, except phenolphthalein (3.7560 g, 11.79 mmol), cyclohexylidenebisphenol (3.7560 g, 11.79 mmol), potassium carbonate (6.52 g, 47.19 mmol), 4-fluorophenylsulfone (6.0000 g, 23.598 mmol), toluene (30 g) and N,N-dimethylacetamide (58 g) were used. The yield was about 10.97 g. The number average molecular weight of the polymer was about 50.9K.
- Polv(phenolphthalein-co-phenylsulfone-co-cvclohexylidenebisphenol-50/50) fPfPHENOLPH-SULFONE- BPZ Polymerization was carried out similar to the P(BPZ-BNZPH) polymerization, except phenolphthalein (3.7560 g, 11.79 mmol), cyclohexylidenebisphenol (3.1663 g, 13.74 mmol), potassium carbonate (6.52 g, 47.19 mmol), 4-fluorophenylsulfone (6.0000 g, 23.59 mmol), toluene (35 g) and N,N-dimethylacetamide (63 g) were used. The yield was about 11.29 g. The number average molecular weight of the polymer was about 40.6K.
- the polyarylethers containing the carbonyl or sulfonyl units were used to prepare dispersions of pigments such as squaraines (HOSq) and Type IV oxotitanium phthalocyanine (TiOPc), in suitable solvent(s).
- pigments such as squaraines (HOSq) and Type IV oxotitanium phthalocyanine (TiOPc)
- Squaraine dispersions were prepared from HOSq pigment, PAEK comprising poly(bisphenol-A-benzophenone) (Polymer 1), described above, in a mixture of tetrahydrofuran (THF) and cyclohexanone (90/10 w/w).
- the dispersions were stable for about 4-6 hours, and eventually phase separated.
- the dispersions were coated on anodized aluminum drums as a CG layer, followed by dip-coating in a charge transport solution.
- the HOSq/PAEK dispersions were compared to a standard control drum, prepared by using polyvinylbutyral as a CG binder polymer.
- dispersions containing blends of polyvinylbutyral (BX-55Z) and a PAEK with a HOSq were also prepared and compared to the above dip-coated drums.
- the blend of polyvinylbutyral with PAEK resulted in a highly stable dispersion. Dispersion stability lasting several months, and no phase separation was observed.
- the coating quality was poor in polyvinylbutyral-free dispersions having low levels of PAEK or PAES. That is, at low levels of solids in the polyvinylbutyral-free dispersions, such as from about 1% to about 5%, by weight solids, the coating appeared streaked.
- the coating quality was improved in that there were no apparent streaks, however, the resulting optical density was very high and often resulted in high dark decay.
- the binder blends of polyvinylbutyral and polyaryl ethers resulted in excellent coating quality, even at lower dispersion solids.
- Tables 3 and 4 set forth initial electricals for photoconductor drums in which the CGL's comprise polyvinylbutyral binder, PAEK binder, or polyvinylbutyral/PAEK binder blends, respectively.
- VfJ.42 ⁇ j/cm 2 Voltage at 0.42 ⁇ J/cm 2
- Polymer I Poly(bisphenol-A-benzophenone) Table 4. Initial electricals for drums having a CGL containing 40% HOSq dispersions prepared in BX-55Z, PAEK, or BX-55Z/PAEK blends, and a CTL containing 30% TPD and Mak-5208
- Tables 3 and 4 indicate that the drums in which the CGL comprises a binder blend of polyvinylbutyral and PAEK had improved sensitivity, i.e, it required less laser energy to discharge the photoconductor drum, in comparison to a drum in which the CGL binder comprises solely polyvinylbutyral or solely PAEK. Further, the drum comprising the binder blend exhibited a lower level of dark decay than the drum comprising PAEK binder. A similar experiment was carried out with a PAES binder, at 30% HOSq pigment level and 30% TPD in transport.
- VQ.42 ⁇ j/cm 2 Voltage at 0.42 ⁇ J/cm 2
- VQ.42 ⁇ j/cm 2 Voltage at 0.42 ⁇ J/cm 2
- VQ.42 ⁇ J/cm 2 Voltage at 0.42 ⁇ J/cm 2
- Co-polymers of PAEKs were also evaluated.
- Photoconductor drums comprising CGL's having the PAEK-containing binder blends and 35% TiOPc pigment were evaluated to determine if the sensitivity attained from the lower pigment/binder ratio will match that attained in photoconductors in which the CGL has a higher pigment level (45% TiOPc).
- Photoconductors having CGL's containing the polyvinylbutyral/Co-PAEK blends result in improved sensitivity and are similar or better than those employing a higher pigment/poly vinylbutyral type sensitivity.
- the lower pigment and higher binder evel may result in improved adhesion of the coatings to the core. The results are summarized in Table 8 below.
- VQ.42 ⁇ j/cm 2 Voltage at 0.42 ⁇ J/cm 2
- blends of polyvinylbutyral and homo- or copolymers of PAEKs or PAESs in the CGL result in photoconductors having improved sensitivity and reduced dark decay as compared to binders comprising solely polyvinylbutyral or solely PAEK.
- Polyarylethersulfones were formulated as a 25% blend with polycarbonate-A (Makrolon-5208) in charge transport layers with NN -bis(3-methylphenyl)-NN - bisphenylbenzidine (TPD) or p-diethylaminobenzaldehyde-(diphenylhydrazone) (DEH) charge transport materials.
- TPD NN -bis(3-methylphenyl)-NN - bisphenylbenzidine
- DEH p-diethylaminobenzaldehyde-(diphenylhydrazone)
- the addition of the PAES in the CTL even at 5% concentration, essentially resulted in a photo-insulator for a dual layer negatively charging system.
- Polyaryletherketones were blended with polycarbonate-A in the CTL, which further comprised either TPD or DEH charge transport materials.
- Table 9 shows effects of adding PAEK in the CTL.
- the CGL was a 40% HOSq in a mixture of BX-55Z/epoxy resin (25/75), and the charge transfer molecule (CTM) used was DEH (40%).
- VQ .42 ⁇ j/cm 2 Voltage at 0.42 ⁇ J/cm 2
- the effect of the PAEK was then studied in photoconductors having a TiOPc based CGL.
- the CTL binder comprised 75% PC-A and 25% PAEK and the CGL contained a 45% type IV TiOPc and 55% BX-55Z polyvinylbutyral. Electricals are given below in Table 10, measured using a 76 ms expose-to-develop time.
- PC-Z Polycarbonate-Z
- PC-Z is less crystalline than PC-A
- PAEK PAEK
- Formulations based on PC-Z/PAEK (75/25 blend ratio) gave results similar to PC-A/PAEK.
- the effect of molecular weight was also studied. The crystallization/phase separation was observed at molecular weights ranging from 2-120K daltons.
- PAEK PAEK
- the electricals are about 40V higher and about 50-200 V for the 10% PAEK concentration.
- cardo groups such as cyclohexylidene, fluorenylidene groups helps improve the initial sensitivity, whereas groups such as isopropylidene increase the residual voltage and make the drum slower.
- the binder blend comprises no more than about 15% PAEK.
- the ratio of polycarbonate to PAEK is from about 99:1 to about 85:15.
- the effect of the PAEK on the print-performance of the photoconductor drum was evaluated by life-testing the drums in a Lexmark Optra-S 2450 laser printer.
- the photoconductor drum should exhibit minimum fatigue, and the prints at the start and end-of-life should be similar or have minimal change.
- One method for tracking the stable print-performance is to evaluate the gray scale pattern in a 1200dpi (dots-per-inch). This corresponds to a systematic change in a gray scale page from an all-black to white through a series of 128 boxes corresponding to various shades of gray (WOB, White-on-Black).
- the box corresponding to the start of life gray scale should be similar to that at the end-of-life.
- Table 12 illustrates the effect of the PAEK on the print stability of the photoconductor drum. Table 12. Life-test results for drums having a CTL containing PC-A/PAEK and TPD
- Mn number average molecular weight
- C. Wt. coat weight (mg/in 2 );
- P.Ct. page count;
- CV charge voltage;
- SV streak voltage;
- DV discharge voltage;
- WOB white on black;
- OD Isopel OD start/avg.
- the data in Table 12 indicates that the WOB value, which relates to resolution of prints in a graphic mode, was improved by the addition of a PAEK to polycarbonate solution.
- the stable print-performance of the PC-A/PAEK system results in higher page yield, for the same amount of toner.
- the use of co-polymers containing at least one group as a isopropylidene group and at least one cardo group such as cyclohexyl, fluorenyl or phthalidenyl may exhibit better performance than a homopolymer.
- the cyclic groups can help achieve electricals similar to a control (PC-A) and the isopropylidene group can give stable print-performance, as evident from Table 12.
- PC-Z charge transport solutions containing polycarbonate
- PC-A based charge transport solutions are susceptible to gelation due to the crystalline nature of PC-A.
- PAEK extends the pot-life of such solutions.
- Example G Additional prior art comparative examples and example photoconductors in accordance with the invention are set forth below.
- Charge generation formulations comprising a squaraine pigment/binder weight ratio 40/60 were prepared for photoconductor drums as follows in Comparative Examples 1 and 2, photoconductor drums of the prior art, and Examples 1 and 2, photoconductor drums in accordance with the invention. Comparative Example 1
- the transport layer formulation was prepared from a bisphenol-A polycarbonate (MAK-5208, Bayer, 62.30 g), benzidine (26.70 g) in tetrahydrofuran (THF, 249 g) and 1,4-dioxane (106 g).
- the CG layer coated drum was dip-coated in the CT formulation, dried at 120°C for 1 hour, to obtain a coat weight of about 19.43 mg/in 2 .
- the transport layer formulation was prepared from a bisphenol-A polycarbonate (MAK-5208, Bayer, 62.30 g), benzidine (26.70 g) in tetrahydrofuran (THF, 249 g) and 1,4-dioxane (106 g).
- the CG layer coated drum was dip-coated in the CT formulation and dried at 120°C for 1 hour to obtain a coat weight of about 16.54 mg/in 2
- the electrical characteristics of this drum were: charge voltage (Vo): -603V, V(0.21 ⁇ J/cm 2 ): -376V, V(0.42 ⁇ j/cm 2 ): -246V, residual voltage (Vr): -125V and dark decay (49V/sec) (OD: 1.22).
- Hydroxysquaraine (4.0 g), polyvinylbutyral (BX-55Z, 4.5 g) and poly(bisphenol-A-benzophenone ( 1.5 g) with Potter's glass beads (60 ml) was added to tetrahydrofuran (33 g) and cyclopentanone (15.0 g), in an amber glass bottle, and agitated in a paint-shaker for 12 h and diluted to about 6% solids with 2-butanone (118 g). An anodized aluminum drum was then dip-coated with the CG formulation and dried at 100°C for 5 min.
- the CG layer coated drum was dip-coated with the transport layer formulation of Comparative Example 1 and dried to obtain a coat weight of about 20.35 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -601V, V(0.21 ⁇ J/cm 2 ): -350V, V(0.42 ⁇ j/cm 2 ): -214V, residual voltage (Vr): -96V and dark decay (41 V/sec) (OD: 1.22).
- Example 2 Hydroxysquaraine (4.0 g), polyvinylbutyral (BX-55Z, 1.5 g) and poly(bisphenol-A-benzophenone ( 4.5 g) with Potter's glass beads (60 ml) was added to tetrahydrofuran (33 g) and cyclopentanone (15.0 g), in an amber glass bottle, and agitated in a paint-shaker for 12 h and diluted to about 6% solids with 2-butanone (118 g). An anodized aluminum drum was then dip-coated with the CG formulation and dried at 100°C for 5 min.
- the CG layer coated drum was dip-coated with the transport layer formulation of Comparative Example 1 and dried to obtain a coat weight of about 18.18 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -601V, V(0.21 ⁇ J/cm 2 ): -370V, V(0.42 ⁇ J/cm 2 ): -224V, residual voltage (Vr): -72V and dark decay (12V/sec) (OD: 1.08).
- Charge generation formulations comprising a squaraine pigment/binder weight ratio at 30/70 were prepared for photoconductor drums as follows in Comparative Example 3, a prior art photoconductor drum and Examples 3-5, photoconductor in accordance with the invention.
- the transport layer formulation was prepared from a bisphenol-A polycarbonate (MAK-5208, Bayer, 62.30 g), benzidine (26.70 g) in tetrahydrofuran (THF, 249 g) and 1,4-dioxane (106 g).
- the CG layer coated drum was dip-coated in the CT formulation and dried at 120°C for 1 hour to obtain a coat weight of about 18.82 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -596V, V(0.42 ⁇ J/cm 2 ): -464V, V(1.0 ⁇ J/cm 2 ): -368V, residual voltage (Vr): -305V (OD: 1.07).
- Example 3 Hydroxysquaraine (2.0 g), poly(bisphenol-A-phenylsulfone ( 2.33 g) and polyvinylbutyral (BX-55Z, 2.33 g ) with Potter's glass beads (20 ml) was added to tetrahydrofuran (55.5 g) , in an amber glass bottle, and agitated in a paint-shaker for 12 h and diluted to about 4% solids with tetrahydrofuran (88 g) and cyclohexanone (16 g). An anodized aluminum drum was then dip-coated with the CG formulation and dried at 100°C for 5 min.
- the CG layer coated drum was dip-coated with the transport layer formulation of Comparative Example 1 and dried to obtain a coat weight of about 17.62 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -598V, V(0.42 ⁇ J/cm 2 ): -455V, V(1.0 ⁇ J/cm 2 ): -332V, residual voltage (Vr): -250V (OD: 1.03).
- Hydroxysquaraine (4.0 g), polyvinylbutyral (BX-55Z, 2.33 g) and poly(cyclohexylidenebisphenol-phenylsulfone) ( 2.33 g) with Potter's glass beads (20 ml) was added to tetrahydrofuran (55.5 g) , in an amber glass bottle, and agitated in a paint-shaker for 12 h and diluted to about 4% solids with tetrahydrofuran (88 g) and cyclohexanone (16 g). An anodized aluminum drum was then dip-coated with the CG formulation and dried at 100°C for 5 min.
- the CG layer coated drum was dip-coated with the transport layer formulation of Comparative Example 1 and dried to obtain a coat weight of about 18.11 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -599V, V(0.42 ⁇ j/cm 2 ): -392V, V(1.0 ⁇ J/cm 2 ): -248V, residual voltage (Vr): -164V (OD: 1.11).
- An anodized aluminum drum was then dip-coated with the CG formulation and dried at
- the CG layer coated drum was dip-coated with the transport layer formulation of Comparative Example 1 and dried to obtain a coat weight of about 18.80 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -600V,
- Charge generation formulations consisting of a titanyl phthalocyanine pigment/binder weight ratio 45/55 were prepared for photoconductor drums as follows in Comparative Example 5-6, photoconductor drums of the prior art, and Examples 6-8, photoconductor drums in accordance with the present invention:
- the transport layer formulation was prepared from a bisphenol-A polycarbonate (MAK-5208, Bayer, 62.30 g), benzidine (26.70 g) in tetrahydrofuran (THF, 249 g) and 1,4-dioxane (106 g).
- the CG layer coated drum was dip-coated with the transport layer formulation of Comparative Example 1 and dried at 120°C for 1 hour to obtain a coat weight of about 16.40 mg/in2.
- An anodized aluminum drum was then dip-coated with the CG formulation and dried at 100°C for 5 min.
- the CG layer coated drum was dip-coated with the transport layer formulation of Comparative Example 1 and dried to obtain a coat weight of about 15.88 mg/in 2 .
- An anodized aluminum drum was then dip-coated with the CG formulation and dried at 100°C for 5 min.
- the CG layer coated drum was dip-coated with the transport layer formulation of Comparative Example 1 and dried to obtain a coat weight of about 15.88 mg/in 2 .
- Oxotitanium phthalocyanine (7.0 g), polyvinylbutyral (BX-55Z, 6.83 g), poly(phenolphthalein-benzophenone) ( 2.27 g) with Potter's glass beads (50 ml) was added to tetrahydrofuran (80 g) , in an amber glass bottle, and agitated in a paint-shaker for 12 h and diluted to about 4.5% solids with 2-butanone (262 g).
- An anodized aluminum drum was then dip-coated with the CG formulation and dried at 100°C for 5 min.
- the CG layer coated drum was dip-coated with the transport layer formulation of Comparative Example 1 and dried to obtain a coat weight of about 17.14 mg/in 2 .
- Oxotitanium phthalocyanine (7.0 g), polyvinylbutyral (BX-55Z, 6.83 g), poly(bisphenol-A-benzophenone) ( 2.27 g) with Potter's glass beads (50 ml) was added to tetrahydrofuran (80 g) , in an amber glass bottle, and agitated in a paint-shaker for 12 h and diluted to about 4.5% solids with 2-butanone (262 g). An anodized aluminum drum was then dip-coated with the CG formulation and dried at 100°C for 5 min. The CG layer coated drum was dip-coated with the transport layer formulation of Comparative Example 1 and dried to obtain a coat weight of about 17.14 mg/in 2 .
- Oxotitanium phthalocyanine (7.0 g), polyvinylbutyral (BX-55Z, 6.83 g), poly(cyclohexylidenebisphenol-benzophenone) ( 2.27 g) with Potter's glass beads (50 ml) was added to tetrahydrofuran (80 g) , in an amber glass bottle, and agitated in a paint-shaker for 12 h and diluted to about 4.5% solids with 2-butanone (262 g). An anodized aluminum drum was then dip-coated with the CG formulation and dried at 100°C for 5 min.
- the CG layer coated drum was dip-coated with the transport layer formulation of Comparative Example 1 and dried to obtain a coat weight of about 15.99 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -698V, V(0.21 ⁇ J/cm 2 ): -132V, V(0.42 ⁇ J/cm2): -94V, residual voltage (Vr): -79V and dark decay (29V/sec) (OD: 1.48).
- Comparative Examples 7 and 8 are photoconductor drums comprising a prior art charge transport layer, while Examples 9-13 are photoconductor drums comprising charge transport layers in accordance with the invention. Comparative Example 7
- a standard 45/55 type IV oxotitanium phthalocyanine (4.5 g) and polyvinylbutyral (5.5 g)in a mixture of 2-butanone/cyclohexanone (90/10) at 3% solids was used to coat an anodized aluminum drum, and dried at 100°C for 15 min.
- a transport solution corresponding to bisphenol-A polycarbonate (Makrolon-5208, 56 g), TPD (24 g) were dissolved in THF (240 g) and 1 ,4-dioxane (80 g), with a surfactant (DC-200, 6 drops).
- the anodized drum previously coated with a CG layer was dip-coated with the transport solution and was dried at 120°C for 1 hour to obtain a coat weight of 14.53 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -852V; voltage (0.21 ⁇ J/cm 2 ): -322V, voltage (0.42 ⁇ J/cm 2 ): -129V, residual voltage: -77V.
- a standard 45/55 type IV oxotitanium phthalocyanine (4.5 g) and polyvinylbutyral (5.5 g) in a mixture of 2-butanone/cyclohexanone (90/10) at 3% solids was used to coat an anodized aluminum drum, and was dried at 100°C for 15 min.
- a transport solution corresponding to bisphenol-A polycarbonate (Makrolon-5208, 52 g), poly(bisphenol-A-benzophenone) (4.0 g) and TPD (24 g) were dissolved in THF (240 g) and 1,4-dioxane (80 g), with a surfactant (DC-200, 6 drops).
- the anodized drum previously coated with a CG layer was dip-coated with the transport solution and was dried at 120°C for 1 hour to obtain a coat weight of 13.43 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -849V; voltage (0.21 ⁇ J/cm 2 ): -355V, voltage (0.42 ⁇ j/cm 2 ): -201V, residual voltage: -152V.
- Example 10 A standard 45/55 type IV oxotitanium phthalocyanine (4.5 g) and polyvinylbutyral (5.5 g) in a mixture of 2-butanone/cyclohexanone (90/10) at 3% solids was used to coat an anodized aluminum drum, and was dried at 100°C for 15 min.
- a transport solution corresponding to bisphenol-A polycarbonate (Makrolon-5208, 52 g), poly(cyclohexylidenebisphenol-benzophenone) (4.0 g) and TPD (24 g) were dissolved in THF (240 g) and 1,4-dioxane (80 g), with a surfactant (DC-200, 6 drops).
- the anodized drum previously coated with a CG layer was dip-coated with the transport solution, and was dried at 120°C for 1 hour to obtain a coat weight of 14.67 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -848V; voltage (0.21 ⁇ J/cm 2 ): -361V, voltage (0.42 ⁇ J/cm 2 ): -174V, residual voltage: -115V.
- a standard 45/55 type IV oxotitanium phthalocyanine (4.5 g) and polyvinylbutyral (5.5 g) in a mixture of 2-butanone/cyclohexanone (90/10) at 3% solids was used to coat an anodized aluminum drum, and was dried at 100°C for 15 min.
- a transport solution co ⁇ esponding to bisphenol-A polycarbonate (Makrolon-5208, 52 g), poly(fluorenylidenebisphenol-benzophenone) (4.0 g) and TPD (24 g) were dissolved in THF (240 g) and 1,4-dioxane (80 g), with a surfactant (DC-200, 6 drops).
- the anodized drum previously coated with a CG layer was dip-coated with the transport solution, and was dried at 120°C for 1 hour to obtain a coat weight of 15.36 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -847V; voltage (0.21 ⁇ J/cm 2 ): -343V, voltage (0.42 ⁇ J/cm 2 ): -178V, residual voltage: -122V.
- a standard 45/55 type IV oxotitanium phthalocyanine (4.5 g) and polyvinylbutyral (5.5 g) in a mixture of 2-butanone/cyclohexanone (90/10) at 3% solids was used to coat an anodized aluminum drum, and was dried at 100°C for 15 min.
- a transport solution co ⁇ esponding to bisphenol-A polycarbonate (Makrolon-5208, 52 g), poly(cyclohexylidenebisphenol-benzophenone) (8.66 g) and TPD (26 g) were dissolved in THF (240 g) and 1,4-dioxane (80 g), with a surfactant (DC-200, 6 drops).
- An anodized drum previously coated with a CG layer was dip-coated with the transport solution and was dried at 120°C for 1 hour to obtain a coat weight of 15.84 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -851V; voltage (0.21 ⁇ J/cm 2 ): -364V, voltage (0.42 ⁇ J/cm 2 ): -232V, residual voltage: -180V.
- Comparative Example 8 A standard 45/55 type IV oxotitanium phthalocyanine (4.5 g) and polyvinylbutyral (5.5 g) in a mixture of 2-butanone/cyclohexanone (90/10) at 3% solids was used to coat an anodized aluminum drum, and was dried at 100°C for 15 min.
- a transport solution co ⁇ esponding to bisphenol-A polycarbonate (Makrolon-5208, 18 g), and DEH (12 g), Savinyl Yellow (0.2 g) were dissolved in THF (90 g) and 1,4-dioxane (30 g), with a surfactant (DC-200, 3 drops).
- An anodized drum previously coated with a CG layer was dip-coated with the transport solution, and was dried at 120°C for 1 hour to obtain a coat weight of 17.48 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -848V; voltage (0.21 ⁇ J/cm 2 ): -361V, voltage (0.42 ⁇ J/cm 2 ): -174V, residual voltage: -115 V.
- PAEKs 1,1-diphenylhydrazine hydrochloride, or a hydrazone, 9-fluorenone hydrazone, respectively.
- the pre-polymers (PAEKs) were synthesized by the aromatic nucleophilic displacement reaction of difluorobenzophenone using various potassium bisphenolates in N,N-dimethylacetamide solvent, as discussed above. All polymers were isolated by precipitation in water and the resulting polymer was chopped in a high speed blender.
- Typical work-up included the steps of stirring the off-white fibrous polymer in water, neutralizing with aqueous acid (-5% HCl), filtering, sti ⁇ ing in boiling water for about one hour, filtering, sti ⁇ ing in boiling methanol for about 0.5 hours, filtering and drying at 100°C for about 16 hours in a vacuum oven.
- the yield for the polymerization was about 90%.
- appropriate amounts of two or more bisphenols were used, and the polymerization procedure was similar to the one outlined above.
- PAEK-hydrazones poly(bisphenol-A-benzophenone)
- Mn Number average molecular weight
- Mw Weight average molecular weight
- Polyd. Polydispersity
- the PAEK-azines were isolated as orange fibrous solids, and were typically soluble in tetrahydrofuran, 1 ,4-dioxane and chlorinated hydrocarbons, and were partially soluble in ethyl acetate, acetone and toluene.
- the polymers comprised the structure:
- the orange fibrous polymer was isolated by filtration, washed in boiling water (about 45 min.), filtered, washed in boiling methanol (about 45 min.), filtered and dried at 100°C for about 16 hours. The yield was about 4.31 g. The number average molecular weight of the polymer was about 14.8K. Polv(fluorenylidenebisphenol-benzophenone-fluorenone azine)
- the orange fibrous polymer was isolated by filtration, washed in boiling water (45 min.), filtered, washed in boiling methanol (45 min.), filtered and dried at 100°C for about 16 hours. The yield was about 6.43 g. The number average molecular weight of the polymer was about 31.9K.
- the orange fibrous polymer was isolated by filtration, washed in boiling water (about 45 min.), filtered, washed in boiling methanol (about 45 min.), filtered and dried at about 100°C for about 16 hours. The yield was about 6.78 g. The number average molecular weight of the polymer was about 33.8K.
- the yellow fibrous polymer was isolated by filtration, washed in boiling water (about 45 min.), filtered, washed in boiling methanol (about 45 min.), filtered and dried at about 100°C for about 16 hours. The yield was about 5.29 g. The number average molecular weight of the polymer was about 11.8K.
- Poly(cyclohexylidenebisphenol-benzophenone-diphenylhydrazone) was synthesized from poly(cyclohexylidenebisphenol-benzophenone) (5.000 g, 11.19 mmol), 1,1-diphenylhydrazine hydrochloride (2.47 g, 11.19 mmol) , THF (18 g) and N,N-dimethyl acetamide (18 g) in a manner similar to poly(bisphenol-A-benzophenone-diphenylhydrazone). The yield was about 5.74 g. The number average molecular weight of the polymer was about 12.9K.
- Poly(cyclohexylidenebisphenol-benzophenone-diphenylhydrazone-bisphenol-A) was synthesized from poly(cyclohexylidenebisphenol-benzophenone-bisphenol-A) (5.000 g, 5.86 mmol), 1,1-diphenylhydrazine hydrochloride (2.58 g, 11.72 mmol) , THF (17 g) and N,N-dimethyl acetamide (17 g) in a manner similar to poly(bisphenol-A-benzophenone-diphenylhydrazone). The yield was about 5.87 g. The number average molecular weight of the polymer was about 52.3K.
- Example I Charge transport layers were prepared using NN -bis(3-methylphenyl)-NN - bisphenylbenzidine (TPD).
- the CTL binder was a 90/10 w/w ratio blend of polycarbonate (PC-A) and the PAEK-azine, with 30% TPD concentration.
- the transport layer was coated on top of a CG layer comprising 45% type IV TiOPc and 55% polyvinylbutyral (BX-55Z).
- the initial electricals for the PC-A PAEK-azines are given in Table 15.
- VQ 21 ⁇ j/cm 2 Voltage at 0.21 ⁇ j /cm 2
- VQ 42 ⁇ j/cm 2 Voltage at 0.42 ⁇ J/cm 2
- PAEK-azine to the TPD transport does not adversely affect the initial electricals of the TPD system.
- the coating quality for the PAEK-azine blends was similar to the control (PC-A).
- PC-A control
- PAEK at a 7% dopant level increased the residual voltage of the photoconductor somewhat.
- PAEK-azines at a 10% dopant level increased the residual voltage by only 10V.
- Mn number average molecular weight
- C. Wt. coat weight (mg/in 2 );
- P.Ct. page count;
- CV charge voltage;
- SV streak voltage;
- DV discharge voltage;
- WOB white on black;
- OP Isopel OD start/avg.
- Table 16 demonstrates that the print-performance from a PC-A/PAEK-azine drum is improved relative to a PC-A drum.
- the WOB (white-on-black) box appears to be more severely affected in the PC-A case, but shows a very small change for the blends. Based upon comparison of the start and end-of-life electricals, the charge voltage and streak voltage are severely affected in the PC-A case; in contrast, the blends exhibited improved stability. In the PC-A case, the prints get too dark with life, as indicated by the change in Isopel optical density from 0.75 to an average of 0.92. In contrast, the blends showed a smaller change through life.
- the stable print-performance of the PC-A/PAEK-azine system in turn results in higher page yield for the same amount of toner.
- the binder blend drums averaged about 2000 more pages than the control drum (PC-A).
- the print usage is another tool to assess the amount of toner consumed per page.
- the toner-to-page and toner-to-cleaner (unused toner) was 17.0 and 4.3, respectively.
- the drums comprising binder blends required 14.9-15.7 mg/page for the toner-to-page and only about 3.9 mg went to the cleaner.
- PAEK-azine copolymers give similar results.
- Example K The PAEK-hydrazones were also formulated in a transport layer, and photoconductor drums comprising the transport layer were evaluated for initial electrical performance and fatigue/electrical stability.
- the initial electricals given in Table 17, set forth below co ⁇ espond to a drum having a CGL containing 45% Type IV TiOPc/55% BX-55Z polyvinylbutyral, and a CTL containing 40% DEH transport in PC-A/PAEK-hydrazone blend.
- a homopolymer and co-polymer were used for the initial electricals and print-test through life.
- PAEK-hydrazone did not adversely affect the initial electricals of this system.
- PAEK-azines or PAEK-hydrazones increased the pot-life of a polycarbonate-containing charge transport solution about 3-fold relative to a polycarbonate-containing charge transport solution which is free of PAEK-azines and
- PAEK-hydrazones The extended pot-life leads to cost-savings for the charge transport solution will be discarded and replaced less frequently.
- Comparative Examples 9 and 10 are photoconductor drums comprising a prior art charge transport layer
- Examples 14-17 are photoconductor drums comprising charge transport layers in accordance with the invention.
- Comparative Example 9 A standard 45/55 weight ratio mixture of type IV oxotitanium phthalocyanine
- the anodized drum previously coated with a CG layer was dip-coated with the transport solution and was dried at 120°C for 1 hour to obtain a coat weight of about 17.71 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -850V; voltage (0.21 ⁇ J/cm 2 ): -330V, voltage (0.42 ⁇ J/cm 2 ): -185V, residual voltage: -131V.
- a standard 45/55 weight ratio mixture of Type IV oxotitanium phthalocyanine (4.5 g) and polyvinylbutyral (5.5 g) in a mixture of 2-butanone/cyclohexanone (90/10) at 3% solids was used to coat an anodized aluminum drum and was dried at about 100°C for about 15 min.
- Transport materials co ⁇ esponding to bisphenol-A polycarbonate (Makrolon-5208, 28.04 g), poly(bisphenol-A-benzophenone-fluorenone azine) (Mn ⁇ 14.8K, 3.11 g) and TPD (13.35 g), were dissolved in THF (133.5 g) and 1,4-dioxane (44.5 g), with a surfactant (DC-200, 3 drops).
- the anodized drum previously coated with a CG layer was dip-coated with the transport solution and was dried at 120°C for about one hour to obtain a coat weight of about 16.91 mg/in 2 .
- Example 15 A standard 45/55 weight ratio mixture of Type IV oxotitanium phthalocyanine
- the anodized drum previously coated with a CG layer was dip-coated with the transport solution and was dried at about 120°C for about one hour to obtain a coat weight of about 16.85 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -846V; voltage (0.21 ⁇ J/cm 2 ): -345V, voltage (0.42 ⁇ j/cm 2 ): -207V, residual voltage: -149V.
- a standard weight ratio mixture of 45/55 Type IV oxotitanium phthalocyanine (4.5 g) and polyvinylbutyral (5.5 g) in a mixture of 2-butanone/cyclohexanone (90/10) at 3% solids was used to coat an anodized aluminum drum, and was cured at about 100°C for about 15 min.
- the anodized drum previously coated with a CG layer was dip-coated with the transport solution and was dried at about 120°C for about one hour to obtain a coat weight of about 16.93 mg/in 2 .
- a standard 45/55 weight ratio mixture of Type IV oxotitanium phthalocyanine (4.5 g) and polyvinylbutyral (5.5 g) in a mixture of 2-butanone/cyclohexanone (90/10) at 3% solids was used to coat an anodized aluminum drum and was dried at about 100°C for about 15 min.
- Transport materials co ⁇ esponding to bisphenol-A polycarbonate (Makrolon-5208, 18 g), DEH (12 g) and Savinyl Yellow (0.20 g) were dissolved in THF (90 g) and 1,4-dioxane (30 g), with a surfactant (DC-200, 3 drops).
- the anodized drum previously coated with a CG layer was dip-coated with the transport solution and was dried at about 120°C for about one hour to obtain a coat weight of about 17.48 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -850V; voltage (0.21 ⁇ J/cm 2 ): -361V, voltage (0.42 ⁇ J/cm 2 ): -194V, residual voltage: -150V.
- a standard 45/55 weight ratio mixture of Type IV oxotitanium phthalocyanine (4.5 g) and polyvinylbutyral (5.5 g) in a mixture of 2-butanone/cyclohexanone (90/10) at 3% solids was used to coat an anodized aluminum drum and was dried at about 100°C for about 15 min.
- Transport materials co ⁇ esponding to bisphenol-A polycarbonate (Makrolon-5208, 16.74 g), poly(cyclohexylidenebisphenol-benzophenone-fluorenone azine-bisphenol-A) (1.26 g), DEH (12 g) and Savinyl Yellow (0.20 g) were dissolved in THF (90 g) and 1,4-dioxane (30 g), with a surfactant (DC-200, 3 drops).
- the anodized drum previously coated with a CG layer was dip-coated with the transport solution and was dried at about 120°C for about one hour.
- the electrical characteristics for a drum with coat weight of 12.63 mg/in 2 were: charge voltage (Vo): -848V; voltage (0.21uJ/cm2): -381V, voltage (0.42 ⁇ j/cm 2 ): -236V, residual voltage: -186V.
- the electrical characteristics for a drum with coat weight of 28.52 mg/in 2 were: charge voltage (Vo): -849V; voltage (0.21 ⁇ J/cm 2 ): -387V, voltage (0.42 ⁇ J/cm 2 ): -217V, residual voltage: -159V.
- PAPFAEs Poly aryl-perfluoroaryl ether
- PAPFAE polymerizations were carried out by the reaction of stoichiometric amounts of a bisphenol or a bisphenolate salt with decafluorobiphenyl in N,N-dimethylacetamide, at a temperature of about 120°C.
- the reactions were catalyzed by a base, either potassium carbonate or cesium fluoride. Two equivalents of the base was used with respect to the bisphenol or bisphenolate salt. All polymerizations were quenched in water, and the resulting product chopped in a high speed blender.
- the polymer was isolated by filtration, neutralized, and sti ⁇ ed in boiling water for about 1 hour, and then sti ⁇ ed in boiling methanol for about 1 hour.
- the white fibrous polymers were dried in a vacuum-oven at 100°C for 16 hours. Near quantitative yields were obtained in all cases.
- the polymers comprised the structure:
- reaction times were less than about 3 hours in all cases.
- the reaction time co ⁇ esponds to the time following the azeotropic removal of water followed by removal of toluene.
- the glass-transition temperature of the polymers increased on introducing bulky cardo groups in the polymer backbone.
- Tg of a fluorenylidene-containing backbone was greater than Tg of a cyclohexylidene-containing backbone which was greater than Tg of isopropylidene- containing backbone.
- the solution was stirred for about 3 hours, and then precipitated in water.
- the off-white polymer was chopped in a high-speed blender, neutralized and filtered.
- the white polymer was sti ⁇ ed in boiling water for about 1 hour, filtered, and then sti ⁇ ed in boiling methanol for about 1 hour and filtered.
- the polymer was then dried in an vacuum oven for about 16 hours at 100°C. The yield was about 13.12 g.
- the number average molecular weight of the polymer was about 71.7K.
- the white polymer was sti ⁇ ed in boiling water for about 1 hour, filtered, and then sti ⁇ ed in boiling methanol for about 1 hour and filtered.
- the fibrous white polymer was then dried in an vacuum oven for about 16 hours at about 100°C. The yield was about 9.02 g.
- the number average molecular weight of the polymer was about 25.5K.
- the white polymer was stirred in boiling water for about 1 hour, filtered, and then sti ⁇ ed in boiling methanol for about 1 hour and filtered.
- the fibrous white polymer was then dried in an vacuum oven for about 16 hours at about 100°C. The yield was about 9.98 g.
- the number average molecular weight of the polymer was about 20.5 K.
- Charge transport solutions comprising a polcarbonate, a PAPFAE and a charge transport molecule were prepared. Unlike polytetrafluoroethylene systems, the perfluoroarylpolymers are soluble and were dissolved in the transport solution, following the addition of polycarbonate. Generally the solutions appeared nearly homogeneous and clear. However, at the 25% perfluoropolymer level, the solutions were slightly translucent. Charge transport layers comprising
- N,N'-bis(3-methylphenyl)-N,N'-bisphenylbenzidine (TPD) in a mixture of polycarbonate-A and a perfluoroarylpolymer were coated on a type IV TiOPc/BX-55Z polyvinylbutyral charge generation layer, and the results are summarized in Table 19.
- VQ.22 ⁇ J/cm 2 Voltage at 0.22 ⁇ J/cm 2
- PAPFAE polymers comprise cyclohexylidene and/or fluorenylidene groups.
- the mixture of polycarbonate and PAPFAE comprises less then 25% PAPFAE, by weight of total mixture.
- the charge transport solutions preferably comprise a blend of a polycarbonate and a PAPFAE in a weight ratio of about 95:5.
- Fomblin Z-Dol poly(perfluoropropylene oxide-co-perfluoroformaldehyde, Mn -6600) was dispersed in the charge transport layer consisting of TPD and PC-A.
- the fluoropolymer was used at 1% and 5% levels. Table 20, set forth below, illustrates the effect of the fluoropolymer systems on the electricals characteristics of a photoconductor drum.
- the photoconductor drum containing the isopropylidene based perfluoropolymer (Mn ⁇ 71K, 5%) in the CTL was evaluated for life in an Optra-S printer.
- the results from this experiment are set forth below in Table 21.
- the incorporation of the soluble PAPFAE in the transport layer improves the drum-end wear.
- the PAPFAE has a significant effect even at 5% loading (with respect to the binder), this co ⁇ esponds to about 3.5% of all solids in the CTL.
- the print-quality appears to be stable over life. This is evidenced by the severe positive fatigue observed in the case of the control drum (PC-A), with the streak page voltage changing by about 150V. This causes more toner to be deposited on the print-page, whereby the graphics become dark with life.
- PC-A control drum
- the PAPFAE system shows a nominal 50V fatigue, and nearly stays constant through life, thereby resulting in a stable print-quality.
- the PAPFAE drum was relatively more wear resistant; some drum end-wear was observed at about 20,000 prints, a 40% improvement in the wear.
- Another advantage observed using the PAPFAE as a blend with the polycarbonate, in particular PC-A is the improvement in pot-life of the transport solution.
- the pot-life of a transport solution containing PC-A and TPD (70/30 w/w) is about a week, after which the solution gels.
- the pot-life was found to increase at least about 2- fold, preferably at least about 3-fold. This relates to a significant cost-savings when using PC-A containing solutions.
- Comparative Example 11 is a photoconductor drum comprising a prior art charge transport layer, while Examples 18-21 are photoconductor drums comprising charge transport layers in accordance with the invention.
- a charge generation formulation consisting of a 45/55 pigment/binder ratio was prepared as follows.
- the transport layer formulation was prepared by a dissolving a bisphenol-A polycarbonate (MAK-5208, Bayer, 62.30 g), benzidine (26.70 g) in tetrahydrofuran (THF, 249 g) and 1,4-dioxane (106 g).
- the CG layer coated drum was dip-coated with the CT formulation and dried at about 120°C for about 1 hour to obtain a coat weight of about 16.80 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -848V, residual voltage (Vr): -95V (OD: 1.63).
- Example 18 Example 18:
- the charge generation formulation used in Comparative Example 11 was used to coat an anodized aluminum drum, and was dried at about 100°C for about 5 min.
- the transport layer formulation was prepared by dissolving bisphenol-A polycarbonate (19.0 g), poly(bisphenol-A-perfluorobiphenyl) (P(BPA-PFBP), Mn ⁇ 70.7K, 1.0 g) and TPD (8.57 g) in a mixture of THF (97.6 g) and dioxane (32.5 g), along with a surfactant (DC-200, 3 drops).
- the CT solution was coated on the CGL to obtain a coat weight of about 17.25 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -850V, residual voltage (Vr): -133V (OD: 1.63).
- the charge generation formulation used Comparative Example 11 was used to coat an anodized aluminum drum, and was dried at about 100°C for about 5 min.
- the transport layer formulation was prepared by dissolving bisphenol-A polycarbonate (19.0 g), poly(bisphenol-A-perfluorobiphenyl) (P(BPA-PFBP), Mn ⁇ 25.5K, 1.0 g) and TPD (8.57 g) in a mixture of THF (97.6 g) and dioxane (32.5 g), along with a surfactant (DC-200, 3 drops).
- the CT solution was coated on the CGL to obtain a coat weight of about 17.40 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -849V, residual voltage (Vr): -139V (OD: 1.51).
- the charge generation formulation used in Comparative Example 11 was used to coat an anodized alumina drum, and was dried at about 100°C for about 5 min.
- the transport layer formulation was prepared by dissolving bisphenol-A polycarbonate (19.0 g), poly(cyclohexylidenebisphenol-perfluorobiphenyl) (P(CYCLBP-PFBP), Mn ⁇ 20.8K, 1.0 g) and TPD (8.57 g) in a mixture of THF (97.6 g) and 1,4-dioxane (32.5 g), along with a surfactant (DC-200, 3 drops).
- the CT solution was coated on the CGL to obtain a coat weight of about 15.80 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -851V, residual voltage (Vr): -101V (OD: 1.63).
- Example 21 Example 21:
- the charge generation formulation used in Comparative Example 11 was used to coat an anodized alumina drum, and was dried at about 100°C for about 5 min.
- the transport layer formulation bisphenol-A polycarbonate (19.0 g), poly(fluorenylidenebisphenol- perfluorobiphenyl) (P(FLUOBP-PFBP), Mn ⁇ 68.8K, 1.0 g) and TPD (8.57 g) in a mixture of THF (97.6 g) and 1,4-dioxane (32.5 g), along with a surfactant (DC-200, 3 drops).
- the CT solution was coated on the CGL to obtain a coat weight of about 17.50 mg/in 2 .
- the electrical characteristics of this drum were: charge voltage (Vo): -846V, residual voltage (Vr): -113V (OD: 1.63).
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Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01901892A EP1247142A4 (en) | 2000-01-10 | 2001-01-09 | Electrophotographic photoconductors comprising polyaryl ethers |
AU2001227745A AU2001227745A1 (en) | 2000-01-10 | 2001-01-09 | Electrophotographic photoconductors comprising polyaryl ethers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/480,026 | 2000-01-10 | ||
US09/480,026 US6232025B1 (en) | 2000-01-10 | 2000-01-10 | Electrophotographic photoconductors comprising polaryl ethers |
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WO2001051995A1 true WO2001051995A1 (en) | 2001-07-19 |
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Family Applications (1)
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PCT/US2001/000612 WO2001051995A1 (en) | 2000-01-10 | 2001-01-09 | Electrophotographic photoconductors comprising polyaryl ethers |
Country Status (5)
Country | Link |
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US (2) | US6232025B1 (en) |
EP (1) | EP1247142A4 (en) |
CN (1) | CN1236363C (en) |
AU (1) | AU2001227745A1 (en) |
WO (1) | WO2001051995A1 (en) |
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DE102005001599A1 (en) * | 2005-01-12 | 2006-07-20 | Basf Ag | Functionalized polyaryl ethers |
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US8940466B2 (en) | 2012-12-31 | 2015-01-27 | Lexmark International, Inc. | Photo conductor overcoat comprising radical polymerizable charge transport molecules and hexa-functional urethane acrylates |
US8802339B2 (en) | 2012-12-31 | 2014-08-12 | Lexmark International, Inc. | Crosslinkable urethane acrylate charge transport molecules for overcoat |
US8951703B2 (en) | 2012-12-31 | 2015-02-10 | Lexmark International, Inc. | Wear resistant urethane hexaacrylate materials for photoconductor overcoats |
US20150185640A1 (en) * | 2013-03-15 | 2015-07-02 | Lexmark International, Inc. | Overcoat Formulation for Long-Life Electrophotographic Photoconductors and Method for Making the Same |
US9360822B2 (en) | 2013-12-13 | 2016-06-07 | Lexmark International, Inc. | Photoconductor overcoat having radical polymerizable charge transport molecules containing two ethyl acrylate functional groups and urethane acrylate resins containing six radical polymerizable functional groups |
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CN108350261A (en) * | 2015-10-30 | 2018-07-31 | 沙特基础工业全球技术有限公司 | High impact-resistant polyaryletherketone-polycarbonate Alloys |
CN105694041B (en) * | 2016-03-15 | 2017-10-13 | 吉林大学 | The polyarylether sulfone copolymer of a kind of side chain containing porphyrin and preparation method thereof |
CN113698590B (en) * | 2021-09-17 | 2022-08-19 | 吉林大学 | Melt-processable end-capped fluorine-containing polyarylether resin as well as preparation method and application thereof |
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- 2001-01-09 CN CNB018044263A patent/CN1236363C/en not_active Expired - Fee Related
- 2001-01-09 EP EP01901892A patent/EP1247142A4/en not_active Withdrawn
- 2001-01-09 AU AU2001227745A patent/AU2001227745A1/en not_active Abandoned
- 2001-01-09 WO PCT/US2001/000612 patent/WO2001051995A1/en active Application Filing
- 2001-01-23 US US09/766,997 patent/US6350553B2/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
EP1247142A4 (en) | 2006-06-07 |
AU2001227745A1 (en) | 2001-07-24 |
EP1247142A1 (en) | 2002-10-09 |
US20010023047A1 (en) | 2001-09-20 |
US6232025B1 (en) | 2001-05-15 |
US6350553B2 (en) | 2002-02-26 |
CN1236363C (en) | 2006-01-11 |
CN1397030A (en) | 2003-02-12 |
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