EP0423158B1

EP0423158B1 - Dual color imaging method and apparatus

Info

Publication number: EP0423158B1
Application number: EP89906820A
Authority: EP
Inventors: Benzion Landa; Yehuda Niv; Israel Grossinger; Yossi Adam; Moshe Levanon
Original assignee: Indigo BV
Current assignee: HP Indigo BV
Priority date: 1988-06-06
Filing date: 1989-06-05
Publication date: 1996-05-01
Anticipated expiration: 2009-06-05
Also published as: JP2866689B2; EP0423158A1; WO1989012257A2; DE68926393D1; HK152396A; DE68926393T2; WO1989012257A3; JPH04501616A

Abstract

An imaging system comprising apparatus for forming a latent image on a surface, said latent image including a first portion having a high level of electrostatic charge, a second portion having a low level of electrostatic charge and a third portion having an intermediate level of electrostatic charge, the charges on the first, second and third portions being of the same polarity; and apparatus for developing the latent image by contacting it with a liquid toner composition comprising an insulating, nonpolar liquid having admixed therewith a first type of pigmented particles having charges of a first polarity and a second type of pigmented particles having charges of an opposite polarity, such that the first type of pigmented particles becomes deposisted onto the first portion and the second type of pigmented particles becomes deposited onto the second portion.

Description

The present invention relates to an imaging apparatus according to the preamble of claim 1.
In color imaging systems, it is known to print two or more superimposed colors on a substrate by separate operations. Printing in two colors is useful, for example, when it is desired to highlight particular sections of documents such as in accounts, where material may be typewritten in two colors, in stationery with two printed colors and so forth. Printing (or copying) in two or more colors generally requires a process which incorporates two passes as well as accurate registration of the two or more superimposed colors.
In U.S. Patent No. 4,068,938 (Robertson), there is described a process in which a two color plus background copy is obtained from a two color plus background original. According to Robertson's concept, the pairs of colors are chosen according to the response characteristics of the photoconductive surface on which the electrostatic latent image is formed. Thus the electrostatic latent image is characterized by a high level of potential corresponding to locally uniform areas of one of the colors, an intermediate level of potential corresponding to locally uniform areas of the second color, and a low level of potential corresponding with locally uniform areas of the background.
There are two steps in the development of the images this process: (1) particles of one color are attracted to areas of the electrostatic latent image of high potential and (2) particles of a second color are attracted to areas of low potential. It should be noted that this process depends in practice on the provision of different inks in separate baths so as to develop in separate steps two different areas of the electrostatic latent image.
U.S. Patent No. 4,264,185 (Ohta) describes a process in which areas of an electrostatic latent image corresponding to two colors in an original document are developed. Ohta's process applies toners of different colors and polarities to the latent image, using separate mechanisms. In order to repel other, undesired toner particles from one development unit, a bias voltage of opposite polarity is applied to the latter unit, and vice-versa.
Ohta's process may use separate baths of the two toners, or a single partitioned bath with liquid communication between the compartments. Even where a single partitioned bath is used, the latent image is developed in two distinct steps. It is unclear from the disclosure in this patent how the question of clean-up of the background is to be dealt with, if at all.
In U.S. Patent No. 4,562,129 (Tanaka), there is described a method of forming monochromatic or dichromatic copy images by use of a developer comprising a high-resistivity magnetic carrier and a nonmagnetic insulating toner which are triboelectrically chargeable, with the result that the toner and carrier adhere to first and second image portions, respectively, of the electrostatic latent image which has at least three levels of potential.
In "Experimental Example 1" of Tanaka, a toner of 14 microns mean particle size and resistivity of at least 10¹⁵ ohm-cm, triboelectrically chargeable to positive polarity, comprised styrene-acrylic copolymer (100) and red colored charge controlling pigment (5); while a carrier of 20 microns mean particle size, resistivity of 10¹⁴ ohm-cm, triboelectrically chargeable to negative polarity, comprised styrene-acrylic copolymer (100), magnetic fine powder (200), carbon black (4) and silica fluidity agent (1.5); parts indicated in parentheses are by weight. The developer comprised a 1:9 mixture of toner and carrier.
The disclosures of U.S. Patents Nos. 4,068,938, 4,264,185 and 4,562,129 are incorporated by reference herein.
U.S. Patent 4,411,976 describes a method of increasing the density of liquid developed gap transferred electrophotographic images and developing composition for use therein wherein the carrier sheet is heated either before or after transfer to a temperature less than 100 degrees C at which the binder or polymer forming the toner particles will solvate the liquid entrained in the transferred image to increase the density of the image.
Reference is now made to the following United States patents in the field of electrophotography: 3,907,423; 4,068,938; 4,264,185; and 4,562,129, the disclosures of which are incorporated by reference herein.
U.S. Patent 4,830,945; 4,880,720 and 4,877,698 were filed in the U.S. before the filing of the present application but were published after the filing of the present applicaction. These patents describe two color liquid toner composition having two kinds of toner particles which are charged to opposite polarities using a single charge director admixed in a carrier liquid. Also described is a process for forming a two color image on a tri-level photoconductor.
The present invention seeks to provide an improved imaging system and process.
There is thus provided in accordance with the present invention an imaging system according to claim 1.
According to a further preferred embodiment of the present invention, there is provided an imaging system comprising means for forming a latent image on a surface, the latent image including a first portion having a high level of electrostatic charge, a second portion having a low level of electrostatic charge and a third portion having an intermediate level of electrostatic charge, means for developing the latent image by contacting it with a liquid toner composition comprising an insulating, nonpolar liquid having admixed therewith at least one charge director, a first type of pigmented particles having charges of a first polarity and a second type of pigmented particles having charges of an opposite polarity, such that the first type of pigmented particles becomes deposited onto the first portion and the second type of pigmented particles becomes deposited onto the second portion, and means for regulating the concentration of the at least one charge director in the liquid toner composition.
According to still a further preferred embodiment of the present invention, there is provided an imaging system comprising means for forming a latent image on a surface, the latent image including a first portion having a high level of electrostatic charge, a second portion having a low level of electrostatic charge and a third portion having an intermediate level of electrostatic charge, means for developing the latent image by contacting it with a liquid toner composition comprising an insulating, nonpolar liquid having admixed therewith a first type of pigmented particles having charges of a first polarity and a second type of pigmented particles having charges of an opposite polarity, such that the first type of pigmented particles becomes deposited onto the first portion and the second type of pigmented particles becomes deposited onto the second portion and means for removing unwanted pigmented particles from a region of the developed image defined by the third portion, the means for removing comprising first removal means biased at a potential between (i) the average surface potential of the third portion and (ii) the potential of the first portion, for the removal of the first type of pigmented particles from the third portion, and second removal means biased at a potential between (i) the average surface potential of the third portion and (ii) the potential of the second portion, for the removal of the second type of pigmented particles from the third portion.
According to yet a further preferred embodiment of the present invention, there is provided an imaging system comprising means for forming a latent image on a surface, the latent image including a first portion having a high level of electrostatic charge, a second portion having a low level of electrostatic charge and a third portion having an intermediate level of electrostatic charge and means for developing the latent image by contacting it with a liquid toner composition comprising an insulating, nonpolar liquid having admixed therewith at least one charge director, a first type of pigmented particles having charges of a first polarity and a second type of pigmented particles having charges of an opposite polarity, such that the first type of pigmented particles becomes deposited onto the first portion and the second type of pigmented particles becomes deposited onto the second portion, wherein the at least one charge director comprises first and second charge directors and wherein the charges of the first polarity on the first type of pigmented particles are induced by the first charge director and the charges of the opposite polarity on the second type of pigmented particles are induced by the second charge director.
Further according to a preferred embodiment of the present invention, the toner composition also includes at least one charge director and the system also comprises means for regulating the concentration of the at least one charge director in the liquid toner composition.
Still further according to a preferred embodiment of the present invention, the system also comprises means for removing unwanted pigmented particles from a region of the developed image defined by the third portion, the means for removing unwanted pigmented particles comprising first removal means biased at a potential between (i) the average surface potential of the third portion and (ii) the potential of the first portion, for the removal of the first type of pigmented particles from the third portion, and second removal means biased at a potential between (i) the average surface potential of the third portion and (ii) the potential of the second portion, for the removal of the second type of pigmented particles from the third portion.
Additionally according to a preferred embodiment of the present invention, the at least one charge director comprises first and second charge directors and the charges of the first polarity on the first type of pigmented particles are induced by the first charge director and the charges of the opposite polarity on the second type of pigmented particles are induced by the second charge director.
Still further according to a preferred embodiment of the present invention, the means for developing comprises a development electrode biased at an electrostatic potential level near to the surface potential of the intermediate level of electrostatic charge.
Further according to a preferred embodiment of the present invention, the charges of the first polarity on the first type of pigmented particles and the charges of the opposite polarity on the second type of pigmented particles are induced by the at least one charge director.
Additionally in accordance with a preferred embodiment of the present invention, the at least one charge director comprises first and second charge directors and the means for regulating the concentration of the at least one charge director in the liquid toner composition comprises means for separately regulating the concentrations of the first and second charge directors.
According to a further preferred embodiment of the present invention, there is provided an imaging process comprising the steps of forming a latent image on a surface, the latent image including a first portion having a high level of electrostatic charge, a second portion having a low level of electrostatic charge and a third portion having an intermediate level of electrostatic charge, the charges on the first, second and third portions being of the same polarity, and developing the latent image by contacting it with a liquid toner composition comprising an insulating, nonpolar liquid having admixed therewith a first type of pigmented particles having charges of a first polarity and a second type of pigmented particles having charges of an opposite polarity, such that the first type of pigmented particles becomes deposited onto the first portion and the second type of pigmented particles becomes deposited onto the second portion.
According to still a further preferred embodiment of the present invention, there is provided a dual color imaging process which comprises the steps of forming an image having adjacent first and second areas respectively containing first and second types of pigmented resin, undesirably separated by third areas relatively free of resin of the first and second types, and causing the image to flow into the third areas, thereby at least partially eliminating the third areas.
Further in accordance with a preferred embodiment of the present invention, the step of causing comprises the step of heating the image.
Still further in accordance with a preferred embodiment of the present invention, the image is produced by employing a liquid toner composition which comprises an insulating, nonpolar liquid having admixed therewith two different particulate pigments carrying opposite charges.
Additionally in accordance with a preferred embodiment of the present invention, the particulate pigments comprise at least one binder wax.
Further in accordance with a preferred embodiment of the present invention, the particulate pigments also comprise at least one polymeric material.
Still further in accordance with a preferred embodiment of the present invention, the at least one polymeric material comprises an ethylene copolymer including carboxylic acid functionality.
According to a further embodiment of the present invention there is provided liquid toner composition for use in development of a latent electrostatic image in an electrostatic imaging process, which comprises an insulating, nonpolar, nontoxic liquid having admixed therewith two different particulate pigments carrying charges which are opposite from each other, wherein the composition comprises also at least one charge director which promotes charging of the two particulate pigments in an opposite sense, respectively.
Further in accordance with a preferred embodiment of the present invention, the composition also comprises at least one polymeric carrier for the particulate pigments.
Still further in accordance with a preferred embodiment of the present invention, the at least one charge director comprises a single charge director.
Additionally in accordance with a preferred embodiment of the present invention, the at least one charge director comprises two charge directors, which are effective to charge one of the two particulate pigments positively, and the other of the two particulate pigments negatively.
In accordance with still a further embodiment of the present invention, there is provided a process for preparing a liquid toner composition which comprises the step of combining first and second types of pigmented particles and at least one charge director to provide a liquid toner composition wherein the first type of pigmented particles acquire charges of a first polarity and the second type of pigmented particles acquire charges of a second polarity, opposite to the first polarity.
Still further in accordance with a preferred embodiment of the present invention, the step of combining also comprises the step of polarizing the first and second types of pigmented particles, whereby the first type of pigmented particles acquires charges of the first polarity and the second type of pigmented particles acquires charges of the second polarity.
Additionally in accordance with a preferred embodiment of the present invention, the polarizing step may be effected either prior to, in the course of, or after combining the first and second types of pigmented particles with each other.
Still further in accordance with a preferred embodiment of the present invention, the at least one charge director is operative to cause the first type of pigmented particles to acquire charges of the first polarity and the second type of pigmented particles to acquire charges of the second polarity.
Additionally in accordance with a preferred embodiment of the present invention, the at least one charge director comprises two charge directors, which are operative to cause the first type of pigmented particles to acquire charges of the first polarity and the second type of pigmented particles to acquire charges of the second polarity.
According to a further preferred embodiment of the present invention, there is provided a method for maintaining first and second concentrations of respective first and second charge directors suspended in a toner composition comprising pigmented particles at respective given first and second values, the method comprising at least two of the following steps: (a) developing at least one color patch using the toner composition, obtaining measurements of the optical densities of the at least one color patch, (b) obtaining a measurement of the conductivity of a toner composition and comparing the conductivity measurement to a reference, (c) removing pigmented particles from a sample of the toner composition and measuring the amount of absorption of light of at least one given wavelength by the sample, determining the respective amounts of the first and second charge directors which need be added to the composition to restore the first and second concentrations of the first and second charge directors in the toner composition to the respective first and second given values; and adding the non-zero ones of the respective amounts of the first and second charge directors to the composition.
The present invention will be more fully understood and appreciated from the following detailed description, taken in conjunction with the drawings, in which:

Fig. 1 is a schematic sectional illustration of apparatus useful in carrying out the process of the invention;
Figs. 2A to 2D illustrate, in schematic fashion, various steps of dichromatic electrostatic imaging according to an embodiment of the invention;
Fig. 3 is an enlarged schematic sectional illustration of apparatus shown in Fig. 1 for cleaning the background of the developed image;
Fig. 4 is a schematic illustration of a pigmented particle replenishment system useful in association with the apparatus shown in Fig. 1;
Fig. 5 is a flow chart showing operation of microprocessor apparatus useful in the pigmented particle replenishment system shown in Fig. 4; and
Fig. 6 is a graphical illustration of the interface between two different colored areas on an image bearing surface which gives rise to the presence of undesired non-colored areas.

Referring to Fig. 1 there is shown electrostatic imaging apparatus employing a liquid toner composition comprising two oppositely charged and differently colored pigmented particles. There is shown a metal drum 2 which carries a photoconductor 4 and which is mounted by disks 6 onto a shaft 8 to which the disks are secured by a key 10 so that the shown assembly, which is provided in a light-proof housing (not shown) is operative to rotate a shaft 8.
Shaft 8 is driven in any appropriate manner (not shown) in the direction of arrow 9 past a corona discharge device 12 adapted to charge the surface of the photoconductor 4. The image to be reproduced is focused by a lens 14 upon the charged photoconductor. Since shaft 8 is grounded at 17 and disks 6 are conductive, the areas struck by light conduct the charge, or a portion thereof, to ground, thus forming an electrostatic latent image. Formation of the electrostatic latent image in this way is shown in Fig. 2A.
The developing liquid containing two different pigmented particles, as described herein, is circulated from any suitable source (not shown) through a pipe 16 into a development tray 18 from which it is drawn through a pipe 20 for recirculation. Development electrodes 22, which may be appropriately biased as known to the art, assist in toning the electrostatic latent image as it passes into contact with the developing liquid.
Referring now to Fig. 2, charged toner particles referenced 23 and 25, suspended in the carrier liquid, travel by electrophoresis to the electrostatic latent image. If, as shown in Fig. 2B, photoconductor 4 is positively charged, e.g. if a selenium photoconductor is used, negatively charged pigmented particles 23 will travel to electrostatic latent image areas having generally the highest positive potential, here shown at 1000 V, while positively charged pigmented particles 25 will travel to the latent image areas having generally the lowest positive potential of near 0 V, typically 50 V to 100 V. It is noted that the background carries a charge of typically 500 V. Some positively and negatively charged toner particles 25 and 23 respectively adhere thereto.
If the photoconductor is negatively charged, e.g. if a cadmium sulfide photoconductor is used, negatively charged pigmented particles travel to electrostatic latent image areas having generally the lowest negative potential, while positively charged pigmented particles travel to the latent image areas having generally the highest negative potential.
As shown in Fig. 1, the developed image, from which excess liquid has been removed by a background clean-up unit 30 and which contains differently pigmented areas having respectively positive and negative charges, is passed under a corona discharge device 44, which imposes, for example, a negative DC electrical discharge so as to convert image areas of positive charge to a negative charge and image areas of negative charge to a relatively greater negative charge.
With particular reference to the example shown in Fig. 2C, particles 23 now carry a greater negative charge than before and particles 25, which previously carried a positive charge, now carry a relatively small negative charge. As the entire developed image now carries a charge of single polarity, transfer of the image to a carrier sheet 100 (Fig. 1) may be effected, as described below in detail, by provision of a single corotron operative to charge the sheet to a polarity opposite to that of the developed image.
In an alternative embodiment, the negative DC electrical discharge may be combined with AC electrical discharge so as to narrow (or if desired to reduce to zero) the difference in surface potentials between the differently pigmented areas.
As shown in Fig. 1, a pair of register rollers 32 and 34 is adapted to feed a carrier sheet 100, which is to receive the developed image, to a transfer station, where, as shown particularly in Fig. 2D, a corona discharge device 46 is operative to impress upon the rear of the carrier sheet a charge of polarity opposite to that of the toner particles forming the image after electrical treatment of the image by corona discharge device 44. The developed image is thus drawn towards the carrier sheet by electrophoresis. Rollers 32 and 34 are mounted onto and secured for rotation with respective axles 36 and 38.
A pick-off-member 48 assists in the removal of the carrier sheet bearing the developed image from the photoconductor. The image is then fixed onto carrier sheet 100 prior to delivery to an exit tray.
A cleaning roller 56, formed of any synthetic resin known to the art and appropriate for this purpose, is driven in a direction of rotation opposite to that of the photoconductor, to scrub clean the surface thereof. To assist in this action, insulating, nonpolar liquid may be fed through a pipe 58 to the surface of the cleaning roller 56. A wiper blade 60 completes the cleaning of the photoconductive surface. Any residual charge left on the photoconductive drum is neutralized by flooding the photoconductor surface with light from a lamp 62.
As shown in Fig. 3, a background clean-up unit, referenced generally 30, comprises, according to the illustrated embodiment, a pair of rollers 74 and 76 which are rotated (by means not shown) on axles 78 and 80 respectively, in the indicated direction, counter to that of photoconductor surface 4 (arrow 9). Background clean-up unit 30 is also operative to remove excess liquid from the photoconductive surface 4, by virtue of the reverse rotation of roller 74 as indicated in Fig. 3. The use of a reverse rotating roller for removal of excess liquid is described in U.S. Patent 3,907,423, the disclosure of which is incorporated herein by reference.
By way of example, it will be supposed that the image includes areas of negative black toner particles developed at 1000 volts positive potential, and areas of positive red toner particles developed at near zero potential and background areas having potential at 500 volts to which some red and black toner particles adhere.
Roller 74 is charged with a positive potential of, for example, 600 volts and thus attracts black particles from the background without detaching of red toner particles from the image. Roller 76, however, is charged with a positive potential of, for example, 400 volts and thus attracts red particles from the background without detaching black toner particles from the image. Rollers 74 and 76 are provided with respective wiper blades 82 and 84 for removal and transfer of adherent pigmented particles to circulating insulating, nonpolar liquid which may be fed into the clean-up unit through a pipe 70 and out through a pipe 72.
According to an alternative embodiment, as the liquid passes through pipe 72 in the shown direction, any pigmented particles suspended in the liquid are removed by a filter 31, which may be any type of conventional filtering apparatus suited for this purpose. The filtered liquid may subsequently be recirculated into clean-up unit 30 via pipe 70. It is appreciated that due to the efficient cleaning activity of rollers 74 and 76 in the region therebetween and between photoconductor surface 4, it is possible to feed unfiltered liquid toner through pipe 70.
It is to be expected in practice that some black particles will be repelled from roller 76 towards the photoconductor surface 4. Such particles are removed therefrom together with other black particles on the background areas by the operation of roller 74.
Rollers 74 and 76 are spaced about 50 to 200 microns apart, so that red particles repelled by roller 74 are attracted to roller 76 and black particles repelled by roller 76 are attracted to roller 74.
The operation of rollers 74 and 76 in the structure of Fig. 3 described above is operative to remove from the photoconductor surface particles from regions having voltages between 400 and 600 volts.
Referring now to Fig. 6, it is noted that for two adjacent colored areas the transition of photoconductor voltages is not entirely sharp, as illustrated at A, but instead is more correctly represented by a curve B. Thus there are defined at the transitions between areas of black and red color, regions at which the voltage is between 400 and 600 volts. The width of these regions is indicated by D. At these regions, the operation of the background removal apparatus is effective to remove both the red and black toner particles thus producing undesired uncolored areas in these regions.
Notwithstanding that the width D is relatively small, due to the fact that the undesired uncolored areas occur at a color transition, they are noticed by the human eye.
The insulating, nonpolar liquid used as the medium for toner particles as well as for other optional purposes as described herein, preferably has a resistivity in excess of about 10⁹ ohm-cm and a dielectric constant below about 3.0. Suitable such liquids are hydrocarbons, preferably aliphatic and more preferably isomerized aliphatic hydrocarbons, as, for example, those marketed by Exxon Corporation under such trade marks as ISOPAR-G, ISOPAR-H, ISOPAR-L and ISOPAR-M, which meet the preferred resistivity and dielectric requirements. Polymers useful as binders for the pigmented particles may be thermoplastic. The presently preferred polymers are known under the trade mark ELVAX II, manufactured by E.I. Du Pont de Nemours & Company. The ELVAX II family are ethylene copolymers combining carboxylic acid functionality, high molecular weight and thermal stability.
The presently preferred ELVAX II resins are those designated 5720 and 5610. Other polymers which may be used are the ELVAX polymers and the ethylene/ethyl acrylate series made by Union Carbide such as those designated DPD 6169, DPDA 6182 Natural and DTDA 9169 Natural. Still other useful polymers made by Union Carbide are those designated DQDA 6479 Natural 7 and DQDA 6832 Natural 7; these are ethylene/ vinyl acetate resins.
The polymers are pigmented so as to render the latent image visible in two colors. The pigments may be present generally in an amount of 1-60% by weight with respect to the weight of the polymer. The selection of two pigments from the examples listed in the description which follows or/and from those otherwise known in the art may be readily performed by a person of ordinary skill in the art.
As has been set out above, two colors may be developed simultaneously by use of a toner liquid composition which comprises an insulating, nonpolar liquid having admixed therewith two different pigmented particles carrying opposite charges. It should be emphasized that the choice of colors of the pigmented particles is entirely at the discretion of the person operating the process, subject only to the condition that the pigmented particles should be adapted to be oppositely charged in the same medium.
Illustrative examples of potentially suitable pigments are Cabot Mogul L (black), Monastral Blue G (C.I. Pigment Blue 15 C.I. No. 74160), Quindo Magenta (Pigment Red 122), Indo Brilliant Scarlet Toner (Pigment Red 123, C.I. No. 71145), Dalamar Yellow (Pigment Yellow 74, C.I. No. 11741), blue pigment BT-383D (DuPont), yellow pigment YT-717D (DuPont), red pigment RT-455D (DuPont) and blue pigment Helioecht Blue GO (Bayer).
One of the two pigments may be, if desired, a finely ground ferromagnetic material, e.g. Mapico Black. Other suitable materials are metals including iron, cobalt, nickel and various magnetic oxides including Fe₂O₃ and Fe₃O₄; and others known in the art. Mixtures of known magnetic materials may also be used.
In general, the liquid toner composition employed may be prepared by a method which comprises the steps of: separately wet-grinding two pigments, which are respectively adapted to acquire charges of opposite polarities, preferably together with a thermoplastic polymeric binder for the pigments, in an inert medium until homogeneous and until the dispersed solids have predetermined characteristics selected from the group consisting of a desired particle size range and a fibrous structure; and polarizing the pigmented particles in the resultant wet-ground composition, whereby the pigmented particles acquire charges of opposite polarities, respectively.
The polarizing step is preferably carried out by addition of either one or two charge directors to the wet-ground composition, as otherwise described herein.
More particularly, the liquid toner composition may be prepared (e.g.) by initially mixing a suitable polymer together with a plasticizer and separately with each of the two selected pigments, until homogeneity is achieved. Thereafter, the mixture is allowed to cool while mixing is continued. The mixing temperature may range from about 65 to about 100°C, preferably about 90°C. Mixing times prior to cooling, typically about 90 minutes, may range between about 10 minutes and 3 hours. Any suitable mixing or blending device may be employed, such as the Ross double planetary mixer (manufactured by Charles Ross & Son of Hauppauge, New York).
After the mixture has been cooled, it is charged to an attritor, disk mill, sand mill, impeller attrition mill, vibro-energy mill, or the like. The liquid used during the grinding operation may be e.g., ISOPAR-H, which is present in an amount of 70-90% by weight in respect of the polymer. During the grinding, the particle size is determined, for example, by centrifugal analysis using, e.g., a Horiba Centrifugal Particle Size Analyzer, Model CAPA 500, manufactured by Horiba Instruments Inc. of Irvine, California.
The ground material for each pigment is then dispersed e.g. in ISOPAR-H and mixed with a charge director to form a working dispersion having a solids content of about 0.5 to about 3% by weight. The amount of charge director is dependent on its characteristics and the requirements of the use of the particular toner in question. The working dispersions for both pigments are then combined or alternatively they may be combined prior to mixing with the charge director.
As mentioned above, charge directors may be used in either one of two ways, in one of which a single charge director may be used to induce opposite charges on two different pigmented particles, respectively. The use of a single charge director in conjunction with the selection of two suitable pigmented particles may be done as e.g. is illustrated in certain of the Examples, below.
Alternatively, two charge directors are used simultaneously in the same composition, whereby there is induced a positive charge on one species of particles and a negative charge on the other species of particles. Illustration of the use of two charge directors is given in certain of the Examples below.
The phenomenon that oppositely charged toner particles can exist in the same liquid toner composition is of practical utility in the present context.
Examples of charge directors which according to the prior art were regarded as inducing negative charges are e.g. magnesium, calcium and barium petronates; aluminum stearate, metal dialkylsulfosuccinates, other metal soaps such as copper oleate, and lecithin.
Examples of charge directors which according to the prior art were regarded as inducing positive charges are e.g. manganese naphthenate, manganese octoate, zirconium octoate and cobalt octoate.
It will be appreciated by persons skilled in the art that the mechanism of charge on pigmented particles is not fully understood. The determination of polarity and degree of charge on pigmented particles is usually determined empirically, by trial and error.
When using a toner liquid which comprises two different pigmented particles, it is evidently advantageous to monitor the amount of these pigmented particles at any particular time, in order to know the amounts of each which need to be added to bring their respective concentrations in the liquid up to the desired level.
Referring now to Fig. 4, there is shown a two pigmented particle monitoring and replenishment system. Monitoring may be effected, for example, by measuring the optical density of the toner liquid as it passes through development tray feed pipe 16 (see also Fig. 1). This may be effected by way of two LEDs (light emitting diodes) referenced 92 and 94, emitting two different wavelengths of light and by a pair of connected light detectors, referenced 96 and 98, respectively.
The different light wavelength intensities are passed on, as in digital form, to a microprocessor 90, which contains information useful in correlating the different light wavelengths' intensities with concentrations of the two pigmented particles. The information contained in the microprocessor may be compiled by means of studies on similar liquids containing known concentrations of the two pigmented particles.
By way of example, it is assumed that black and blue pigmented particles are used and that the blue pigmented particle is blue light transparent and red light absorbing. For example, detector 96 utilizing blue light may thus be used to determine the concentration of black pigmented particles, while detector 98 utilizing red light may be similarly used to determine the total concentration of the two pigmented particles; thus the concentrations of both pigmented particles in the toner liquid may be determined.
Referring additionally to Fig. 5, upon receiving input from detectors 96 and 98 as described, microprocessor 90 is programmed to operate either or both pigmented particle pumps, respectively referenced 101 and 102, once it has determined that the concentration of either or both of the pigmented particles has fallen below a desired concentration. In this way, continuous regulation and, if necessary, replenishment, of the pigmented particles is possible.
It is also clearly advantageous to be able to monitor the amount of charge director in a given toner liquid, in order to know the amount needed for replenishment, i.e. to bring its concentration in the toner liquid up to the desired level. By way of example, this may be effected by compiling tables relating the conductivity of a toner liquid to various concentrations of the particular charge director therein and, when required, measuring the conductivity of operational toner liquid for determination of the charge director concentration by reference to the tables.
When, in accordance with a particular embodiment, there are employed two charge directors in the same toner liquid whose concentrations may not necessarily change at the same rate, it appears unlikely that conductivity measurements alone could give the necessary information as to the nature of the adjustment to be made in the concentrations. In this instance it may, therefore, be necessary to measure a different physical property, e.g. the amount(%) of absorption of light at particular wave lengths, on the clear liquid (a sample of which may prepared, for example, electrophoretically). The obtained light absorption information should also be correlated with pre-prepared tables. It is evident that the combination of conductivity and light absorption measurements enables determination of the amount of each charge director to be added to the liquid, and also that such measurements and determination are within the competence of a person of ordinary skill in the art.
A further indication of the depletion of charge director(s) in the toner liquid may be obtained by developing patches of each color and measuring their optical densities. Optical densities which are too high indicate depletion of charge director(s), while the contrary is indicated by optical densities which are too low. Such information could be utilized in conjunction with that obtained from conductivity measurements and also from light measurements, as applicable.
When using the dual color toner composition for development, it is necessary that the electrostatic latent image to be developed comprises areas of high, low and intermediate levels of electrostatic charge. In order to generate these three levels of charge, it will be most convenient, for example, to start with material to be copied which has a uniform grey background, besides white and black areas, such as white and black typed areas, which could be imaged by conventional optical means onto the photoreceptor.
In this example, the grey will be represented in the latent image by an intermediate charge level, while the white and black areas will be represented by the two other levels of charge. In a printer, the three charge levels could be generated, for example, by modulating the power of the exposing laser beams (in a laser printer) or the amount of charge which is supplied to a latent image holding substrate (in an electrostatic or ionographic printer).
Thus, in general terms, the system described herein need not be applied to copy colors which are similar to those in a colored original. As those skilled in the art will be aware, a process including copying similar colors can be made feasible by the combined use of color filters, a reading element and a printing head, with the result that the colored original will be stored and used in the form of digital information which may be utilized so as to give the desired three level latent image.
The invention will now be illustrated by the following non-limiting examples. The formulations therein were used to develop latent images from black and white Letraset originals which had either a grey or colored background. The electrostatic imaging response of the photoconductor results in a latent image composed of areas of approximately 1300V (first color) and 50V (second color) on a 600V background. The development bias was set at about 600V.
When using the formulations of Examples I - IV, 5 the developed image was removed from the photoconductor surface with Scotch tape, in a Savin 870 copier. When using the formulations of Examples V - VII, the developed image was transferred to paper using an additional pre-transfer corotron with a standard Savin 870 copier configuration. In Examples I - VII no background cleaning mechanism was employed.
When using the formulation of Example VIII, the developed image was transferred to paper using an additional pre-transfer corotron with a test copier configuration, and in addition a separate background cleaning station with clear liquid input, as described herein, was used. For this Example, the electrostatic imaging response of the photoconductor resulted in a latent image composed of areas of approximately 1000 Volts (first color), 50 Volts (second color) and a 500 Volt background. The development bias was set at about 600 Volts and the cleaning rollers 74 and 76 in the configuration of Fig. 3 were set at positive 600 Volts and 400 Volts respectively.
It is to be particularly noted that in accordance with the present invention, the developed image in all cases may be subjected to fusing temperatures at about 120°C or higher on a hot plate fuser, in order to eliminate undesired relatively uncolored areas between adjacent colors. In an alternative procedure which achieves the same result, a roll fuser configuration is used with some pressure, at about 100°C.
It is noted that even though such heating eliminates some or all of the undesired relatively uncolored areas, the narrow width of such areas requires only a minimal amount of image flow and thus such image flow has an insubstantial effect on image resolution.

These temperatures relate to the use of Elvax II as binder, but in the case of other polymeric binders the appropriate temperatures necessary for elimination of the uncolored areas may be readily ascertained by one skilled in the art. Replacing part of the polymeric binder with a wax has been found to lower the temperature needed in order to achieve the objective of the invention i.e. elimination of the white fringes. Suitable waxes for this purpose are e.g. those described in the following table, in which the listed physical properties are to be regarded as approximate values:

Wax	m.p. (°C)	iodine value	acid value
Bamboo leaf
	80	8	14.5
Caranda	80-84	8- 9	5-10
Carnauda	83-86	7-13	3-10
Montan	76-86	14-17	23-31
Ouricury	79-84	7- 8	3-21
Palm	74-86	9-17	5-11
Hydrogenated Castor Oil	84-88	2- 9	1- 5
Chinese insect	81-84	1.4	2- 1.5
Indian Corn	81	4.2	1.9
Shellac	79-82	6- 8	12-24

Examples I-IV and VI illustrate an embodiment of the invention in which a single charge director suffices for the two pigmented particles in the toner compositions to become oppositely charged. Examples V, VII and VIII illustrate an embodiment of the invention in which two charge directors are used to render the two pigmented particles in the toner compositions oppositely charged.

EXAMPLE I

(a) 1000g. Elvax II 5720 resin (DuPont) and 500g. Isopar L were mixed in a Ross double planetary mixer for 1 hour at 90°C, then for a further hour after addition of 250g. Mogul L carbon black (Cabot) which had been wetted by 500g. Isopar L, and finally for another hour after addition of 2000g. Isopar L pre-heated to 110°C. Stirring was continued in absence of heating until the temperature reached 40°C. 3050g. of the resultant mixture was milled in a Sweco M-18 vibratory mill (containing 0.5" alumina cylinders) with 4000g. Isopar L for 20 hours at 34°C; the average particle size of the product was 2.4 microns.
(b) 1200g. Elvax II 5720 (DuPont) and 1000g. Isopar L were mixed together in a Ross double planetary mixer at 90°C for 1 hour; 2600g. preheated Isopar L were then added and the mixing continued for a further 30 minutes at 100°C. The mixture was allowed to cool while continuing stirring until the temperature reached 40°C.
(c) An S-O attritor with 3/16" stainless steel balls was charged with 125g. of the product from part (b), 2.5g. blue pigment BT-383D (DuPont), 0.2g. nigrosine (Solvent Black 7, Bayer) and 80g. Isopar L. The mixture was ground for 15 hours; the final average particle size was 2.6 microns.
(d) The product of part (c) was diluted to a 1.5% solids content with Isopar H, and 800 grams of it were mixed with 800g. of the diluted product of part (a), which had already been separately diluted to a 1.5% solids content with Isopar H, and with 15 ml. of 6% Zirconium Octoate (ICN Biomedicals K+K Labs.). In this mixture, the Zirconium Octoate charge director renders the black pigmented particles negatively charged and the blue pigmented particles positively charged.

EXAMPLE II

(a) 500g. Elvax II 5720 (DuPont) and 500g: Isopar L were mixed together in a Ross double planetary mixer at 90°C for 1 hour. Then 80g. Cab-O-Sil M5 (Cabot) and 58.6g. YT-717D yellow pigment were added and mixing was continued for 30 minutes; 1000g. preheated Isopar L were then added and the mixing continued for 1 hour. The mixture was allowed to cool while continuing stirring until the temperature reached 40°C.
(b) 535g. of the product of part (a) and 803g. Isopar L were ground together in a Sweco M-18/5 VM-2 vibratory mill with 0.5" alumina grinding medium for 250 hours; the average particle size of the product was 1.96 microns.
(c) The product of part (b) was diluted to a 1.5% solids content with Isopar H, and 800 grams of it were mixed with 800g. of the diluted product of part (a) of Example I, which had already been separately diluted to a 1.5% solids content with Isopar H, and with 8 ml. of 6% Zirconium Octoate (ICN Biomedicals K+K Labs.). In this mixture, the Zirconium Octoate charge director renders the black pigmented particles negatively charged and the yellow pigmented particles positively charged.

EXAMPLE III

(a) An S-O attritor with 3/16" stainless steel balls was charged with 100. of the product from part (b) of Example I, 2g. red pigment RT-455D (DuPont), 0.2g. nigrosine (Solvent Black 7, Bayer) and 80g. Isopar L. The mixture was ground for 24 hours; the final average particle size was 1.6 microns.
(b) The product of part (a) was diluted to a 1.5% solids content with Isopar H, and 750 grams of it were mixed with 750g. of the diluted product of part (a) of Example I, which had already been separately diluted to a 1.5% solids content with Isopar H, and with 15 ml. of 6% Manganese Naphthenate (ICN Biomedicals K+K Labs.). In this mixture, the Manganese Naphthenate charge director renders the black pigmented particles negatively charged and the red pigmented particles positively charged.

EXAMPLE IV

(a) An S-O attritor with 3/16" stainless steel balls was charged with 100g. of the product from part (b) of Example I, 2g. red pigment RT-455D (DuPont), 0.2g. Dimanine (quaternary ammonium salt, Bayer) and 80g. Isopar L. The mixture was ground for 24 hours; the final average particle size was 1.6 microns.
(b) The product of part (a) was diluted to a 1.5% solids content with Isopar H, and 1200 grams of it were mixed with 1200g. of the diluted product of part (a) of Example I, which had already been separately diluted to a 1.5% solids content with Isopar H, and with 12 ml. of 6% Manganese Naphthenate (ICN Biomedicals K+K Labs.). In this mixture, the Manganese Naphthenate charge director renders the black pigmented particles negatively charged and the red pigmented particles positively charged.

EXAMPLE V

(a) 1000g. Elvax II 5720 (DuPont) and 1000g. Isopar L were mixed together in a Ross double planetary mixer at 90°C for 1 hour. Then 60.2g. Cab-O-Sil M5 (Cabot) and 189.75g. RT-455 D red pigment (DuPont) were added and mixing was continued for 30 minutes; 1000g. preheated Isopar L were then added and the mixing continued for 1 hour. The mixture was allowed to cool while continuing stirring until the temperature reached 40°C.
(b) An S-1 attritor with 3/16" stainless steel balls was charged with 940g. of the product from part (a) and 940g. Isopar L. The mixture was ground for 22 hours; the final average particle size was 1.6 microns.
(c) The product of part (b) was diluted to a 3.0% solids content with Isopar H, and 750 grams of it were mixed with 750g. of the diluted product of part (a) of Example I, which had already been separately diluted to a 3.0% solids content with Isopar H, and with 10 ml. of 18% Zirconium Octoate (Nuxtra, Nuodex Inc.) and 3 ml. OLOA 1200 (Oronite Division of Chevron Chemical Co.). In this mixture, both the Zirconium Octoate and the OLOA act as charge directors and render the black pigmented particles negatively charged and the red pigmented particles positively charged. While the mechanism of action of the two charge directors is at present not entirely understood, it is believed that one charge director renders the black pigmented particles negatively charged, and that the other charge director renders the red pigmented particles positively charged.

EXAMPLE VI

(a) An S-O attritor with 3/16" stainless steel balls was charged with 100g. of the product from part (b) of Example I, 2.8g. blue pigment BT-383D (DuPont), 0.56g. oxalic acid and 80g. Isopar L. The mixture was ground for 21 hours; the final average particle size was 2.7 microns.
(b) The product of part (a) was diluted to a 3.0% solids content with Isopar H, and 800 grams of it were mixed with 800 grams of the diluted product of part (a) of Example I, which had already been separately diluted to a 3.0% solids content with Isopar H, and with 10 ml. of 10% lecithin solution (Fisher Scientific Co.) in Isopar H. In this mixture, the lecithin charge director renders the black pigmented particles negatively charged and the blue pigmented particles positively charged.

EXAMPLE VII

(a) 1000g. Elvax II 5720 resin (DuPont) and 500g. Isopar L were mixed in a Ross double planetary mixer for 1 hour at 90°C, then for a further hour after addition of 250g. Mogul L carbon black (Cabot) which had been wetted by 500g. Isopar L, and finally for another hour after addition of 2000g. Isopar L pre-heated to 110°C. Stirring was continued in absence of heating until the temperature reached 40°C. 3050g. of the resultant mixture was milled in a Sweco M-18 vibratory mill (containing 0.5" alumina cylinders) with 4000g. Isopar L for 20 hours at 40°C; the average particle size of the product was 2.5 microns.
(b) An S-O attritor with 3/16" stainless steel balls was charged with l00g. of the product from part (b) of Example I, 2.8g. red pigment RT-455D (DuPont) and 70g. Isopar L. The mixture was ground for 22 hours; the final average particle size was 1.6 microns.
(c) The product of part (a) was diluted to a 3.0% solids content with Isopar H, and 1000 grams of it were mixed with 10 ml. of 10% lecithin solution (Fisher Scientific Co.) in Isopar H.
(d) The product of part (b) was diluted to a 3.0% solids content with Isopar H, and 1000 grams of it were mixed with 1 ml. of SN-6535 B (Philip A. Hunt Chemical Corp.).
(e) The products of parts (c) and (d) were mixed together after 1 hour. In this mixture, the lecithin and SN-6535 B act as charge directors and render the black pigmented particles negatively charged and the red pigmented particles positively charged. While the mechanism of action of the two charge directors is at present not entirely understood, it is believed that one charge director renders the black pigmented particles negatively charged, and that the other charge director renders the red pigmented particles positively charged.

EXAMPLE VIII

(a) An S-1 attritor with 3/16" stainless steel balls was charged with l000g. of the product from part (b) of Example I, 28g. Helioecht Blue GO blue pigment (Bayer) and 700g. Isopar L. The mixture was ground for 21 hours; the final average particle size was 2.1 microns.
(b) The product of part (a) of Example VII was diluted to a 3.0% solids content with Isopar H, and 1500 grams of it were mixed with 6 ml. of 10% lecithin solution (Fisher Scientific Co.) in Isopar H.
(c) The product of part (a) of Example VIII was diluted to a 3.0% solids content with Isopar H, and 1500 grams of it were mixed with 0.75 ml. of SN-6535 B (Philip A. Hunt Chemical Corp.).
(d) The products of parts (b) and (c) were mixed together after 3 hours. In this mixture, the lecithin and SN-6535 B act as charge directors and render the black pigmented particles negatively charged and the blue pigmented particles positively charged. While the mechanism of action of the two charge directors is at present not entirely understood, it is believed that one charge director renders the black pigmented particles negatively charged, and that the other charge director renders the blue pigmented particles positively charged.

While the invention has been particularly described with respect to certain embodiments, it will be appreciated by the person skilled in the art that many modifications and variations may be made. The invention is therefore not to be regarded as limited to such embodiments, which are merely illustrative. Rather, the invention is defined only in accordance with the claims which follow:

Claims

Imaging apparatus comprising:
an image forming member comprising an image forming surface (4) arranged for movement in a first direction;

means for forming (14) an electrostatic latent image on the image forming surface, said latent image having image and non-image areas at respective first and second electrical potentials;

means for developing (22) said electrostatic latent image using a liquid developer comprising charged toner particles which are desirably deposited on the image areas and are undesirably deposited on said non image areas;

means for removing (30) toner particles from said non-image areas and excess liquid from both said image and non-image areas after development of the image, said means for removing comprising:
a member having a second surface (74) spaced from the image forming surface (4) and moving in a direction opposite to said first direction;

means for transferring (46) said image to a substrate after removal of excess liquid and of toner particles from the non-image areas, characterized in that

the means for removal further comprises:

means for supplying (70) a cleaning liquid to at least a portion of the space between said image forming surface and said second surface.
Apparatus according to claim 1 including a member having a first surface (76) spaced from the image forming surface (4) and moving in a direction opposite to said first direction where said first and second surfaces are charged to respective third and fourth electrical potentials intermediate said first and second potentials and different from each other.
Apparatus according to claim 2 wherein said moving image forming member is a drum (2) rotating about an axis of rotation perpendicular to said first direction.
Apparatus according to claim 3 wherein said member having said first surface (76) is a rotating cylinder having an axis of rotation perpendicular to said first direction.
Apparatus according to claim 4 wherein said rotating cylinder and said rotating drum have parallel axes and wherein they rotate in the same sense.
Apparatus according to any of the preceding claims wherein said member having said second surface (74) is a rotating cylinder having an axis of rotation perpendicular to said first direction.
Apparatus according to any of claims 3-5 wherein said member having said second surface (74) is a second rotating cylinder having an axis parallel to the axis of said drum (2) and wherein said rotating cylinder and said rotating drum rotate in the same sense.
Apparatus according to claim 1 wherein said moving image forming member is a drum (2) rotating about an axis of rotation perpendicular to said first direction.
Apparatus according to claim 8 wherein said member having said first surface (76) is a rotating cylinder having an axis of rotation perpendicular to said first direction.
Apparatus according to claim 9 wherein said rotating cylinder and said rotating drum have parallel axes and wherein they rotate in the same sense.
Apparatus according to claim 6 or claim 7 wherein said means for supplying comprises:
a liquid retaining housing associated with said rotating cylinder incorporating said second surface; and

means for circulating said cleaning liquid within said housing.
Apparatus according to any of the preceding claims wherein said means for supplying also includes means for removing (31) pigmented particles from said cleaning liquid.