Developer compositions and processes

Abstract

A liquid developer comprised of a nonpolar liquid, thermoplastic resin, optional colorant, and an alumina charge acceptance additive.

Description

BACKGROUND OF THE INVENTION

This invention is generally directed to liquid developer compositions and processes thereof and wherein there can be generated improved developed images thereof in bipolar ion charging processes, and reverse charge imaging and printing development (RCP) processes, reference U.S. Pat. No. 5,826,147, the disclosure of which is totally incorporated herein by reference, and wherein the developer contains no charge director, or wherein the developer contains substantially no charge director. More specifically, the liquid developer of the present invention is clear in color and is comprised of a resin, a hydrocarbon carrier, and a charge acceptor component with, for example, a high dielectric constant, and yet more specifically, wherein the charge acceptor component is comprised of an alumina, especially neutral, acid, or basic aluminas with a nanoparticle size, such as zirconates, like calcium zirconate, metal tungstates, calcium titanates, barium titanates, and the like.

The present invention is also specifically directed to a electrostatographic imaging process wherein an electrostatic latent image bearing member containing a layer of marking material, toner particles, or liquid developer as illustrated herein and containing a charge acceptance additive, which additive may be coated on the developer, is selectively charged in an imagewise manner to create a secondary latent image corresponding to the electrostatic latent image on the imaging member. Imagewise charging can be accomplished by a wide beam charge source for introducing free mobile charges or ions in the vicinity of the electrostatic latent image coated with the layer of marking material or toner particles. The latent image causes the free mobile charges or ions to flow in an imagewise ion stream corresponding to the latent image. These charges or ions, in turn, are accepted by the marking material or toner particles, leading to imagewise charging of the marking material or toner particles with the layer of marking material or toner particles itself becoming the latent image carrier. The latent image carrying toner layer is subsequently developed by selectively separating and transferring image areas of the toner layer to a copy substrate for producing an output document.

The present invention also relates to an imaging apparatus wherein an electrostatic latent image, including image and non-image areas, is formed in a layer of marking material, and further wherein the latent image can be developed by selectively separating portions of the latent image bearing layer of the marking material such that the image areas reside on a first surface and the non-image areas reside on a second surface. In a simple embodiment, the invention can be defined as an image development apparatus, comprising a system for generating a first electrostatic latent image on an imaging member, wherein the electrostatic latent image includes image and non-image areas having distinguishable charge potentials, and a system for generating a second electrostatic latent image on a layer of marking materials situated adjacent the first electrostatic latent image on the imaging member, wherein the second electrostatic latent image includes image and non-image areas having distinguishable charge potentials of a polarity opposite to the charge potentials of the charged image and non-image areas in the first electrostatic latent image.

The liquid developers and processes of the present invention possess a number of advantages including the development and generation of images with excellent image quality, the avoidance of a charge director, the use of the developers in a reverse charging development process, excellent, for example, about 90 to about 98 percent image transfer, and the avoidance of complex chemical charging of the developer. Poor transfer can, for example, result in poor solid area coverage if insufficient toner is transferred to the final substrate and can also cause image defects such as smears and hollowed fine features. Overcharging the toner particles can result in low reflective optical density images or poor color richness or chroma since only a few very highly charged particles can discharge all the charge on the dielectric receptor causing too little toner to be deposited. To overcome or minimize such problems, the liquid toners, or developers and processes of the present invention were arrived at after extensive research. Other advantages are as illustrated herein and also include minimal or no image blooming, the generation of excellent solid area images, minimal or no developed image character defects, the enablement of clear, or colorless liquid developers, excellent image resolution, and the like.

PRIOR ART

A latent electrostatic image can be developed with toner particles dispersed in an insulating nonpolar liquid. These dispersed materials are known as liquid toners or liquid developers. The latent electrostatic image may be generated by providing a photoconductive imaging member or layer with a uniform electrostatic charge, and developing the image with a liquid developer, or colored toner particles dispersed in a nonpolar liquid which generally has a high volume resistivity in excess of 10 9 ohm-centimeters, a low dielectric constant, for example below about 3, and a moderate vapor pressure. Generally, the toner particles are less than about 30 μm (microns) average by area size as measured with the Malvern 3600E particle sizer.

U.S. Pat. No. 5,019,477, the disclosure of which is totally incorporated herein by reference, discloses a liquid electrostatic developer comprising a nonpolar liquid, thermoplastic resin particles, and a charge director. The ionic or zwitterionic charge directors illustrated may include both negative charge directors, such as lecithin, oil-soluble petroleum sulfonates and alkyl succinimide, and positive charge directors such as cobalt and iron naphthanates. The thermoplastic resin particles can comprise a mixture of (1) a polyethylene homopolymer or a copolymer of (i) polyethylene and (ii) acrylic acid, methacrylic acid or alkyl esters thereof, wherein (ii) comprises 0.1 to 20 weight percent of the copolymer; and (2) a random copolymer (iii) of vinyl toluene and styrene and (iv) butadiene and acrylate.

U.S. Pat. No. 5,030,535, the disclosure of which is totally incorporated herein by reference, discloses a liquid developer composition comprising a liquid vehicle, a charge additive and toner pigmented particles. The toner particles may contain pigment particles and a resin selected from the group consisting of polyolefins, halogenated polyolefins and mixtures thereof. The liquid developers can be prepared by first dissolving the polymer resin in a liquid vehicle by heating at temperatures of from about 80° C. to about 120° C., adding pigment to the hot polymer solution and attriting the mixture, and then cooling the mixture whereby the polymer becomes insoluble in the liquid vehicle, thus forming an insoluble resin layer around the pigment particles.

Moreover, in U.S. Pat. No. 4,707,429, the disclosure of which is totally incorporated herein by reference, there are illustrated, for example, liquid developers with an aluminum stearate charge adjuvant. Liquid developers with charge directors are also illustrated in U.S. Pat. No. 5,045,425. Further, of interest with respect to liquid developers are U.S. Pat. Nos. 5,034,299; 5,066,821 and 5,028,508, the disclosures of which are totally incorporated herein by reference.

Illustrated in U.S. Pat. No. 5,306,591, the disclosure of which is totally incorporated herein by reference, is a liquid developer comprised of a liquid component, thermoplastic resin; an ionic or zwitterionic charge director, or directors soluble in a nonpolar liquid, and a charge additive, or charge adjuvant comprised of an imine bisquinone; in U.S. Statutory Invention Registration No. H1483 there is described a liquid developer comprised of thermoplastic resin particles, and a charge director comprised of an ammonium AB diblock copolymer, and in U.S. Pat. No. 5,307,731 there is disclosed a liquid developer comprised of a liquid, thermoplastic resin particles, a nonpolar liquid soluble charge director, and a charge adjuvant comprised of a metal hydroxycarboxylic acid, the disclosures of each of the above patent, and the Statutory Registration being totally incorporated herein by reference.

SUMMARY OF THE INVENTION

Examples of features of the present invention include:

It is a feature of the present invention to provide a liquid developer with many of the advantages illustrated herein, such as (1) an increase both positive and negative ion charging levels, as measured by surface voltages after charging and which are proportional to toner charging levels; (2) increased positive and negative surface charging voltages thus providing for improvements in RCP development contrast potential, forming sharp images and a clean background, and which advantages may be attributed, for example, to the small alumina particle size. The smaller the charge acceptor particle, the higher the charge per charge acceptor particle.

Another feature of the present invention resides in the provision of a liquid develop, especially a clear colored developer with no colorant, capable of modulated particle charging with, for example, corona ions for image quality optimization.

It is a further feature of the invention to provide positively charged, and/or negatively charged liquid developers, especially colorless or clear in color developers, wherein there are selected as charge acceptance agents or charge acceptance additives alumina, especially neutral, acid, or basic aluminas and the like.

It is still a further feature of the invention to provide positively, and negatively charged liquid developers wherein developed image defects, such as smearing, loss of resolution and loss of density, and color shifts in prints having magenta images overlaid with yellow images are eliminated or minimized and wherein the charge level of negative and positive polarities are balanced or substantially equal.

Also, in another feature of the present invention there are provided positively charged liquid developers with certain charge acceptance agents that are in embodiments superior to liquid developers with no charge director in that they can be selected for RCP development, reference U.S. Pat. No. 5,826,147, the disclosure of which is totally incorporated herein by reference, and wherein there can be generated result high quality images.

Furthermore, in another feature of the present invention there are provided liquid toners that enable excellent image characteristics, and which toners enhance the positive charge of the resin selected, such as ELVAX®, based resins.

These and other features of the present invention can be accomplished in embodiments by the provision of liquid developers.

Aspects of the present invention relate to a liquid developer comprised of a nonpolar liquid, thermoplastic resin, optional colorant, and an alumina charge acceptance additive; a developer wherein the charge acceptance agent or additive is neutral, acid, basic or mixtures thereof; a developer wherein the charge acceptance additive is neutral alumina with an optional particle size of from about 5 to about 6 nanometers, an optional specific surface area of from about 150 to about 160 m 2 /g and a pH of an aqueous suspension thereof of from about 6.5 to about 7.5, acidic alumina with an optional particle size of about 5 to about 6, an optional specific surface area of about 150 to about 160 m 2 /g and a pH of an aqueous suspension thereof of from about 4 to about 5, or basic alumina with a particle size of about 5 to about 6, a specific surface area of about 150 to about 160 m 2 /g and a pH of an aqueous suspension thereof of about 9 to about 10; a liquid developer wherein the alumina is from about 1 nanometer to about 100 nanometers in diameter; a developer wherein the colorant is present in an amount of from about 1 to about 60 percent by weight based on the total weight of the developer solids; a developer wherein the colorant is carbon black, cyan, magenta, yellow, blue, green, orange, red, violet and brown, or mixtures thereof, each optionally present in an amount of from about 15 to about 50 weight percent a developer wherein the charge acceptance agent is present in an amount of from about 0.05 to about 10 weight percent based on the weight of the developer solids of resin, colorant, and charge acceptance additive; a developer wherein the alumina is of a nanoparticle size and is present in an amount of from about 1 to about 7 weight percent, and wherein the alumina possesses a BET of from about 10 m 2 /g to about 300 m 2 /g; a developer wherein the liquid for the developer is an aliphatic hydrocarbon; a developer wherein the aliphatic hydrocarbon is a mixture of branched hydrocarbons of from about 8 to about 16 carbon atoms, or a mixture of normal hydrocarbons of from about 8 to about 16 carbon atoms; a developer wherein the resin is an alkylene polymer, a styrene polymer, an acrylate polymer, a polyester, mixtures thereof or copolymers thereof; a developer wherein the resin is poly(ethylene-co-vinylacetate), poly(ethylene-co-methacrylic acid), poly(ethylene-co-acrylic acid), or poly(propoxylated bisphenol) fumarate; a developer wherein the resin is selected from the group consisting of alpha-olefin/vinyl alkanoate copolymers, alpha-olefin/acrylic acid copolymers, alpha-olefin/methacrylic acid copolymers, alpha-olefin/acrylate ester copolymers, alpha-olefin/methacrylate ester copolymers, copolymers of styrene/n-butyl acrylate or methacrylate/acrylic or methacrylic acid, and unsaturated ethoxylated and propoxylated bisphenol A polyesters; a developer further containing a charge additive comprised of a mixture of I. a nonpolar liquid soluble organic aluminum complex that has been rendered insoluble by chemical bonding to the toner resin or by adsorption to the toner particles II. a nonpolar liquid soluble organic phosphate mono and diester mixture derived from phosphoric acid and isotridecyl alcohol that has been rendered insoluble by bonding to the insoluble organic aluminum complex, or mixtures thereof of the formulas

wherein R 1 is selected from the group consisting of hydrogen and alkyl, and n represents a number; a developer wherein the developer further includes a charge adjuvant; a developer wherein the alumina is an acidic alumina; a positively or negatively charged clear liquid developer comprised of a liquid, resin, and a charge acceptance agent comprised of an alumina; a developer wherein the alumina possesses a pH of from about 7.5 to about 12 for a basic alumina, from about 2 to about 6.5 for an acid alumina, and about 7 for a neutral alumina; a developer wherein the developer possesses a charge of from about −100 volts to about −250 volts, and which charge is measured by electrostatic voltmeter; a developer further containing a colorant, and wherein the developer is optionally comprised of from about 1 to about 20 percent solids of from about 0 to about 60 weight percent colorant, from about 0.05 to about 10 weight percent charge acceptance additive, and from about 30 to about 99.95 weight percent resin, and wherein the developer also contains from about 80 to about 99 weight percent of a nonpolar liquid; a developer comprised of a liquid, thermoplastic resin, colorant, and alumina; a liquid developer wherein the resin is a thermoplastic resin and the alumina is a basic, acid or neutral pH alumina charge acceptance component; a printing process wherein the liquid developer illustrated herein is selected; a liquid developer wherein the liquid has a viscosity of from about 0.5 to about 500 centipoise and resistivity equal to or greater than 5×10 9 , and the thermoplastic resin particles have a volume average particle diameter of from about 0.1 to about 30 microns; a xerographic imaging apparatus comprised of a charging component, an imaging member component, a developer component and a fusing component, and wherein the developer component contains the liquid developer illustrated herein and liquid developers comprised of a nonpolar liquid, resin, preferably a thermoplastic resin, as a charge acceptor an alumina or aluminum oxide, such as a neutral alumina with a pH of about 7.0±0.5; acidic alumina with a pH of about 6 to about 6.9; or a pH of from about 4 to about 6; basic alumina with a pH of greater than about 7.5, and more specifically, with a pH of from about 8 to about 10, which aluminas were obtained from Aldrich Chemicals, catalog numbers of 19,997-4, 19,996-6, or 19,944-3, respectively, and with, for example, a diameter of from about 1 nanometer to about 500 nanometers, and more specifically, from about 10 to about 100 nanometers. In embodiments thereof of the present invention, the liquid developers can be charged in a device which first charges the developer to a first polarity, such as a positive polarity, followed by a second charging with a second charging device to reverse the developer charge polarity, such as to a negative polarity in an imagewise manner. Subsequently, a biased image bearer (IB) separates the image from the background corresponding to the charged image pattern in the toner, or developer layer. Thus, the liquid developers are preferably charged by bipolar ion charging (BIC) rather than with chemical charging.

The charge capture alumina, especially neutral, acid, or basic alumina's capture ions. Although not being desired to be limited by theory, it is believed that the alumina possesses metal ion sites that can capture negative ions from a corona effluent by forming covalent or coordinate covalent (dative) bonds with these negative ions. The surface metal ion site then becomes negatively charged, and therefore, the charge acceptor particles dispersed in the toner particle becomes negatively charged. Since the negatively charged charge acceptor particle resides in the immobile toner particle and not in the mobile phase or liquid carrier, the immobile toner layer itself on the dielectric surface becomes negatively charged in an imagewise manner dependent upon the charge acceptor concentration. As the charge acceptor concentration can be the same throughout the toner layer, it is the amount of toner at a given location in the toner layer that governs the amount of charge acceptor and charge at that location. The amount of charge at a given location then results in differential development (due to different potentials) in accordance with the imagewise pattern deposited on the dielectric surface.

The negative oxide ions at the surface of alumina particles can capture positive ions from the corona effluent by forming covalent or coordinate covalent (dative) bonds with these positive ions. The oxide in alumina particles then becomes positively charged, and therefore, the alumina charge acceptor itself becomes positively charged. Since this positively charged particle resides in the immobile toner particle and not in the mobile phase or liquid carrier, the immobile toner layer itself on the dielectric surface becomes positively charged in an imagewise manner dependent upon the charge acceptor concentration. As the charge acceptor concentration can be the same throughout the toner layer, it is the amount of toner at a given location in the toner layer that controls the amount of charge acceptor and charge at that location. The amount of charge at a location then results in differential development (due to different potentials) in accordance with the imagewise pattern deposited on the dielectric surface.

Basic alumina may possess basic surface functionality, such as amine functional groups, as a result of surface modification or manufacturing process, which reside at the surface of alumina nanoparticle and which can capture positive ions from the corona effluent by forming covalent or coordinate covalent (dative) bonds with these positive ions. The neutral nitrogen atom in the alumina molecule then becomes a positively charged nitrogen atom, and therefore, the alumina charge acceptor itself becomes positively charged. Since this positively charged alumina nanoparticle resides in the immobile toner particle and not in the mobile phase or liquid carrier, the immobile toner layer itself on the dielectric surface becomes positively charged in an imagewise manner dependent upon the charge acceptor molecule concentration. As the charge acceptor concentration can be the same throughout the toner layer, it is the amount of toner at a given location in the toner layer that governs the amount of charge acceptor and charge at that location. The amount of charge at a given location then results in differential development (due to different potentials) in accordance with the imagewise pattern deposited on the dielectric surface.

In addition to the above-described nitrogen (positive) charge acceptance mechanism, two other mechanisms may coexist when using acidic or basic alumina charge acceptor, with or without nitrogen groups present. These mechanisms involve corona ion-acceptance (both involving both ion polarities) or acceptance of ions derived from the interaction of corona ions with other components in the toner layer. One mechanism involves hydroxyl groups present at the surface of alumina particles, which can capture either positive or negative corona effluent ions or species derived therefrom. In regard to the hydroxyl charge (ion) acceptance mechanism, it is believed that non-bonded electron pairs on one or more of the oxygen atoms in adjacent hydroxyl groups can bond positive ions from the corona effluent or from species derived therefrom, from which there results a positive charge dispersed on one or more hydroxyl oxygen atoms. Although the strength of a hydroxyl oxygen-positive ion bond is not as large as that of the amine nitrogen-positive ion bond, multiple oxygen atoms can participate at any given instant in time to complex the positive ion thereby resulting in a sufficient bonding force to acquire permanent positive charging. Optionally, the positive ion from the corona effluent or from species derived therefrom can bind to only one hydroxyl oxygen atom at any instant in time, but the positive ions can then migrate around all the hydroxyl oxygen atoms at the surface of alumina particle thereby providing positive charge stability by a charge dispersal mechanism. Also, in the hydroxyl oxygen-positive ion bonding mechanism, the hydroxyl group hydrogen atom is further capable of hydrogen bonding to negative ions originating from the corona effluent or from species derived therefrom. Thus, the hydroxyl group itself is ambivalent in its ability to chemically bind positive and negative ions. In the hydroxyl hydrogen bonding mechanism, hydrogen bonding is an on again-off again mechanism, meaning that when one hydrogen bond forms and then breaks there is an adjacent hydroxyl hydrogen atom that replaces the first broken hydrogen bond so that hydrogen bonding charge dispersion occurs to again provide charge stability by a charge dispersal mechanism.

The acidic alumina may contain typical acidic functional groups including a carboxylic acid and a hydroxyl group. Three bonding mechanisms are plausible between positive ions and the carboxylate charge acceptors and generate positively charged aluminum-containing molecules and a positively charged toner layer. Although not being desired to be limited by theory (1) a low steady-state concentration of free carboxylate anions, dissociated from the carboxylate complex but contained therein, could accept positive ions; (2) the carboxylate complex positive ion acceptance mechanism could also occur by positive ion-hydrogen bonding with water of hydration surrounding the carboxylate charge acceptor; and (3) the carboxylate complex positive ion acceptance mechanism could also occur by positive ion-hydrogen bonding with hydroxyl groups, attached to the aluminum atom in the aluminum carboxylate complex.

While not being desired to be limited by theory, although similar to the function of charge control agents in chemically charged liquid developers in that charge acceptance agents in ion-charged liquid developers are directly involved in charging liquid developers, capturing charge using a charge acceptance agent versus a charge control agent is different mechanistically. A first difference resides in the origin and location of the species reacting with a charge acceptance agent versus the origin and location of the species reacting with a charge control agent. The species reacting with a charge acceptance agent originate in the corona effluent, which after impinging on the toner layer, become trapped in the solid phase thereof. The species reacting with a charge control agent, i.e. the charge director, originates by purposeful formulation of the charge director into the liquid developer and remains soluble in the liquid phase of a toner layer. Both the charge acceptance agent (in BIC-RCP developers) and the charge control additive or agent (in chemically charged developers) are insoluble in the liquid developer medium and reside on and in the toner particles, but charge directors, used only in chemically charged developers, dissolve in the developer medium. A second difference between a charge acceptance agent and a charge control agent is that charge directors in chemically charged liquid developers charge toner particles to the desired polarity, while at the same time capturing the charge of opposite polarity so that charge neutrality is always maintained during this chemical equilibrium process. Charge separation occurs only later when the developer is placed in an electric field during development. In the BIC-RCP development process, the corona effluent used to charge the liquid developer is generated from any corona generating device and the dominant polarity of the effluent is fixed by the device. Corona ions first reach the surface of the toner layer, move through the liquid phase, and are adsorbed onto the particle and captured by the charge acceptance agent. The mobile or free corona ions in the liquid phase rapidly migrate to the ground plane. Some of these mobile ions may include counterions, if counterions are formed in the charging process. Counterions bear the opposite polarity charge versus the charged toner particles in the developer. The corona ions captured by the charge acceptance agent in or on the toner charge the developer to the same polarity as the dominant polarity charge in the corona effluent. The ion-charged liquid developer particles remain charged and most counterions, if formed in the process, exit to the ground plane so fewer counter charges remain in the developer layer. Electrical neutrality or equilibrium is not attained in the BIC-RCP development process and development is not interfered with by species containing counter charges.

The charge acceptance agent initially resides in the liquid phase but prior to charging the toner layer the charge acceptance agent deposits on the toner particle surfaces. The concentration of charge acceptor in the nonpolar solvent is believed to be close to the charge acceptor insolubility limit at ambient temperature especially in the presence of toner particles. The adsorption affinity between soluble charge acceptor and insoluble toner particles is believed to accelerate charge acceptor adsorption such that charge acceptor insolubility occurs at a lower charge acceptor concentration versus when toner particles were not present. When the insoluble or slightly soluble charge acceptors accept (chemically bind) ions from the impinging corona effluent (BIC) or from species derived therefrom, there is obtained a net charge on the toner particles in the liquid developer. Since the toner layer contains charge acceptors capable of capturing both positive and negative ions, the net charge on the toner layer is not determined by the charge acceptor but instead is determined by the predominant ion polarity emanating from the corona. Corona effluents rich in positive ions give rise to charge acceptor capture of more positive ions, and therefore, provide a net positive charge to the toner layer. Corona effluents rich in negative ions give rise to charge acceptor capture of more negative ions, and therefore, provide a net negative charge to the toner layer. Also, in the charging mechanism of a charge acceptance agent versus a charge control agent after charging a liquid developer via the standard charge director (chemical charging) mechanism, the developer contains an equal number of charges of both polarity. An equal number of charges of both polarities in the developer hinders reverse charge imaging, so adding a charge director to the developer before depositing the uncharged developer onto the dielectric surface is undesirable. However, if corona ions in the absence of a charge director are used to charge the toner layer, the dominant ion polarity in the effluent will be accepted by the toner particles to a greater extent resulting in a net toner charge of the desired polarity and little if any counter-charged particles. When the toner layer on the dielectric receiver has more of one kind (positive or negative) of charge on it, reverse charge imaging is facilitated.

With further respect to the present invention is the presence in the liquid developer of the charge acceptor which function to, for example, increase the Q/M of both positive and negatively charged developers. The captured charge, Q=fCV where C is the capacitance of the toner layer, V is the measured surface voltage, and f is a proportionality constant which is dependent upon the distribution of captured charge in the toner layer. M in Q/M is the total mass of the toner solids and wherein it is believed that all charges are associated with toner particles.

In embodiments of the present invention, the charge acceptance agents are selected in various effective amounts, such as for example from about 0.01 to about 10, and preferably from about 1 to about 7 weight percent based on the total weight percent of the resin solids, other charge additives, colorant, such as pigments when present, and alumina, especially neutral, acid, or basic aluminas and the like, and wherein the total of all solids is about 1 to about 20 percent and the total of nonpolar liquid carriers is about 80 to about 99 percent based on the weight of the total liquid developer. The toner solids contain, for example, about 1 to about 7 weight percent alumina of a nanoparticle size, about 15 to about 60 weight percent colorant, about 33 to about 83 weight percent resin, and which developer possesses high bipolar charging voltage values, such as for example from about 100 volts to about −300 volts and preferably from about 150 volts to about −250 volts.

Examples of nonpolar liquid carriers or components selected for the developers of the present invention include a liquid with an effective viscosity of, for example, from about 0.5 to about 500 centipoise, and preferably from about 1 to about 20 centipoise, and a resistivity equal to or greater than for example, 5×10 9 ohm/cm, such as 5×10 13 . Preferably, the liquid selected is a branched chain aliphatic hydrocarbon. A nonpolar liquid of the ISOPAR® series (manufactured by the Exxon Corporation) may also be used for the developers of the present invention. These hydrocarbon liquids are considered narrow portions of isoparaffinic hydrocarbon fractions with extremely high levels of purity. For example, the boiling range of ISOPAR G® is between about 157° C. and about 176° C.; ISOPAR H® is between about 176° C. and about 191° C.; ISOPAR K® is between about 177° C. and about 197° C.; ISOPAR L® is between about 188° C. and about 206° C.; ISOPAR M® is between about 207° C. and about 254° C.; and ISOPAR V® is between about 254.4° C. and about 329.4° C. ISOPAR L® has a mid-boiling point of approximately 194° C. ISOPAR M® has an auto ignition temperature of 338° C. ISOPAR G® has a flash point of 40° C. as determined by the tag closed cup method; ISOPAR H® has a flash point of 53° C. as determined by the ASTM D-56 method; ISOPAR L® has a flash point of 61° C. as determined by the ASTM D-56 method; and ISOPAR M® has a flash point of 80° C as determined by the ASTM D-56 method. The liquids selected are generally known and should have an electrical volume resistivity in excess of 10 9 ohm-centimeters and a dielectric constant below 3 in embodiments of the present invention. Moreover, the vapor pressure at 25° C. should be less than 10 Torr in embodiments.

While the ISOPAR® series liquids can be the preferred nonpolar liquids for use as dispersant in the liquid developers of the present invention, the essential characteristics of viscosity and resistivity may be satisfied with other suitable liquids. Specifically, the NORPAR® series available from Exxon Corporation, the SOLTROL® series available from the Phillips Petroleum Company, and the SHELLSOL® series available from the Shell Oil Company can be selected.

The amount of the liquid employed in the developer of the present invention is, for example, from about 80 to about 99 percent, and preferably from about 85 to about 95 percent by weight of the total liquid developer. The term dispersion is used to refer to the complete process of incorporating a fine particle into a liquid medium such that the final product consists of fine toner particles distributed throughout the medium. Since liquid developer consists of fine particles dispersed in a nonpolar liquid, it is often referred to as dispersion. The liquid developer dispersion consists of fine toner particles, here referred to as toner solids, and nonpolar liquid. However, other effective amounts may be selected. The total solids, which include resin, other charge additives such as adjuvants, optional colorants, and the cyclodextrin or aluminum complex charge acceptance agent, content of the developer in embodiments is, for example, 0.1 to 20 percent by weight, preferably from about 3 to about 17 percent, and more preferably, from about 5 to about 15 percent by weight.

Typical suitable thermoplastic toner resins can be selected for the liquid developers of the present invention in effective amounts, for example, in the range of about 99.9 percent to about 40 percent, and preferably 80 percent to 50 percent of developer solids comprised of thermoplastic resin, charge acceptance component, and charge additive, and in embodiments other components that may comprise the toner. Generally, developer solids include the thermoplastic resin, charge additive, and charge acceptance agent. Examples of resins include ethylene vinyl acetate (EVA) copolymers (ELVA®) resins, E.I. DuPont de Nemours and Company, Wilmington, Del.); copolymers of ethylene and an alpha, beta-ethylenically unsaturated acid selected from the group consisting of acrylic acid and methacrylic acid; copolymers of ethylene (80 to 99.9 percent), acrylic or methacrylic acid (20 to 0.1 percent)/alkyl (C1 to C5) ester of methacrylic or acrylic acid (0.1 to 20 percent); polyethylene; polystyrene; isotactic polypropylene (crystalline); ethylene ethyl acrylate series available as BAKELITE® DPD 6169, DPDA 6182 NATURAL™ (Union Carbide Corporation, Stamford, Conn.); ethylene vinyl acetate resins like DQDA 6832 Natural 7 (Union Carbide Corporation); SURLYN® ionomer resin (E.I. DuPont de Nemours and Company); or blends thereof; polyesters; polyvinyl toluene; polyamides; styrene/butadiene copolymers; epoxy resins; acrylic resins, such as a copolymer of acrylic or methacrylic acid, and at least one alkyl ester of acrylic or methacrylic acid wherein alkyl is 1 to 20 carbon atoms, such as methyl methacrylate (50 to 90 percent)/methacrylic acid (0 to 20 percent)/ethylhexyl acrylate (10 to 50 percent); and other acrylic resins including ELVACITE® acrylic resins (E.I. DuPont de Nemours and Company); or blends thereof.

The liquid developers of the present invention preferably contain a colorant dispersed in the resin particles. Colorants, such as pigments or dyes and mixtures thereof may be present to render the latent image visible.

The colorant, when present, may be contained in the developer in an effective amount of, for example, from about 0.1 to about 60 percent, and preferably from about 15 to about 60, and in embodiments of about 25 to about 45 percent by weight based on the total weight of solids contained in the developer. The amount of colorant used may vary depending on the use of the developer. Examples of colorants which may be selected include carbon blacks available from, for example, Cabot Corporation, FANAL PINK™, PV FAST BLUE™, the colorants as illustrated in U.S. Pat. No. 5,223,368, the disclosure of which is totally incorporated herein by reference; other known colorants, such as cyan, magenta, yellow, red, blue, brown, green, and the like. Dyes are known and include food dyes.

To further increase the toner particle charge and, accordingly, increase the transfer latitude of the toner particles, charge adjuvants can be added to the developer, such as metallic soaps like magnesium stearate or octoate in an amount of from about 0.1 percent to about 15 percent of the total developer solids, and preferably from about 3 percent to about 7 percent of the total weight percent of solids contained in the developer.

The liquid electrostatic developer of the present invention can be prepared by a variety of processes such as, for example, mixing in a nonpolar liquid the thermoplastic resin, charge acceptance component, other charge additives such as charge adjuvants, and optional colorant in a manner that the resulting mixture contains, for example, about 30 to about 60 percent by weight of solids; heating the mixture to a temperature of from about 40° C. to about 110° C. until a uniform dispersion is formed; adding an additional amount of nonpolar liquid sufficient to decrease the total solids concentration of the developer to about 10 to about 30 percent by weight solids and isolating the developer by, for example, cooling the dispersion to about 10° C. to about 30° C.

In the initial mixture, the resin, charge acceptance component, optional colorant and charge acceptance additive may be added separately to an appropriate vessel such as, for example, an attritor, heated ball mill, heated vibratory mill, such as a Sweco Mill manufactured by Sweco Company, Los Angeles, Calif., equipped with particulate media for dispersing and grinding, a Ross double planetary mixer manufactured by Charles Ross and Son, Hauppauge, N.Y., or a two roll heated mill, which usually requires no particulate media. Useful particulate media include materials like a spherical cylinder of stainless steel, carbon steel, alumina, ceramic, zirconia, and the like. Carbon steel particulate media are particularly useful when colorants other than black are used. A typical diameter range for the particulate media is in the range of about 0.04 to 0.5 inch (approximately 1 to approximately 13 millimeters).

Sufficient nonpolar liquid is added to provide a dispersion of from about 30 to about 60, and more specifically, from about 35 to about 45 percent solids. This mixture is then subjected to elevated temperatures during the initial mixing procedure to plasticize and soften the resin. The mixture is sufficiently heated to provide a uniform dispersion of all the solid materials of, for example, optional colorant, charge acceptance component, charge acceptance agent, and resin. However, the temperature at which this step is undertaken should not be so high as to degrade the nonpolar liquid or decompose the resin or colorant if present. Accordingly, the mixture in embodiments is heated to a temperature of from about 50° C. to about 110° C., and preferably from about 50° C. to about 80° C. The mixture may be ground in a heated ball mill or heated attritor at this temperature for about 15 minutes to 5 hours, and preferably about 60 to about 180 minutes.

After grinding at the above temperatures, an additional amount of nonpolar liquid may be added to the dispersion. The amount of nonpolar liquid to be added should be sufficient in embodiments to decrease the total solids concentration of the dispersion to about 10 to about 30 percent by weight.

The dispersion is then cooled to about 10° C. to about 30° C., and preferably to about 15° C. to about 25° C., while mixing is continued until the resin admixture solidifies or hardens. Upon cooling, the resin admixture precipitates out of the dispersant liquid. Cooling is accomplished by methods such as the use of a cooling fluid like water, glycols such as ethylene glycol, in a jacket surrounding the mixing vessel. Cooling is accomplished, for example, in the same vessel, such as an attritor, while simultaneously grinding with particulate media to prevent the formation of a gel or solid mass; without stirring to form a gel or solid mass, followed by shredding the gel or solid mass and grinding by means of particulate media; or with stirring to form a viscous mixture and grinding by means of particulate media. The resin precipitate is cold ground for about 1 to about 36 hours, and preferably from about 2 to about 4 hours. Additional liquid may be added at any time during the preparation of the liquid developer to facilitate grinding or to dilute the developer to the appropriate percent solids needed for developing. Other processes of preparation are generally illustrated in U.S. Pat Nos. 4,760,009; 5,017,451; 4,923,778; 4,783,389, the disclosures of which are totally incorporated herein by reference.

As illustrated herein, the developers or inks of the present invention can be selected for RCP imaging and printing methods wherein, for example, there can be selected an imaging apparatus, wherein an electrostatic latent image including image and nonimage areas is formed in a layer of marking material, and further wherein the latent image can be developed by selectively separating portions of the latent image bearing layer of the marking material such that the image areas reside on a first surface and the nonimage areas reside on a second surface. In embodiments, the present invention also related to an image development apparatus comprising a system for generating a first electrostatic latent image on an imaging member, wherein the electrostatic latent image includes image and non-image areas having distinguishable charge potentials, and a system for generating a second electrostatic latent image on a layer of marking materials situated adjacent the first electrostatic latent image on the imaging member, wherein the second electrostatic latent image includes image and nonimage areas having distinguishable charge potentials of a polarity opposite to the charge potentials of the charged image and nonimage areas in the first electrostatic latent image.

Embodiments of the invention will be illustrated in the following nonlimiting Examples, it being understood that these Examples are intended to be illustrative only, and that the invention is not intended to be limited to the materials, conditions, process parameters and the like recited. The toner particles in the liquid developer can range in diameter size of from about 0.1 to about 3 micrometers with the preferred particle size being about 0.5 to about 1.5 micrometers. Particle size, when measured, was measured by a Horiba CAPA-700 centrifugal automatic particle analyzer manufactured by Horiba Instruments, Inc., Irvine, Calif.

Control=100 Percent of DuPont RX-76®; No Charge Acceptance Agent

Two hundred seventy (270) grams of NUCREL RX-76® (a copolymer of ethylene and methacrylic acid with a melt index of about 800, available from E.I. DuPont de Nemours & Company, Wilmington, Del.), and 405 grams of ISOPAR-M® (Exxon Corporation) were added to a Union Process 1S attritor (Union Process Company, Akron, Ohio) charged with 0.1857 inch (4.76 millimeters) diameter carbon steel balls. The resulting mixture was milled in the attritor, which was heated with running steam through the attritor jacket to 80° C. to 115° C. for 2 hours. 675 Grams of ISOPAR-M® were added to the attritor at the conclusion of 2 hours, and cooled to 23° C. by running water through the attritor jacket, and the contents of the attritor were ground for an additional 4 hours. Additional ISOPAR-M®, about 900 grams, was added and the mixture was separated from the steel balls.

The liquid developer solids contained 100 percent NUCREL RX-76® toner resin. The solids level was 10.067 percent and the ISOPAR M® level was 89.933 percent of this liquid developer. The liquid developer was used as is.

EXAMPLE I

95 Percent of DuPont RX-76®; 5 Percent Neutral Alumina Charge Acceptance Agent

Two hundred fifty six point five (256.5) grams of NUCREL RX-76® (a copolymer of ethylene and methacrylic acid with a melt index of about 800, available from E.I. DuPont de Nemours & Company, Wilmington, Del.), 13.5 grams of neutral alumina charge acceptor (available from Aldrich Chemicals, catalog #19,997-4) and 405 grams of ISOPAR-M® (Exxon Corporation) were added to a Union Process 1 Sattritor (Union Process Company, Akron, Ohio) charged with 0.1857 inch (4.76 millimeters) diameter carbon steel balls. The resulting mixture was milled in the attritor, which was heated with running steam through the attritor jacket to 80° C. to 115° C. for 2 hours. 675 Grams of ISOPAR-M® were added to the attritor at the conclusion of 2 hours, and cooled to 23° C. by running water through the attritor jacket, and the contents of the attritor were ground for an additional 4 hours. Additional ISOPAR-M®, about 900 grams, was added and the mixture was separated from the steel balls.

The liquid developer solids contained 95 percent NUCREL RX-76® toner resin and 5 percent neutral alumina charge acceptance agent.

EXAMPLE II

95 Percent of DuPont RX-76®; 5 Percent Basic Alumina Charge Acceptance Agent

Two hundred fifty-six point five (256.5) grams of NUCREL RX-76® (a copolymer of ethylene and methacrylic acid with a melt index of about 800, available from E.I. DuPont de Nemours & Company, Wilmington, Del.), 13.5 grams of basic alumina (available from Aldrich Chemicals, catalog # 19,944-3) and 405 grams of ISOPAR-M® (Exxon Corporation) were added to a Union Process 1S attritor (Union Process Company, Akron, Ohio) charged with 0.1857 inch (4.76 millimeters) diameter carbon steel balls. The resulting mixture was milled in the attritor, which was heated with running steam through the attritor jacket to 80° C. to 115° C. for 2 hours. 675 Grams of ISOPAR-M® were added to the attritor at the conclusion of 2 hours, and cooled to 23° C. by running water through the attritor jacket, and the contents of the attritor were ground for an additional 4 hours. Additional ISOPAR-M®, about 900 grams, was added and the mixture was separated from the steel balls.

The liquid developer solids contained 95 percent NUCREL RX-76® toner resin and 5 percent basic alumina charge acceptance agent.

EXAMPLE III

95 Percent of DuPont RX-76®, 5 Percent Acidic Alumina Charge Acceptance Agent

Two hundred fifty six point five (256.5) grams of NUCREL RX-76® (a copolymer of ethylene and methacrylic acid with a melt index of about 800, available from E.I. DuPont de Nemours & Company, Wilmington, Del.), 13.5 grams of acidic alumina (available from Aldrich Chemicals, catalog #19,996-6) and 405 grams of ISOPAR-M® (Exxon Corporation) were added to a Union Process 1S attritor (Union Process Company, Akron, Ohio) charged with 0.1857 inch (4.76 millimeters) diameter carbon steel balls. The mixture was milled in the attritor, which was heated with running steam through the attritor jacket to 80° C. to 115° C. for 2 hours. 675 Grams of ISOPAR-M® were added to the attritor at the conclusion of 2 hours, and cooled to 23° C. by running water through the attritor jacket, and the contents of the attritor were ground for an additional 4 hours. Additional ISOPAR-M®, about 900 grams, was added and the mixture was separated from the steel balls.

The liquid developer solids contained 95 percent NUCREL RX-76® toner resin and 5 percent acidic alumina charge acceptance agent.

Charging Properties:

Considering a DC corona (ions of one polarity), the ions move along the field lines (produced between the corotron device and ground plane and distorted by the presence of the dielectric particle) to charge the particle. For a fixed external applied field, a saturation charge Q p , the Pauthenier limit, is reached when the attractive field due to the field distortion equals the repulsive field due to the charge on the particle:

Q p =4π∈ 0 E 0 r 2 [3∈ r /(∈ r +2)],

where ∈ r is the relative permittivity of the dielectric particle with respect to its surrounding medium and r is the particle radius. [3∈ r /(∈ r +2)] varies between 3 for a conducting particle (often dark-colored) with its infinite dielectric constant and 1 for an insulator with a dielectric constant of unity. The relative dielectric constant of all insulating materials range between one and ten so the dependence of Q p on dielectric constant is as much as a factor of 2.5 enhancement for ∈ r =10. The Pauthenier charging does not account for the chemistry of the toner particle, and it is postulated that certain particle surface functional groups may play an important role in ion charge acceptance in liquid developers. Alumina nanoparticles near the surface of the liquid toner particle in Examples I, II and III can (1) increase surface ∈ r of the particle, (2) create a lot of resin/alumina interface for capturing corona ions, and (3) provide functional groups for acid-base interactions with corona ions, which characteristics are not achieved, it is believed, with the above comparative Example developer. Also, the highly mobile conductive species in the continuous phase of the liquid developer can inhibit reversible positive or negative ion charging, and alumina nanoparticles should not generate a conductive species in the continuous phase. Further, the above liquid developers with the alumina charge acceptor permits excellent transfer of developed images, for example about 95 to about 99 percent, compared to a transfer of about 80 percent for the above Comparative Example liquid developer.

Other embodiments and modifications of the present invention may occur to those skilled in the art subsequent to a review of the information presented herein; these embodiments and modifications, as well as equivalents thereof, are also included within the scope of this invention.

Claims

1. A liquid developer comprised of a nonpolar liquid, thermoplastic resin, optional colorant, and an alumina charge acceptance additive.

2. A developer in accordance with claim 1 wherein said charge acceptance agent or additive is neutral, acid, basic or mixtures thereof.

3. A developer in accordance with claim 1 wherein said charge acceptance additive is neutral alumina with an optional particle size of from about 5 to about 6 nanometers, an optional specific surface area of from about 150 to about 160 m2/g and a pH of an aqueous suspension thereof of from about 6.5 to about 7.5, acidic alumina with an optional particle size of about 5 to about 6, an optional specific surface area of about 150 to about 160 m2/g and a pH of an aqueous suspension thereof of from about 4 to about 5, or basic alumina with a particle size of about 5 to about 6, a specific surface area of about 150 to about 160 m2/g and a pH of an aqueous suspension thereof of about 9 to about 10.

4. A liquid developer in accordance with claim 1 wherein said alumina is from about 1 nanometer to about 100 nanometers in diameter.

5. A developer in accordance with claim 1 wherein the colorant is present in an amount of from about 1 to about 60 percent by weight based on the total weight of the developer solids.

6. A developer in accordance with claim 1 wherein the colorant is carbon black, cyan, magenta, yellow, blue, green, orange, red, violet and brown, or mixtures thereof, each optionally present in an amount of from about 15 to about 50 weight percent.

7. A developer in accordance with claim 1 wherein the charge acceptance agent is present in an amount of from about 0.05 to about 10 weight percent based on the weight of the developer solids of resin, colorant, and charge acceptance additive.

8. A developer in accordance with claim 1 wherein the alumina is of a nanoparticle size and is present in an amount of from about 1 to about 7 weight percent, and wherein the alumina possesses a BET of from about 10 m2/g to about 300 m2/g.

9. A developer in accordance with claim 1 wherein the liquid for said developer is an aliphatic hydrocarbon.

10. A developer in accordance with claim 9 wherein the aliphatic hydrocarbon is a mixture of branched hydrocarbons of from about 8 to about 16 carbon atoms, or a mixture of normal hydrocarbons of from about 8 to about 16 carbon atoms.

11. A developer in accordance with claim 1 wherein the resin is an alkylene polymer, a styrene polymer, an acrylate polymer, a polyester, mixtures thereof or copolymers thereof.

12. A developer in accordance with claim 1 wherein the resin is poly(ethylene-co-vinylacetate), poly(ethylene-co-methacrylic acid), poly(ethylene-co-acrylic acid), or poly(propoxylated bisphenol) fumarate.

13. A developer in accordance with claim 1 wherein the resin is selected from the group consisting of alpha-olefin/vinyl alkanoate copolymers, alpha-olefin/acrylic acid copolymers, alpha-olefin/methacrylic acid copolymers, alpha-olefin/acrylate ester copolymers, alpha-olefin/methacrylate ester copolymers, copolymers of styrene/n-butyl acrylate or methacrylate/acrylic or methacrylic acid, and unsaturated ethoxylated and propoxylated bisphenol A polyesters.

14. A developer in accordance with claim 1 further containing a charge additive comprised of a mixture of I. a nonpolar liquid soluble organic aluminum complex that has been rendered insoluble by chemical bonding to the toner resin or by adsorption to the toner particles II. a nonpolar liquid soluble organic phosphate mono and diester mixture derived from phosphoric acid and isotridecyl alcohol that has been rendered insoluble by bonding to the insoluble organic aluminum complex, or mixtures thereof of the formulas wherein R1 is selected from the group consisting of hydrogen and alkyl, and n represents a number.

15. A developer in accordance with claim 1 wherein said developer further includes a charge adjuvant.

16. A developer in accordance with claim 1 wherein the alumina is an acidic alumina.

17. A positively or negatively charged clear liquid developer comprised of a liquid, resin, and a charge acceptance agent comprised of an alumina.

18. A developer in accordance with claim 17 wherein the alumina possesses a pH of from about 7.5 to about 12 for a basic alumina, from about 2 to about 6.5 for an acid alumina, and about 7 for a neutral alumina.

19. A developer in accordance with claim 17 wherein the developer possesses a charge of from about −100 volts to about −250 volts, and which charge is measured by electrostatic voltmeter.

20. A developer in accordance with claim 17 further containing a colorant, and wherein said developer is optionally comprised of from about 1 to about 20 percent solids of from about 0 to about 60 weight percent colorant, from about 0.05 to about 10 weight percent charge acceptance additive, and from about 30 to about 99.95 weight percent resin, and wherein the developer also contains from about 80 to about 99 weight percent of a nonpolar liquid.

21. A developer comprised of a liquid, thermoplastic resin, colorant, and alumina.

22. A liquid developer in accordance with claim 21 wherein said resin is a thermoplastic resin and said alumina is a basic, acid or neutral pH alumina charge acceptance component.

23. A printing process wherein the liquid developer of claim 1 is selected.

24. A liquid developer in accordance with claim 1 wherein said liquid has a viscosity of from about 0.5 to about 500 centipoise and resistivity equal to or greater than 5×109, and said thermoplastic resin particles have a volume average particle diameter of from about 0.1 to about 30 microns.

25. A xerographic imaging apparatus comprised of a charging component, an imaging member component, a developer component and a fusing component, and wherein said developer component contains the liquid developer of claim 1.

26. A liquid developer consisting essentially of a nonpolar liquid, thermoplastic resin, colorant, and an alumina charge acceptance additive, and wherein said charge acceptance additive is neutral, acid, basic or mixtures thereof.