MXPA99008269A - Improved process for printing by it jet - Google Patents

Abstract

A process, characterized in that it comprises (a) incorporating in an ink jet recording apparatus (1) a developer composition comprising a liquid vehicle and a color developer; (2) an oxidizing composition comprising a liquid carrier and an agent oxidant; (3) a coloring composition comprising a liquid vehicle and a dye coupler; and (4) a fixing composition comprising a liquid vehicle and a fixative, (b) causing the drops of the developing composition to be ejected or ejected. in a pattern of imaging on the substrate, (c) causing the droplets of the oxidizing composition to be ejected or ejected (in a pattern of imaging the substrate, (d) causing the droplets of the coloring composition to be ejected or ejected in a pattern of imaging on the substrate, and (e) causing droplets of the fixative composition to be ejected or ejected in a pattern of imaging on the substrate, where the process results in at least some portions of the substrate containing images, comprising all four of the developer composition, the oxidizing composition, the coloring composition and the fixing composition, the portions forming a printed image. The specific embodiments of the present invention are directed to the realization of continuous shades and gray scales in images by (1) the control of the time at which the color-forming reactions are inhibited by controlling the period of time between the deposition of the color-forming liquids and the deposition of the fixative liquid, (2) control of the degree of color-forming reactions by limiting the amount of one of the color-forming liquids, or (3) controlling the size of the pixel by the control of the placement of the drop on the superimposed areas of drops of liquid forming cabbage

Description

IMPROVED PROCESS FOR PRINTING BY INK JET BACKGROUND OF THE INVENTION The present invention is directed to a process for printing by ink jet. More specifically, the present invention is directed to a process for printing by ink jet where liquids ("inks") that form color on a substrate are ejected. One embodiment of the present invention is directed to a process which comprises (a) incorporating in a device for printing by ink jet (1) a developing composition comprising a liquid vehicle and a color developer; (2) an oxidizing composition comprising a liquid vehicle and an oxidizing agent; (3) a coloring composition comprising a liquid vehicle and an ink coupler; and (4) a fixing composition comprising a liquid vehicle and a fixative; (b) causing the drops of the developer composition to be ejected or ejected in a pattern of imaging on the substrate; (c) causing the drops of the oxidizing composition to be ejected in a pattern of imaging on the substrate; (d) causing the droplets of the dye composition to be ejected in a pattern of imaging on the substrate; and (e) causing the drops of the fixing composition to be ejected in an image-forming pattern on the REF .: 30873 substrate; where the process results in some portions of the substrate containing images comprising all four of the developer composition, the oxidizing composition, the coloring composition, and the fixing composition, such portions form a printed image. The systems for printing by inkjet are generally of two types: continuous flow and drip on demand. Continuous-flow ink jet systems, the ink is emitted in a continuous flow under pressure through at least one orifice or nozzle. The flow is disturbed, causing it to break into drops at a fixed distance from the hole. At the breaking point, the drops are charged according to digital data signals and are passed through an electrostatic field which adjusts the path of each drop to direct it to the channel for recirculation or to a specific location on a medium registry. In the drop-on-demand systems, a drop is ejected from a hole directly into an over position in the middle of the register according to digital data signals. A drop is not formed or ejected unless it is to be placed on a medium of. registry. Since on-demand drip systems do not require recovery, loading or deflection, the system is much simpler than the continuous flow type. There are three types of drip inkjet systems on demand, a type of drip system on demand has as its main components a channel or passage filled with ink that has a nozzle at one end and a piezoelectric transducer near the other end. to produce pressure pulses. The relatively large size of the transducer avoids closing the nozzle spacing, and the physical limitation of the transducer results in a low speed of the ink droplet. The low speed of the drop seriously decreases the tolerances of variation and directionality of the drop speed, thus impacting the system's ability to produce high quality copies. The drop-on-demand systems that use piezoelectric devices to eject the drops also suffer from the disadvantage of a slow printing speed. Another type of drip system on demand is known as acoustic ink printing. As is known, an acoustic beam exerts a radiation pressure against objects on which it collides. Thus, when an acoustic beam hits a free surface (ie liquid / air interface) of a liquid source from below, the radiation pressure exerted against the surface of the source can reach a high enough level to release individual drops of liquid from the source, despite the restraining force of surface tension. The focus of the beam on or near the surface of the source intensifies the radiation pressure it exerts for a given amount of energy fed. These principles have been applied to proposals for inkjet and acoustic printing. For example, K.A., "Focusing Ink Jet Head," IBM Technical Disclosure Bulletin, Vol. 16, No. 4, September 1973, p. 1168-1170, the description of the. which are incorporated herein by reference, describes an ink jet in which an acoustic beam emanating from a concave surface was used and confined by a conical opening used to eject ink droplets through a small ejection or ejection hole. . Acoustic ink printers typically comprise one or more acoustic radiators for illuminating the free surface of a liquid ink source with respective acoustic beams. Each of these beams is usually focused on / or near the surface of the reservoir (ie, the liquid / air interface). In addition, printing is conventionally effected by independently modulating the excitation of the acoustic radiators according to the? Samples of the input data for the image to be printed. This modulation allows the radiation pressure, which each beam exerts against the free ink surface, to be brief by controlling the excursions at a sufficiently high pressure level to overcome the restraining force of the surface tension. That, in turn, causes individual drops of ink to be ejected from the free ink surface on demand at a suitable speed to cause them to be deposited in the configuration of an image on or near the recording medium. The acoustic beam can be modulated in its intensity or focused / out of focus to control the expulsion time, or an external source can be used to extract droplets of acoustically excited liquid on the surface of the demand source. Regardless of the timing mechanism employed, the size of the droplets ejected is determined by the diameter of the central part of the focused acoustic beam. Acoustic ink printing is attractive because it does not require small nozzles or ejection holes which have caused much of the issues of reliability and accuracy of pixel placement than conventional on-demand and continuous-flow inkjet printers They have suffered. The size of the ejection hole is a critical design parameter of an ink jet because it determines the size of the ink droplets ejected by the jet. As a result, the size of the ejection hole can not be increased, without sacrificing resolution. The acoustic impression has a greater intrinsic reliability because there are no nozzles that clog. As will be appreciated, the elimination of clogged nozzle failure mode is especially relevant to the reliability of large arrays of inkjets, such as page-width arrays comprising several thousand separate vectors. In addition, small ejection or ejection orifices are avoided, so that acoustic printing can be effected with a wide variety of inks that are conventional in ink jet printing, including inks having higher viscosities and inks containing pigments and other particulate components. It has been found that acoustic ink printers incorporating printheads comprising illuminated spherical focusing lenses can print pixels placed with precision (ie, picture elements) or resolutions which are sufficient to print relatively high quality images. complex It has also been found that the size of the individual brushes printed by such a printer can vary over a range of duration, of significant operation, thus accommodating, for example, the printing of variable tone images. In addition, the known droplet ejector technology can be adapted to a variety of print head configurations, including (1) single ejector modes for raster scanning printing, (2) ejector arrangements configured in matrix form for matrix printing, and (3) several different types of page width ejector arrays, ranging from the scarce, single row for hybrid forms of parallel / serial printing to multi-row stacked arrays with individual ejectors for each of the positions or directions of the brushes within an image field across the page (ie, a single ejector / pixel / line) for common line printing. Inks suitable for ink jet acoustic ejection are typically liquid at room temperature (ie, approximately 25 ° C), but in other embodiments the ink is in the solid state at ambient temperatures and measures are taken to liquefy the ink by heating or any other suitable methods prior to the introduction of the ink to the printhead. Images of two or more colors can be generated by several methods, including by processes where a single print head sends sound waves to different color ink sources. In addition, information related to the ink jet printing apparatus and processes is described, for example, in US Pat. No. 4,38,547, US Pat. No. 4,697,195, United States Patent 5,028,937, United States Patent 5,041,849, US Patent 4,751,529, Patent. U.S. 4,751,530, U.S. Patent 4,751,534, U.S. Patent 4,801,953, U.S. Patent 4,797,693, the descriptions of each of which are hereby incorporated by reference in their entirety. The use of focused acoustic beams to eject droplets of controlled velocity and diameter from a free liquid surface is also described in J. Appl. Phys., Vol.65, no.9 (May 1 1989) and the references therein, the description of which is hereby fully incorporated by reference. Another type of drip system on demand is known as thermal ink jet, or bubble jet, and produces high speed drops and allows very little separation between the nozzles. The main components of this type of drip-on-demand system are an ink-filled channel that has a nozzle at one end and a resistor that generates heat near the nozzle. The printing signals representing digital information originate from an electrical current impulse in a resistive layer with each ink passage near the orifice or nozzle, causing the vehicle of the ink (usually water) in the immediate vicinity to evaporate almost instantaneously and create a bubble. The ink in the hole is forced outward like a drop driven as the bubble expands. When the hydrodynamic movement of the. Ink stops, the process is ready to start all over again. With the introduction of a drop ejection or ejection system based on thermally generated bubbles, commonly known as the "bubble jet" system, on-demand drip inkjet printers provide lower-cost, simpler devices than its continuous flow contrast, and still have substantially the same high-speed printing capability. The sequence of operation of the bubble jet system begins with a current pulse through the resistive layer in the ink filled channel, the resistive layer being very close to the orifice or nozzle of that channel. The heat of ink resistance. The ink is overheated above its normal boiling point, and for a water-based ink, it finally reaches the critical temperature for formation of the bubble or nucleation of about 280 ° C. Once hot, the "bubble" or, steam of water thermally insulates the heater ink and ^ psfe apply more heat to the ink. This bubble expands until all the heat stored in the ink that exceeds the normal boiling point is diffused or used to convert liquid to vapor, which removes heat due to the heat of evaporation.

The expansion of the bubble forces the ink drop out of the nozzle, and once the excess heat is removed, the bubble collapses on the resistance. At this point, the resistance is no longer heated because the current pulse has passed, and at the same time as the bubble collapses, the drop is driven at a high speed in a direction toward the middle of the register. The resistive layer finds a severe cavitation force due to the collapse of the bubble, which tends to erode it. Subsequently, the ink channel is filled due to capillary action. The complete sequence of formation and collapse of the bubble occurs in approximately 10 microseconds. The channel can be reactivated after a minimum drying time of 100 to 500 microseconds to allow the channel to be refilled and allow the dynamic refilling factors to be somewhat dampened. Thermal ink jet processes are well known and are described in, for example, US Patent 4,601,777, US Patent 4,251,824, US Patent 4,410,889, US Patent 4,412,224 and US Patent 4,532,530, the descriptions of each of which are fully incorporated herein. as reference. U.S. Patent 3,870,435 (Watanabe et al.), The disclosure of which is hereby incorporated by reference, discloses an almost colorless aqueous ink containing a color coupler which is used to record a record on a "record" sheet. having a coated layer containing fine white powder and a color developer which reacts with the color coupler to form a vivid color visual record of a highly durable nature.

U.S. Patent 3,850,649 (Buerkley et al.), The disclosure of which is hereby incorporated by reference, discloses an ink composition which is particularly suitable for offset (wet) lithography printing and comprising a fixing vehicle fast mixed by an iron complexing agent. The composition provides one. latent storable image (that is, invisible and hidden) when printed on a low iron content paper selected in an appropriate manner. The treatment of the latent image printed with an iron salt reveals the image and becomes clearly visible. The visible material can be printed with the latent material on the same paper using a conventional 2-color offset press. U.S. Patent 5,443,629 (Saville et al.), The disclosure of which is hereby incorporated by reference in its entirety, discloses an ink for latent images that can be used particularly in print forms such as games q coloring books. An offset litho press is used to print a substantially invisible image on a standard sheet of paper. The latent ink used to form the latent image is a mixture of potassium ferrocyanide or other iron complexing compounds, suitable color fixatives, white ink and varnish. Subsequently a developer solution such as ferric chloride or ammonium sulfate is added to the paper to make the image visible. Japanese Patent Publication JP 77049366 B, the disclosure of which is hereby incorporated by reference, discloses a registration system which comprises a pen or pen that applies a colorless ink containing a color developer such as potassium ferrocyanide. and a hygroscopic compound such as glycerol dissolved in water to a paper coated with a white mineral powder and a colorless compound such as iron alum which forms color upon reaction with the color developer. Japanese Patent Publication JP 9030107 A, the disclosure of which is hereby incorporated by reference, describes a process which includes ejecting or ejecting droplets of multiple color ink compositions into a recording medium having an absorbent layer for coloring agents to render the agent dye in the composition of inks will adhere to the image of the record to form a color image. Each of the coloring agents in the color ink compositions are located at a specific depth of the absorbent layer of the coloring agents, the coloring agents having different color shades do not migrate to the same depth in the absorbent layer. Better color reproduction can be achieved when coloring agents of multiple types are printed on the <; isma position. British Patent Publication GB 1398334, the description of which is fully incorporated herein as , describes a composition of printing ink capable of forming latent images which can be made '' 'visible by reaction with metal salts which comprise (1) at least 40 percent by weight of a quick-fix, stable-colored, free • vehicle of metal or dryers and having an adhesion viscosity, hydrophobicity and ability to withstand sufficient pigments to utilize offset lithographic printing, and, dispersed in the vehicle (2) at least 10 percent of a reagent insolubles in light colored solid particulate water having an average particle size of 0.5 to 5.0 microns and which is capable of forming a strongly colored complex with an iron salt coreactant.The composition is particularly useful for the printing of educational aids such as self-answer examination sheets. 0 German Patent Publication DE 2505077, the description of which is hereby incorporated by reference, describes a liquid for writing or printing watery to produce an invisible record which contains ne a mixture of gallic acid and alkaline gallate which will react with heavy metal salts.

"Leuco Dye System for Ink Jet Printing," W.T. Pi bley, IBM Technical Disclosure Bulletin, Vol. 23, No. 4, p. 1387 (September 1980), the description of which is hereby fully incorporated by reference, discloses inkjet printing with archiving properties and improved by the use of leuco or vat dye. The dyes are converted to their permanent form when they are oxidized. The recording medium is first coated or impregnated with an oxidizing agent as acidic materials, such as acid clays, organic acids or polymeric phenols. After being combined with the oxidant, the dyes are converted to their permanent form, becoming insoluble and having a high dyeing strength and excellent archiving properties, such as water resistance and light resistance. Although known compositions and processes are suitable for the intended purposes, there remains a need for improved ink jet printing processes. In addition, there is still a need for inkjet printing processes that allow the generation of photographic quality images on flat paper. In addition, there is still a need for inkjet printing processes that allow a wider range of colors. Additionally, there remains a need for ink jet printing processes that allow a greater color intensity. There is also a need for inkjet printing processes that generate permanent and water resistant images. In addition, there is a need for ink jet printing processes that exhibit a desirable production rate. In addition, there is a need for ink jet printing processes that allow gray-level printing without specific occupancy by the droplet ejector solution, where near-continuous or multi-level gray images with ejectors can be made. of route 300 dpi (dots per inch) simple. Additionally, there is a need for inkjet printing processes that allow the printing of continuous tone cartographic images without specific concern for the resolution of the drop ejector. There also remains a need for inkjet printing processes that allow the production of variable spot sizes. In addition, there continues to be a need for ink jet printing processes that allow the production of high resolution images. BRIEF DESCRIPTION OF THE INVENTION The object of the present invention is to provide ink jet printing processes with the advantages noted above.

Another object of the present invention is to provide improved ink jet printing processes. Another object of the present invention is to provide ink jet printing processes, which allow the generation of photographic quality images on plain paper. Still another object of the present invention is to provide ink jet printing processes that allow a greater range of colors. Another object of the present invention is to provide ink jet printing processes which allow a greater intensity of color. Yet another object of the present invention is to provide an ink jet printing process, which generates permanent and water resistant images. Still another object of the present invention is to provide ink jet printing processes, which exhibit desired production speed. Still another object of the present invention is to provide ink jet printing processes, which allow the printing of gray levels without specifying the resolution of the droplet ejector, where almost continuous tone images or multi-level images can be produced. gray with droplet ejectors of 300 dpi (drops per inch) simple. Still another object of the present invention is to provide ink jet printing processes, which allow the printing of cartographic images regardless of the specific resolution of the drop ejector. Still another object of the present invention is to provide ink jet printing processes, which allow the production of variable dot sizes. Another object of the present invention is to provide ink jet printing processes, which allow the production of high resolution images. These and other objects of the present invention (or specific embodiments thereof) can be achieved by providing a process, which comprises (a) incorporating into an ink jet recording apparatus (1) a regulatory composition comprising a vehicle and a color developer; (2) an oxidizing composition comprising a liquid vehicle and an oxidizing agent; (3) a coloring composition comprising a liquid vehicle and a dye coupler; and (4) a fixing composition comprising a vehicle and a fixative; (b) causing the droplets of the developer composition to be ejected or ejected in a pattern of image formation on a substrate; (c) causing the drops of the oxidized composition to be ejected or ejected in a pattern of imaging on the substrate; (d) causing droplets of the dye composition to be ejected or ejected in a pattern of imaging on the substrate; and (e) causing droplets of the setting composition to be ejected or ejected in a pattern of imaging on the substrate; wherein the process results in at least some portions of the substrate containing images comprising all four of the developer composition, the oxidizing composition, the coloring composition and the fixing composition, the portions forming a printed image.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a perspective view illustrating an ink jet printer, of the thermal type, of multiple, multi-colored print heads, useful for the present invention; Figure 2 is a view taken along line B-B of Figure 1, illustrating the nozzle arrays of the multi-color multiple print head thermal ink jet recording head assembly; Figure 3 is an isometric view of a multi-color single-head thermal inkjet printer having a replaceable ink jet supply tank useful for the present invention; Figure 4 is an isometric view of the partial exploded view of a thermal ink jet cartridge with a single, multi-colored print head used in the printer of Figure 3 with an integral printhead and ink connectors and ink tanks. replaceable ink; Figure 5 is a side elevational view partially showing, schematically, a useful acoustic ink jet printer - for the present invention; Figure 6 is a schematic representation of an acoustic ink jet print head used in the apparatus of Figure 5 and illustrating ink droplets moving towards a recording medium on the transport web; Figure 7 is a cross-sectional view, not scaled, of the first embodiment of the acoustic droplet ejector, which is shown ejecting or ejecting a drop of a marker fluid; Figure 8 is a cross-sectional view, not scaled, of a second embodiment of the acoustic droplet ejector, which is shown ejecting a drop of the marker fluid; Figure 9 is a schematic top-to-bottom description of an array of acoustic droplet ejectors in an ejector unit; Figure 10 is a schematic top-to-bottom view of the organization of a plurality of ejector units in a color print head; Figure 11 is a cross-sectional view of one embodiment of the present invention, a material deposition head has multiple ejection units; Figure 12 is a perspective view of the Figure 11; Figure 13 is a schematic front elevational view of a portion of an extended width or width printhead, which has been assembled from a plurality of thermal ink jet or acoustic inkjet printheads, partially arranged across; and Figure 14 schematically illustrates a process of the present invention where gray scale images are generated by superimposing drops.

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a process which comprises (a) incorporating an ink jet recording apparatus (1) a developing composition comprising a liquid vehicle and a color developer; (2) an oxidizing composition comprising a liquid vehicle and an oxidizing agent; (3) a coloring composition comprising a liquid vehicle and a dye coupler; and (4) a fixing composition comprising a liquid vehicle and a fixative; (b) causing the drops of the developer composition to be ejected in a pattern of imaging on the substrate; (c) causing the drops of the oxidizing composition to be ejected in a pattern of imaging on the substrate; (d) causing the drops of the coloring composition to be ejected in a pattern of. formation of images on the substrate; and (e) causing "drops of the fixing composition to be injected in a pattern of imaging on the substrate, where the process results in at least portions of the substrate containing images comprising all four of the developer composition, oxidizing composition, the coloring composition and the fixing composition, the portions form a printed image., only the coloring composition is incorporated in the printing apparatus, and the resulting images are of a single color. In another embodiment, at least two different colorant compositions are incorporated into the printing apparatus, and the resulting images are of at least two different colors. In a specific embodiment, three different colorant compositions are incorporated into the recording apparatus, one containing a cyan ink coupler, one containing a magenta dye coupler and one containing a yellow ink coupler, thereby allowing the production of full color images. The specific embodiments of the present invention are directed to the realization of continuous tone images in the gray scale (1) by controlling the time at which the color formation reactions are defined by controlling the time period between the position of the liquids that form the color and the deposition of the fixative liquid; (2) controlling the degree of the reactions that form color by limiting the amount of one of the liquids they form in color (ie, the dye composition, the developer composition or the oxidizing composition); or (3) control of the pixel size by controlling the placement of the drop over superimposed areas of droplets of the color forming liquids. The present invention can employ any suitable or desired inkjet printing apparatus, including continuous flow inkjet printers, piezoelectric ink jet printers, thermal inkjet printers, acoustic ink jet printers, printers. of hot melt ink jet of any of the above or similar types. Below, examples of the apparatuses suitable for the present invention are illustrated; these examples are illustrative in nature and should not be construed to limit the scope of the invention in any way. Figure 1 shows a three-color printing mechanism 1, which includes a cartridge 2 marked to oscillate in the directions of arrow A-A on guide rails 3 and 4 secured to a frame (not shown) of the printer. The cartridge is driven along the guide rails by a suitable mechanism, such as a drive belt 5 supported between the pressure pulley 6 and the drive pulley 7, and driven by the motor 8. In the illustrative embodiment, to produce a multi-colored, composite image, register heads 9a, 9b, 9c, 9d, 9e and 9f (distributing a developer composition, an oxidizing composition, a dye composition containing a yellow dye coupler, a dye composition comprising a magenta dye coupler, a dye composition containing a dye coupler cyan, and a setting composition, respectively) in the respective cartridge carriers provided on the cartridge 2. In another embodiment (not shown), four are provided registration heads, with one distributing a coloring composition, where the resulting images are monochromatic. Each cartridge holder includes the appropriate mechanical, electrical and fluid couplings, so that the selected ink actuators can be activated in response to a suitable activation signal from a controller 13 to eject ink from the cartridges onto the recording substrate 14 supported. on a plate 15. The controller 13, which may be a microprocessor or computer, receives signals that represent a composite, color image of an image generator 16. The image generators are well known in the art. Examples of a suitable image generator 16, are a scanning or digitizing device that scans data from a color original and generates signals in the predetermined color space representing the color readings, or a computer, and the programs and systems of associated programming and / or user interfaces that generate digital image signals in a predetermined color space. There are many acceptable standards for the color space format such as RGB, CYMK, CIELAB, CIELUV and others. The signals of the generator 16 are preferably stored, at least temporarily, in a buffer 17. The memory 17 can be a RAM or ROM. As shown in Figure 2, each cartridge 9 is provided with an array of aligned nozzles 18. The nozzles can be any size and spacing depending on the desired resolution of the printing device. For example, if a resolution of 300 dots per inch is preferred, each nozzle should be approximately 50.8 μm (2 mils) in diameter and approximately 83.82 μm (3.3 mils) apart from the centers. The print heads suitable for use in the apparatus illustrated in Figures 1 and 2, including both configurations of "side trigger" an "upper trigger", are described in, for example, US Patent 4,638,337, US Patent 4,601,777, US Patent 5,739,254, US Patent 5,753,783, US Patent 4,678,529, US Patent 4,567,493, US Patent 4,568,953 , US Patent 4,789,425, US Patent 4,985,710, US Patent 5,160,945, US Patent 4, 935, 750, and US Patent Re. 32,572, the descriptions of each of which are hereby incorporated by reference. Figure 3 illustrates an isometric view of a multi-color single-head thermal ink jet printer 19 which is useful for the process of the present invention. In the illustrated embodiment, the printer includes six replaceable ink supply tanks 20 mounted on a removable ink jet cartridge 21. The ink supply tanks supply the developer composition, an oxidizing composition, a dye composition containing an ink coupler. yellow ink, a dye composition containing a magenta ink coupler, a dye composition containing a cyan ink coupler, and a setting composition. In another embodiment (not shown), four replacement dye supply tanks are provided, with one distributing a dye composition, where the resulting images are monochromatic. The removable cartridge is installed on a transposable cartridge 22 which is supported by cartridge guide rails 23 fixedly mounted on the frame 24 of the printer. The removable cartridge is designed to consume or exhaust the ink of at least ten ink supply tanks of the same ink color. The cartridge is moved back and forth along the guide rails by suitable means (not shown), as is well known in the printer industry, under the control of the printer driver (not shown). ). Referring also to Figure 4, the multi-color, single-print thermal ink jet cartridge 21 comprises the housing 25 having an integral multi-color ink jet printhead 26 and a tube connector of dye 27 which projects from a wall 28 of the cartridge to be inserted into the ink tanks when the ink tanks are installed in the cartridge housing. The ink flow paths, represented by dotted lines 29, in the cartridge housing interconnects each of the ink connectors with the separate entries of the print head. The ink jet cartridge, which comprises the replaceable ink supply tanks containing ink for supplying ink to the print head 26, includes a printed circuit board of interconnection (not shown) that is connected to the controller of the printer by means of a ribbon cable 30 through which electrical signals are selectively applied to the print head to selectively eject ink droplets from the print nozzles (not shown). The multi-color print head 26 contains a plurality of ink channels (not shown) which carry ink from each of the ink tanks to the respective groups of ink jet nozzles of the print head. When printing the cartridge 22 it oscillates back and forth along the guide rails 23 in the direction of the arrow 31. When the print head swings back and forth through the recording medium 32, such as the sheets of single-cut paper which are fed from an input stack 33 of sheets, the ink droplets are ejected from the selected print head nozzles towards the recording medium 32. The nozzles are typically arranged in a linear array perpendicular to the oscillating direction of the arrow 34. During each pass of the cartridge 22, the recording medium 32 is maintained in a stationary position. At the end of each step, the recording medium is inclined in the direction of the arrow 34. A single sheet of recording medium 32 is fed from the feed stack 33 through the printer along a path defined by a curved plate 34a and a guide member 35. The sheet is directed along the path by a transport roller 36 as understood by those skilled in the art or, for example, as illustrated in U.S. Patent 5,534,902, the description of which is incorporated here as a reference. When the registration means leaves a slot between the plate 34 and the guide member 35, the sheet 32 is forced to bend backwards so that the sheet is supported by the plate 34a in a flat portion thereof to be printed by the print head 26. Continuing with reference to Figure 4, the ink of each of the ink supply tanks 20 is removed by capillary action through the outlet port 37 in the ink supply tanks, the connectors of the ink tube 38, and the ink flow paths 29 in the cartridge housing to the print head 26. The ink tube connectors and the cartridge housing flow paths supply ink to the ink channels of the ink tube. print head, replenishing the ink after each injection of a drop of the nozzle associated with the ink channel of the print head. It is important that the ink in the nozzles be maintained at a slightly negative pressure, so as to prevent the ink from dripping onto the recording medium 32, and ensuring that the ink drops are placed on the recording medium only when the drop is ejected or ejected by an electrical signal applied to the heating element in the ink channel for the selected nozzle. A negative pressure also ensures that the size of the ink droplets ejected from the nozzle remains substantially constant when the ink runs out of the ink supply tanks. The negative pressure is usually in the range of -1.27 to -12.7 centimeters of water (-0.5 to -5.0 inches of water). A known method for supplying ink at a negative pressure is to place an open cell foam or perforated felt into the ink supply tanks in which the ink is absorbed and suspended by capillary action. Ink tanks containing ink-retaining material are described, for example, in U.S. Patent 5,185,614, U.S. Patent 4,771,295, and U.S. Patent 5,486,855, the descriptions of which are all incorporated herein by reference. In Figure 5, it is a side elevation view partially showing an acoustic ink jet printer 40 described. The printer has a printer driver 41, a conveyor belt 42 entrained on a pressure roller 43 and a drive roller 44 for movement in the direction of the arrow 45, of a plurality of acoustic ink jet printheads. 46 mounted on a cartridge 47 which is translated along guide rails 48 in a direction orthogonal to the direction of the print head cartridge, and a pair of input feed rolls 49 and 50 forming a contact line between the feed register of a recording medium 51, such as a sheet of paper, on the conveyor belt. A pair of output feed rollers 52 and 53 drive the recording means from the conveyor belt, so that the recording means is always attached to either the feed rollers or the output rollers. The printer controller 41 communicates directly with and controls the input feed rollers 49 and 50, which accept the recording means from the feed tray (not shown) after the recording medium leaves a pair of feed rollers. guides 54 which direct the recording means towards the input feeding rollers. The printer controller 41 also communicates directly with and controls the movement of the conveyor belt via a stepper motor (not shown). In the illustrated mode, the acoustic inkjet printheads are portable, printheads of partial width, a print head for each of the liquids to be distributed on the recording medium, the conveyor belt is kept stationary by the controller of the printer while the print heads print a row of an image. The conveyor belt is then inclined a distance equal to the height of the printed row or a portion thereof until the entire image is printed. Other modalities are possible, including the mode in which the print heads are on the width of the page and fixed and the conveyor belt moves relative to the print heads at a constant speed. The printer conveyor 41 communicates directly with and controls the acoustic ink drop ejectors 55 (see Figure 6) on each of the print heads.

Referring to Figure 6, a schematic representation of the apparatus is shown in an elongated cross-sectional view of a portion of the print head 46, the conveyor belt 42 with the registration means 51 on it, and the space "G" between the face 56 of the print head having the openings 57 therein and the conveyor belt. The print head 46 ejects or ejects the ink droplets 58 through the openings of the print head 57 directed towards the recording medium 51 using acoustic ink drop ejectors 55. Each drop ejector of acoustic ink includes a transducer piezoelectric RF source which creates a sound wave 59 in the ink 60 stored in the print head. A lens (not shown), such as a Fresnel lens, focuses the sound wave to the surface of the ink 61 in the openings 57. The acoustic pressure on the surface of the ink 61 causes a drop of ink to be formed. The fully formed and ejected droplet .58 is directed and ejected to the recording medium 51. Refer now to Figure 7 for an illustration of an exemplary acoustic droplet ejector 65. Figure 7 shows the droplet ejector 65 briefly after the ejection or ejection of a drop 66 of marker fluids 67 and before the accumulation 68 on the free surface 69 of the marker fluid 67 has relaxed. When the drops are ejected or ejected from such accumulations, the relaxation of the accumulation and subsequent formation are prerequisites for the ejection of the drops. The formation of the accumulation 68 and the ejection of the drop 66 are the results of the pressure exerted by the acoustic forces created by a ZnO 70 transducer. To generate the acoustic pressure, the RF excitation energy to the ZnO 70 transducer from a source RF driver 71 via a lower electrode 72 and an upper electrode 73. The acoustic energy of the transducer passes through a base 74 towards an acoustic lens 75. The acoustic lens focuses its received acoustic energy on a small focal area which is in , or near, the free surface 69 of the marker fluid 67. As long as the same energy of the acoustic beam is sufficient and is properly focused relative to the free surface 6-9 of the marker fluid, an accumulation 68 is formed and ejected or a droplet 66 is ejected. Suitable acoustic lenses can be manufactured in many ways, for example, by first depositing an adequate thickness of a recordable material onto a sust. little while. Next, the deposited material can be recorded to create the lenses. Alternatively, a master mold may be pressed into the substrate at a location where lenses are designated. Heating the substrate to its softening temperature creates acoustic lenses.

Referring still to Figure 7, the acoustic energy of the acoustic lens 75 passes through a liquid cell 76 filled with a liquid (such as water) having a relatively low attenuation. The bottom of the liquid cell 76 is formed by the base 74, the sides of the liquid cell are formed by surfaces of an opening in an upper plate 77, in the upper part of the liquid cell is sealed by a structure of acoustically thin cap 78. "Acoustically thin" implies that the thickness of the cap structure is less than the wavelength of the acoustic energy applied. The droplet ejector "65 further includes a reservoir 79, located on the structure of the lid 78, which contains marker fluid 67. As shown in FIG. 7, the reservoir includes an opening 80 defined by the side walls 81. Note that the opening 80 is axially aligned with the liquid cell 76. The side walls 81 include a plurality of holes 82 through which the marking fluid passes.The pressure means 83 forces the marking fluid 67 through the holes 82 to create an accumulation of the marker fluid having a free surface on the structure of the cover 78. The droplet ejector 65 is dimensioned in such a way that the free surface 69 of the marker fluid is in, or near, the acoustic focal area. Since the structure of the lid 78 is acoustically thin, the acoustic energy easily passes through the structure of the lid and into the superimposed marker fluid. A droplet ejector similar to droplet ejector 65, which includes the acoustically thin cap structure and reservoir as described in US Patent Application Serial No. 890,211, filed by Quate et. to the. on May 29, 1992, now abandoned, the description of which is fully incorporated here as a reference. A second mode of the acoustic drops ejector 85 is illustrated in Figure 8. The drop ejector 85 does not have a liquid cell 76 sealed by an acoustically thin cap structure 78. And it does not have a reservoir filled with marker fluid 67 or any of the elements associated with the reservoir. Instead, the acoustic energy passes from the acoustic lens 75 directly to the marker fluid 67. However, the drops 66 are still ejected from the accumulations 68 formed on the free surface 69 of the marker fluid. The ejectors of individual acoustic drops 65 and 85 (illustrated in Figures 7 and 8, respectively) are usually manufactured as part of an array of acoustic droplet ejectors. Figure 9 shows a schematic top-to-bottom description of an array 86 of individual drop ejectors 87 which is particularly useful in printing applications. Since each droplet ejector 87 is capable of ejecting a droplet with a smaller radius than the ejector of the drop itself, and since the total coverage of the recording medium is desirable, the individual droplet ejectors are arranged in deviated rows . In Figure 9, each drop ejector in a given row is spaced a distance 88 from its neighbors. That distance 88 is eight (8) times the diameter of a drop ejected or ejected from a drop ejector. By diverting the eight (8) rows of drop ejectors at an angle 89, and moving in the middle of the register in relation to the rows of drop ejectors at a predetermined speed, the array 100. can print fully filled lines or blocks (without spaces between pixels). Figure 9 illustrates an arrangement of drop ejectors capable of printing in a single pass a single color of a marker fluid, i.e. an ejection unit. Multiple ejection units, each capable of ejecting a different material, can be contained in a single material deposition head. Figure 10 schematically describes a material deposition head 90 comprising six arrays, designated as arrays 91, 92, 93, 94, 95, and 96, each similar to array 86 shown in Figure 9 (except that, for clarity, only three rows of drop ejectors are shown 87). Although in many applications the distance between each of the arrangements will be the same, no such thing is required. The benefit of a material deposition head such as the material deposition head 90 is readily apparent. By forming multiple arrays, each capable of printing a different fluid, and moving the recording medium in relation to the material deposition head at a controlled rate, and by timing the ejection of each array correctly, registration can be easily achieved of printed liquids. Figure 11 shows the description of a simplified cross section (again, only three rows of the eight rows of each ejection unit and only two of the six ejection units) of the material deposition head 90, with arrangements 92 and 93. The other arrangements are not shown, but it must be understood that they are from left to right. As shown, the free surface 97 of the material 98 is contained within the openings 99 that are defined in a thin plate 100 which is on a support 101. Figure 12 is a perspective view of Figure 11, illustrating better the openings 99. It should be understood that each material 98 is confined to a chamber defined by a channel 102 and the base. The individual drop ejectors are each aligned with an associated opening 99 which is axially aligned with the acoustic lens of the drop ejector 75 (see also Figures 7 and 8). The drops are ejected or ejected from the free surface 97 through the openings. The holder 101 is directly attached to a glass base 28. It should be noted that Figures 11 and 12 and the subsequent associated text and drawings describe all illustrative individual drop ejectors according to Figure 8. It should be noted that the drop ejectors of according to Figure 7 are also suitable for use in the apparatus illustrated in Figures 11 and 12. In Figure 13, there is shown a schematic front view of a portion of the multi-fluid printhead 105 dotted line. The print head 105 comprises a plurality of partially arranged partial print heads 106 mounted in at least two parallel rows. Each printhead of partial widthwise arrangement has at least four rows of nozzles 107 or, in the case of the acoustic ink jet printheads of the nozzles described with for example U.S. Patent 4,697,195, the printhead of Partial widthwise arrangement has at least four rows of drop ejection sites 107. Each row of nozzles or drop ejection sites 107 ejects or ejects a developer composition, an oxidizing composition, a dye composition containing a yellow dye coupler , a dye composition containing a magenta dye coupler, a dye composition containing a cyan dye coupler, or a fixative composition. In another embodiment (not shown), four rows of nozzles are provided, with one distributing a dye composition, where the resulting images are monochromatic. In the illustrated embodiment, the partially arranged print heads, in width in each of the two rows, are equally spaced apart from each other and the partially arranged widthwise print heads in a row are offset from the print heads of the printhead. partial widthwise arrangement in the other row, with the end portions 108 of the adjacent partial widthwise print heads in the two different rows superimposed on each other. Each partial-width print head 106 has an equal number of droplet ejection locations or at nozzles 107 per row and equal number of droplet ejection locations, or nozzles per print head. A sufficient number of stacked-width partial-width print heads 106 are mounted to provide wide print or widthwise printing of the page, and when the printing is sufficient across the page, such a printhead is used. Print is known as full width print head. An extended width array printhead is one that has a plurality of partial width offset printheads but the rows of such printheads do not contain enough partial width offset printheads to print through the printhead. width of the page. An extended width printhead functions equally to a partial width array print head, which is capable of printing a larger row of information. In all of the above printing apparatuses illustrated in Figures 1 through 13, it should be appreciated that the number of liquids applied to the substrate, and consequently the number of ink supplies or containers, can be varied as desired. For example, for monochromatic printing, the printer will apply to the substrate four liquids, namely a developer composition, an oxidizing composition and a fixing composition, and the coloring composition of the desired color. In multi-color printing, black should be applied in addition to cyan, magenta and yellow, and the printer will apply seven liquids to the substrate, namely a developer composition, an oxidizing composition, a fixing composition, and the cyan, magenta coloring compositions. , yellow and black. Additional examples of printing apparatuses suitable for the present invention are described in, for example, U.S. Patent 5,568,169, U.S. Patent 5,565,113, U.S. Patent 5,596,355, U.S. Patent 5,371,531, U.S. Patent 4,797,693, U.S. Patent 5,198,054, U.S. Application No. Series 08 / 946,935, co-pending, US application Serial No. 08 / 883,988, co-pending, US application Serial No. 08 / 965,316, co-pending, and US application Serial No. 08 / 820,624, co-pending, the descriptions of each of which are hereby incorporated by reference in their entirety. Any order of deposition of the ink coupler, developer and oxidizing agent can be used; typically, the order selected depends on the specific reagents employed and their "formulations." The fixative is always deposited at the end.In one embodiment of the present invention, the tuning of the deposition of the fixative determines the intensity of the color. When the coupler and oxidizer come together, the reaction to form the dye begins.The intensity of the color depends on the amount of dye formed.The deposition of the fixative at different times along the reaction profile stops the dye formation reactions, and the The amount of dye formed at that moment in time determines the tone or intensity of the color.The developer and coupler can usually be deposited regardless of time.After the oxidant and the developer are together, however, the deposition time of the coupler and fixator becomes more important, because the oxidized developer is highly reactive and will react with the coupler relatively I ask after its formation. In one embodiment of the present invention, a multiplicity of intensities or levels of "gray" within a particular color by controlling the time between the point at which the developer composition, the oxidizing composition and the coloring composition are put together at the point at which the fixing composition is deposited. The reaction between the dye coupler and the oxidized developer may stop at a point near the maximum color intensity, thereby creating one or more levels of "gray" color. In another embodiment of the present invention, a multiplicity of intensities or "gray" levels within a particular color can be obtained by dripping fixed amounts of developer composition and coloring composition onto the substrate in combination with varying amounts of oxidizing composition, with the oxidizing agent in the oxidizing composition being present in amounts that limit the reaction with respect to color developer in the developer composition and the dye coupler in the dye composition. More specifically, the print head for blasting the oxidizing composition can have a multiplicity of channels, each of which drips a different volume of oxidizing compound, as required. Alternatively, the print head for blasting the oxidizing composition may drip droplets of very small volume, and multiple small droplets of oxidizing composition may be deposited at the location of a given pixel, depending on the intensity of "darkness" or saturation of the desired color in the location of that 'pixel. In this way, a high-resolution gray level print can be obtained without loss of production speed, which can otherwise be associated with "gray-level" ink jet printing processes. of varying the amount or volume of the oxidizing composition, the amount or volume of developer composition and / or the amount or volume of coloring composition can be varied by the above methods to obtain gray level prints In yet another embodiment of the present invention. invention, high resolution images can be generated in the gray scale by generating spots or spots of varying sizes on the surface More specifically, the developing composition, the coloring composition, and the oxidizing composition are blasted in a pattern of imaging so that the superposition of drops of these three compositions is controlled.The size of the pixel can be therefore, it is modulated to obtain variable dot sizes, and in this way prints of high resolution gray levels can be obtained without loss of production speed which could otherwise be associated with the ink jet printing processes. level of gray. As illustrated schematically in Figure 14, the drops of developer composition 201, the drops of oxidizing composition 203 and the drops of dye composition 205 can be blasted onto substrate 207 with varying amounts of overlap 209, thereby forming image areas. of variable size. In the full-color printing process, three dye compositions are employed to form image areas of different size, for example, cyan, magenta and yellow. The developer composition generally comprises a liquid carrier and a color developer or developer, and functions as a color-forming component in the process of the present invention. For the purpose of simplification, the developing composition will sometimes be referred to herein as an ink. Any liquid can be used as the main component of the liquid vehicle, provided that it dissolves or disperses the components of the composition and is of an appropriate viscosity for the selected droplet ejector. For example, in thermal inkjet printing systems, a preferred liquid carrier is water. In other drop ejectors, such as those that use continuous flow processes, piezoelectric ink jet printers, acoustic ink jet printers and the like, other liquids, such as hydrocarbons, glycols, ethers, sulfones such as sulfolane, pyrrolidinones such as 2-pyrrolidinone and N-methyl pyrrolidinone may also be employed. , other dipolar aprotic solvents, and the like, as well as mixtures thereof. The developer composition may also contain other components which may improve its performance as an inkjet ink, such as wetting agents, penetrants, cosolvents, blasting aids or the like, as discussed in greater detail hereinafter. The developer composition typically contains the color developer in an amount of about 0.05 to about 15 weight percent of the developer composition, preferably about 0.1 to about 10 weight percent of the developer composition, and more preferably from about 0.5 to about 5 weight percent of the developer composition, although the amount may be outside those ranges. Examples of color developers or developer agents include phenylenediamines, of the formulas wherein R is a hydrogen atom, an alkyl group, preferably 1 to about 4 carbon atoms, or a substituted alkyl group, wherein the ring of the benzene may be substituted, and where 2 or more of the substituents may be joined together to form additional rings, such as the p-phenylenediamine of the formula o-Phenylenediamine of the formula monomethyl-p-phenylenediamine of the formula and similar. Particularly preferred as color developers are the N, N-dialkyl-p-phenylenediamines of the general formula wherein each of Ri and R2, independently of each other, is an alkyl group, preferably with about 1 to about 4 carbon atoms, or a substituted alkyl group, wherein the benzene ring may be substituted, and where two may be joined or more substituents to form additional rings. Specific examples of N, N-dialkyl-p-phenylenediamines include N, N-dimethyl-p-phenylenediamine, of the formula N, N-diethyl-p-phenylenediamine, of the formula N, N-diethyl-p-phenylenediamine hydrochloride of the formula N, N-diethyl-p-phenylenediamine hemisulfate formula the sulfur dioxide complex of N, N-diethyl-p-phenylenediamine. of the formula N, N-diethyl-toluene-2,5-diamine hydrochloride of the formula 2- (p-amino-N-ethylanilino) ethanol sulfate of the formula N-ethyl-N- (β-methanesulfonamidoethyl) -4-aminoaniline of the formula N- (2- (4-amino-N-ethyl-m-toluidino) ethyl) -methanesulfonamide sesquisulfate hydrate of the formula 2- ((4-amino-m-tolyl) ethylamino) ethanol sulfate of the formula the sesquisulfate of the 4- (N-ethyl-N-2-methanesulfonylaminoethyl) -2-methylphenylene diamine of the formula and similar. The latter is particularly preferred because, as a function of pH, it can exist in cationic and zerotonic forms and both forms can react with an ionized dye coupler, in addition to different speeds. Also suitable are hydroquinones, of the formula wherein the benzene ring may be substituted, and where 2 or more substituents may be joined to form additional rings, such as hydroquinone, of the formula chlorohydroquinone of the formula the bromohydroquinone of the formula the toluhydroquinone. of the formula methoxyhydroquinone of the formula and similar, the catechol of the formula and its derivatives, such as the pyrogallol of the formula 4-phenyl catechol of the formula the gallic acid of the formula methyl gallate, of the formula the galacetophenone of the formula the methyl ester of the formula gentisic acid. of the formula daphnetin. of the formula ,8-methane-5,6,7,8-tetrahydro-1,4-dihydroxynaphthalene of the formula and similar. Also suitable are the p-aminophenols of the general formula where Ri and R2 are each, independently of the other, hydrogen atoms, alkyl groups, preferably with about 1 to about 4 carbon atoms, substituted alkyl groups, wherein the benzene ring may be substituted, and where two may be attached or more substituents to form additional rings, such as p-aminophenol, of the formula o-aminophenol. of the formula the 2-methyl-p-aminophenol of the formula 2-hydroxymethyl-p-aminophenol of the formula l-amino-2-naphthol-6-sulfonic acid (Eikonogen), of the formula l-amino-2-naphthol-3,6-disulfonic acid (Diogen) of the formula 4-aminophenol hydrochloride of the formula the N-methyl-p-aminophenol (Metol) of the formula 2,4-diaminophenol (Amidol) of the formula 2,4-diaminophenol dihydrochloride of the formula 2, 3, -triaminophenol of the formula Triamol of the formula N- (4-hydroxyphenyl) glycine (Glycin) of the formula 4- (hydroxyethylamino) -3-methyl-l-hydroxybenzene of the formula 4- (di (hydroxyethyl) amino) -1-hydroxybenzene of the formula N- (2 '-hydroxy-5'-aminobenzyl) -3-hydroxyaniline hydrochloride of the formula 4-amino-2-benzylaminophenol of the formula 2-amino-4- (p-hydroxybenzylamino) -phenol of the formula m-methyl-p-hydrox: .- N-phenylmorpholine of the formula 1- (4-hydroxyphenyl) -pyrrolidine of the formula the p-hydrodiphenylamine (Duratol) of the formula p-aminosalicylic acid (Neol) of the formula 2-methyl-4-aminophenol hydrochloride (Monomet) of the formula the N- (hydroxyethyl) -o-aminophenol (Atomal) of the formula the hemisulfate of the 3- (hydroxymethyl) -4-hydroxyaniline (Edinol) of the formula and the like; The Difenal of the formula and similar. Mixtures of two or more developers can also be used. Commercially available examples of suitable developers include CD-2 [diethylamino-o-toluidine hydrochloride, CAS # 2051-79-8], CD-3 [4- (N-ethyl-N-2-methanesulfonylaminoethyl sesquisulfate)] -2-methylphenylene diamine, CAS # 25646-71-3], and CD-4 [2- [(4-amiho-m-tolyl) ethylamino] ethanol sulfate, CAS # 25646-77-9], all available from Estman Kodak, Co., Rochester, NY, and the like. Additional information regarding color developers is described in, for example, SPSE Handbook of Photographic. Science and Engineering, W. Thomas, Jr., ed., John Wiley & Sons (New York 1973); Neblette r Handbook of Photography and Reprography, ed. , J. Sturge, ed., Van Nostrand Reinhold Co. (New York 1977); Modern Photographic Processing, G. Haist, John Wiley & Sons (New York 1979); US Patent 477,486, US Patent 1,799,568, US Patent 1,712,716, US Patent 1,758,892, US Patent 1,758,762, US Patent 2,610,122, US Patent 2,385,763, US Patent 3,622,629, US Patent 3,762,922, US Patent 1,937,844, US Patent 3,265,499, US Patent 3,134,673, US Patent 3,091,530, US Patent 2,193,015, US Patent 2,688,549, US Patent 2,688,548, US Patent 2,691,589, US Patent 3,672,896, US Patent 2,289,367, US Patent 3,241,967, US Patent 3,330,839, US Patent 2,685,516, US Patent 2,852,374, US Patent 3,672,891, US Patent 1,939,231, US Pat. U.S. Patent 2,181,944, U.S. Patent 3,459,549, U.S. Patent 1,390,260, U.S. Patent 1,663,959, U.S. Patent ID No. 2,587,276, US Patent 2,857,275, US Patent 2 ^, 857,274, US Patent 3,293,034, US Patent 3,287,125, US Patent 3,287,124, US Patent 3,455,916, US Patent 2,843,481, US Patent 3,723,117, US Patent 2,596,978, US Patent 1,082,622, US Patent 2,220,929, U.S. Patent 2,419,975, U.S. Patent 2,685,514, U.S. Patent 3,782,949, U.S. Patent 853,643, U.S. Patent 2,943,109, and U.S. Patent 2,397,676; British Patent 1,191,535, British Patent 295,939, British Patent 1,210,417, British Patent 1,273,081, British Patent 1,003,783, British Patent 928,671, British Patent 989,383, British Patent 430,264, British Patent 767,700, British Patent 783,727, British Patent 542,502 British Patent 650,911, British Patent 679,677 , British Patent 728,368, British Patent 757,271, British Patent 997,033, British Patent 761,301, British Patent 954,106, British Patent 679,678, British Patent 757,840, British Patent 459,665, Patent British 479,466, British Patent 1,122,085, Patent British 1,327,033, British Patent 1,191,535, Patent British 1,327,034, British Patent 1,327,035, Patent British 1,154,385, British Patent 943,928, British Patent 466,625, and British Patent 466,626; Patent French 1,480,920, French Patent 1,380,163, and Patent French 325,385; German Patent 945,606, German Patent 955,025, German Patent 158,741, German Patent 875,048, German Patent 870,418, German Patent 945,606, German Patent 1,151,175, German Patent 1,047,618, German Patent 1,079,455, German Patent 34,342, German Patent 36,746, and German Patent 97,596; Canadian Patent 931,009; the descriptions of each of which are fully incorporated here as a reference. In the processes of developing with silver halide, the developer is usually oxidized by the interaction with the silver halide in the film. For the present invention, the developer is reacted with an oxidant or oxidizing agent. The developer, after oxidation, is converted to a form capable of reacting with a dye coupler to form a dye. For example, a developer of the N, N-dialkyl-p-phenylenediamine class, after oxidation, is converted to the chimeric diimine, as follows: where X is an anion derived from the oxidant. The oxidizing composition generally comprises a liquid carrier and an oxidizing agent, and functions as a color-forming component in the process of the present invention. For the purpose of simplification, the revealing composition will sometimes be referred to hereinafter as an ink. Any liquid can be used as the main component of the liquid vehicle, provided that it dissolves or disperses the components of the composition and if it is of an appropriate viscosity for the selected droplet ejector. For example, in thermal inkjet printing systems, a preferred liquid carrier is water. In other droplet ejectors, such as those employing continuous flow processes, piezoelectric ink jet printers, acoustic inkjet printers and the like, other liquids, such as hydrocarbons, glycols, ethers, sulfones, may also be employed. such as sulfolane, pyrrolidinones such as 2-pyrrolidinone and N-methyl pyrrolidinone, other dipolar aprotic solvents, and the like, as well as mixtures thereof. The oxidizing composition may also contain other components which may improve its performance as an inkjet ink, such as wetting agents, penetrants, co-solvents, blasting aids or the like, set forth in greater detail hereinafter. The oxidizing composition typically contains the oxidizing agent an amount of from about 0.05 to about 15 weight percent of the oxidizing composition, preferably from about 0.1 to about 10 weight percent of the oxidizing composition, and more preferably from about 0.5 to about 5 weight percent of the oxidizing composition, although the amount may be outside those ranges. The reaction between the oxidizing agent and the color developer is stoichiometric, and to obtain a full-color intensity, a stoichiometric amount or an excess amount of oxidizing agent is used to oxidize all of the developer. In one embodiment of the present invention, the tone or intensity of the color is controlled by the deposition of stoichiometrically insufficient, variable amounts of the oxidizing agent. Examples of suitable oxidizing agents include potassium peroxydisulfate, ammonium peroxydisulfate, hydrogen peroxide, alkylhydroperoxides of the general formula where Ri, R2 and R3 are each, independently of the others, alkyl groups, preferably with one or two carbon atoms, although the number of carbon atoms may be outside this range, or alkylaryl groups, preferably with from 7 to about 9 carbon atoms, although the number of carbon atoms may be outside this range, such as t-butyl hydroperoxide, cumene hydroperoxide and the like, • dialkyl peroxides of the general formula where Ri, R2, R3, R4, R5 and R6 are each, independently of the others, alkyl groups, preferably with one or two carbon atoms, although the number of carbon atoms may be outside this range, or alkylaryl groups, preferably with 7 to about 9 carbon atoms, although the number of carbon atoms may be outside this range, such as di-t-butyl peroxide, dicumyl peroxide, and the like, where the peroxide class of dialkyl also includes substituted dialkyl peroxides, such as the t-butylperoxybenzoate of the formula the t-butylperoxy isopropyl carbonate of the formula CK CK K 3C-CI -. O-O-C-O-CI -CK3 CK H and the like, diacylperoxides of the general formula O or II II R; -c - o- o- C-R " where Ri and R2 are each, independently of the others, alkyl groups, preferably with 1 or 2 carbon atoms, aryl groups, preferably with 6 to about 9 carbon atoms, or alkylaryl groups, preferably with 7 to about 9 carbon atoms, such as benzoyl peroxide, pivaloyl peroxide, and the like, peroxycarbonates, such as sodium percarbonate and the like, as well as mixtures thereof. Peroxides such as the above are available from, for example, Aldrich Chemical Co., Milwaukee, Wl, and Alfa Aesar, division of Johnson Matthey Catalog Co., Inc., Ward Hill, Ma. As noted, the developer in its form The oxidation can react a coupler in the dye to form a dye. The colorant composition generally comprises a liquid carrier and a dye coupler, and functions as a color-forming component in the process of the present invention. For the purpose of simplification, the revealing composition will here sometimes be referred to as an ink. Any liquid can be used as the main component of the liquid vehicle, provided that it dissolves or disperses the components of the composition and is of an appropriate viscosity for the selected droplet ejector. For example, in thermal ink jet printing systems, a preferred liquid carrier is water. In other droplet ejectors, such as those employing continuous flow processes, piezoelectric ink jet printers, acoustic ink jet printers, and the like, other liquids, such as hydrocarbons, glycols, ethers, sulfones, may also be employed. , such as sulfolane, pyrrolidinones such as 2-pyrrolidinone and N-methyl pyrrolidinone, other dipolar aprotic solvents, and the like, as well as mixtures thereof. The coloring composition may also contain other components which may improve its performance as an inkjet ink, such as wetting agents, penetrants, co-solvents, blasting aids or the like, set forth in greater detail hereinafter. The dye composition typically contains the dye coupler in an amount of about 0.05 to about 15 weight percent of the dye composition, preferably about 0.1 to about 10 weight percent of the dye composition, and more preferably it is from about 0.5 to about 5 weight percent of the coloring composition, although the amount may be outside those ranges. The reaction between the dye coupler and the color developer is stoichiometric, to obtain a full-color intensity, which employs a totally stoichiometric amount or an excess amount of oxidizing agent to oxidize all of the developer. In one embodiment of the present invention, the tone or intensity of the color is controlled by the deposition of stoichiometrically insufficient, variable quantities of the dye coupler. Examples of suitable cyan dye couplers include phenols and substituted a-naphthols, including those of the general formulas and the like, wherein X is a hydrogen atom, a chlorine atom, an alboxi group (-OR), an aryloxy group (-OAr), or a thioaryl group (-SAr), n is an integer representing the number of repeating -CH2- units, and is preferably from about 1 to about 3, R and R 'are each, independently of the other, organic segments which provide the desired solubility characteristics, such as alkyl groups, preferably with 1 to about 22 carbon atoms, or polar solubilizing groups, such as -COOH or -S03H, and Ar is an aryl group, including substituted aryl groups, preferably with 6 to about 14 carbon atoms, or a group arylalkyl, including substituted arylalkyl groups, preferably with 7 to about 36 carbon atoms. Amphiphilic cyan couplers, such as l-N-stearoyl-3-N- (1 '-hydroxy-2'-naphthoyl) -phenylenediamine-4-sulfonic acid, which is believed to be of the formula or a salt thereof, such as a sodium salt, are particularly preferred for water-based ink formulations such as those suitable for thermal inkjet printing.

Examples of suitable yellow dye couplers include ß-ketocarboxamides and pivaloylacetanilides, of the general formulas and wherein X is a hydrogen atom, a chlorine atom, a group -OS02R, a group -S02R, a group -0-C (= 0) R, or a group -SAr, where R is an alkyl group, preferably from 1 to about 22 carbon atoms, and Ar is an aryl group, preferably with 6 to about 22 carbon atoms, Y, Z, and the "equilibrator" are each, independently of the other, solubilizing groups , such as an alkyl group (-R), a carboxyl group, a sulfonyl group, by an alkylamide group (-NH-COR), wherein R is an alkyl group, preferably with 1 to about 22 carbon atoms. The Y and Z substituents can be used to bind the balancing or solubilizing groups and to alter the reactivity of the coupler and the hue of the resulting dyes. Coupling to the oxidized developer generally occurs with displacement of the X substituent. Specific examples of suitable yellow dye couplers include the 4- (p-toluenesulfoniland.no) -? - benzoylacetanilide, of the formula a-benzoyl-o-methoxyacetanilide, of the formula dichloroacetanilide, of the formula and similar. Yellow amphiphilic couplers, such as para-stearoylamino-benzoyl-acetanilide-3 ', 5'-dicarboxylic acid, which is believed to be of the formula or the ethano-stearoylamino-benzoyl-acetanilido-para-carboxylic acid, which is believe is of the formula or salts thereof, such as sodium salts, are particularly preferred for water-based ink formulations such as those suitable for thermal inkjet printing. Examples of suitable magenta dye couplers include those derived from l-aryl-2-pyrazolin-5-ones, of the general formulas where X is OR II -O- C- R, H O I II N-S-R II or -MR -HE -N = N-Ar, R, R ', and R "are each, independently of the others, organic segments which provide the desired solubility characteristics, such as alkyl groups, preferably with 1 to about 22 carbon atoms. carbon, or polar solubilizing groups, such as -COOH or -S03H, and Ar is an aryl group, including substituted aryl groups, preferably with 6 to about 14 carbon atoms, or an arylalkyl group, including substituted arylalkyl groups, preferably with 7 to about 36 carbon atoms, the pyrazolo- (3, 2-c) -5-triazoles and related isomers, of the general formula where X is a chlorine atom, a thioalkyl group (-SR), a thioaryl group (-SAr), or an aryloxy group (-OAr), n is an integer representing the number of -CH 2 -repeated units, and preferably it is from 0 to about 3, and R is an alkyl group, preferably with 1 to about 22 carbon atoms, Ar is a aryl group, preferably with 6 to about 22 carbon atoms, and the "balancer" represents a solubilizing group, such as an aryl group (-R), a carboxyl group, a sulfonyl group, an alkylamide group (-NH-) COR), wherein R is an alkyl group preferably with 1 to about 22 carbon atoms and the like. Also suitable are cyanoacetyl derivatives of cyclic systems, such as cyanoacetylchumane, of the formula indazolones, of the general formula where A is a hydrogen atom or a selected substituent to optimize characteristics such as solubility, reactivity, hue, stability or the like. For example, substituents such as sulfonate (-S03) or carboxylate (-COOH) can increase water solubility and suitability for use in aqueous liquids. Specific examples of magenta dye couplers include 2- cyanoacetyl coumaron, of the general formula 1- (2,4,6-trichlorophenyl) -3-p-nitroanilino-2-pyrazolin-5-one of the formula and similar. Magenta amphiphilic couplers, such as 3-heptadecyl-l- (4'-sulfophenyl) -2-pyrazolin-5-one, which is believed to be of the formula where X is a hydrogen atom or a chlorine atom, or 1- (5 '-sulfo-3'-stearoyl-aminophenyl) -2-pyrazolin-5-one, which is believed to have the formula or salts thereof, such as sodium salts, are particularly preferred for water-based ink formulations such as those suitable for use in thermal inkjet printing. Additional information regarding dye couplers is described in, for example, SPSE Handbook of Photographic Science and Engineering, W. Thomas, Jr., ed., John Wiley & Sons (New York 1973); Neblette's Handbook of Photography and Reprography, ed., J. Sturge, ed., Van Nostrand Reinhold Co. (New York 1977); and "The Chemistry of Color Photography" W. C. Guida et al., Journal of Chemical Education, Vol. 52, No. 10, p. 622 (October 1975); the descriptions of each of which are fully incorporated here as a reference. At least one of the developer composition, the coloring composition and the oxidizing composition is of a sufficiently alkaline pH to direct the coupling reaction between the oxidized developer and the dye coupler. Accordingly, at least one of those compositions typically also includes a base and / or a buffer. Although it is generally simpler to include the base and / or buffer in the oxidizing composition, the developer composition and / or coloring composition may also have their pH adjusted to an appropriate level to allow the coupling reaction. The compositions containing a base and / or a buffer, and having their pH adjusted to allow the coupling reaction, will hereinafter be referred to as the pH-adjusted composition. The pH of the adjusted pH composition is generally about 9, and preferably is about 10 to about 13, although the value may be outside this range. Examples of compositions that can be added to the pH-adjusted composition to obtain the desired pH include hydroxides such as sodium hydroxide, tetramethylammonium hydroxide, and the like, potassium carbonate, sodium phosphate or the like, as well as mixtures thereof. same. The setting composition generally comprises a liquid vehicle and a fixative. For the purpose of simplification, the fixing composition will sometimes be referred to hereinafter as an ink. Any liquid can be used as the main component of the liquid vehicle, provided that it dissolves or disperses the components of the composition and is of an appropriate viscosity for the selected droplet ejector. For example, thermal ink jet printing systems, a preferred liquid vehicle is water. In other droplet ejectors, such as those employing continuous flow processes, piezoelectric inkjet printers, acoustic inkjet printers and the like, other liquids, such as hydrocarbons, glycols, ethers, sulfones, and the like may also be employed. sulfolane, pyrrolidinones such as 2-pyrrolidinone and N-methyl pyrrolidinone, other dipolar aprotic solvents, and the like, as well as mixtures thereof. The fixing composition may also contain other components that can improve its performance as an inkjet ink, such as humectants, penetrants, cosolvents, blasting aids or the like, as discussed in greater detail hereinafter. Typically, the fixative is a mixture of a weakly acid reagent and a reducing agent. The acid is present in the fixing composition in an amount sufficient to neutralize the base of the developer composition, the coloring composition and / or the oxidizing composition in the initially formed image. The reducing agent is present in the fixing composition in an amount sufficient to repress the excess oxidizing components in the initially formed image. The setting composition typically contains the fixing mixture in an amount of about 0.1 to 10 percent by weight of the fixing composition, preferably about 1 to about 5 percent by weight of the setting composition, although the amount may be outside. of those intervals. Examples of suitable weakly acidic binding components include ascorbic acid, phthalic acid, benzoic acid, acetic acid, maleic acid, succinic acid, poly (acrylic acid), poly (methacrylic acid), copoly (styrene / maleic acid), copoly ( methylvinyl ether / maleic acid), and the like, as well as mixtures thereof. Examples of suitable reducing reducing components include ascorbic acid, sodium sulfite, sodium bisulfite, glucose and other reducing sugars, and the like, as well as mixtures thereof. As stated hereinabove, the developer composition, the oxidizing composition, the coloring composition and the setting composition (hereinafter collectively referred to as inks or ink compositions of the present invention) all have generally compositions which make them suitable for use. as ink jet inks in an ink jet printing apparatus. Inkjet inks generally contain an aqueous liquid vehicle. The liquid carrier may consist solely of water, or may comprise a mixture of water and a water-soluble or water-miscible organic component, such as ethylene glycol, propylene glycol, diethylene glycols, glycerin, dipropylene glycols, polyethylene glycols, polypropylene glycols. , amides, ethers, urea, substituted ureas, ethers, carboxylic acids and their salts, esters, alcohols, organosulfides, organosulphoxides, sulfones (such as sulfolane), alcohol derivatives, carbitol, butyl carbitol, cellusolve, tripropylene glycol monomethyl ether, ether derivatives, amino alcohols, ketones, N-methylpyrrolidinone, 2-pyrrolidinone, cyclohexylpyrrolidinone, hydroxyethers, amides, sulfoxides, lactones, polyelectrolytes, methyl sulfonylethanol, imidazole, betaine, and other water-soluble or water-miscible materials, as well as mixtures thereof. When mixtures of water and water soluble or miscible organic liquids are selected as the liquid carrier, the ratio of water to organic compound typically ranges from about 100: 0 to about 30:70, and preferably from about 97: 3 to about 40:60. The non-aqueous component of the liquid vehicle generally serves as a humectant or cosolvent which has a boiling point greater than that of water (100 ° C). In the ink compositions of the present invention, the liquid carrier is typically present in an amount of about 80 to about 99.9 weight percent of the ink, preferably about 90 to about 99 weight percent of the ink, although the amount may be outside those ranges. Other additives optional to the inks of the present invention include pH controlling agents such as acids? or bases, phosphate salts, carboxylate salts, sulfite salts, amide salts and the like, present in an amount of from about 0 to about 1 weight percent of the ink and preferably from about 0.01 to about 1 weight percent by weight of the ink, or similar. One or more surfactants or wetting agents may also be added to the ink. These additives may be of the cationic, anionic or non-ionic types. Suitable surfactants and wetting agents include sodium lauryl sulfate, Tamol® SN, Tamol® LG, those of the Triton® series available from Rohm and Haas Company, those from the Marasperse® series, those from the Igepal® series available from the GAF Company, those from the Tergitol® series, and other commercially available surfactants. These surfactants and wetting agents are present in any desired or effective amounts, generally from about 0 to about 15 weight percent of the ink, and preferably from about 0.1 to about 8 weight percent of the ink, although the amount It may be outside this range. An example of an additive for the inks of the present invention is a polymeric additive consisting of two polyalkylene oxide chains attached to a bisphenol portion of the central type A. This additive is of the formula where R1 and R2 are independently selected from the group consisting of hydrogen, alkyl groups with 1 to about 8 carbon atoms, such as methyl, ethyl, propyl, and the like, and alkoxy groups with 1 to about 8 carbon atoms, such as methoxy, ethoxy, butyloxy and the like, R3 and R4 are independently selected from the group consisting of alkyl groups with 1 to about 4 carbon atoms, and yy are each independently a number from about 100 to about 400, and preferably In general, the molecular weight of the polyalkylene oxide polymer is from about 14,000 to about 22,000, and preferably from about 15,000 to about 20,000, although the molecular weight may be outside this range. The materials of this formula are commercially available; for example, of Carbowax M20, a polyethylene oxide / bisphenol A polymer of the above formula with a molecular weight of. about 18,000, available from Union Carbide Corporation, Danbury, CT, is a polymeric additive suitable for the inks of the present invention. In addition, the compounds of the above formula can be prepared by the methods described in Polyethers, N. G. Gaylord, John Wiley & Sons, New York (1963) and "Laboratory Synthesis of Polyethylene Glycol Derivatives", J. M. Harris, < J. Molecular Science - Rev. Macromol. Chem. ^ Phys. , C25 (3). 325-373 (1985), the descriptions of each of which are fully incorporated herein by reference. The polyalkylene oxide additive is generally present in the ink in an amount of at least about 1 part per million by weight of the ink. Typically, the polyalkylene oxide additive is present in amounts of up to 1 weight percent of the ink, and preferably in amounts up to 0.5 weight percent of the ink; Larger amounts of the additive may increase the viscosity of the ink beyond the desired level, but larger quantities may be used in applications where the increased viscosity of the ink is not a problem. Inks containing such additives are described in U.S. Patent 5,207,825, the disclosure of which is hereby incorporated by reference in its entirety. The ink compositions of the present invention are generally of a viscosity suitable for use in thermal inkjet printing processes. At room temperature (i.e., about 25 ° C), typically, the viscosity of the ink is not greater than about 10 centipoise, and is preferably from about 1 to about 5 centipoise, more preferably from about 1 to about 4 centipoise, although the viscosity may be outside this range, particularly for applications such as acoustic inkjet printing. The ink compositions of the present invention may be of any suitable or desired pH. At least one of the developer composition, the colorant composition and the copolymerizable oxidant is sufficiently alkaline to promote the coupling reaction between the color developer and the dye coupler. Ink compositions suitable for ink jet printing can be prepared by any suitable process. Typically, the inks are prepared by simply mixing the ingredients. One process involves mixing all the ingredients of the ink together and filtering the mixture to obtain an ink. The inks can be prepared by mixing the ingredients, heating if desired, and filtering, after adding any additional additives desired to the mixture and mixing at room temperature with moderate agitation until a homogeneous mixture is obtained, typically from about 5 to about 10. minutes Alternatively, the optional additives of the ink can be mixed with the other ingredients of the ink during the process of preparing the ink, which takes place according to any desired process, such as by mixing all the ingredients, heating if desired and filtration. In a specific embodiment of the present invention, the ink jet recording apparatus employs a thermal ink jet process, where the ink in the nozzles is selectively heated in an image forming pattern, thereby causing the drops of the ink are ejected or ejected in a pattern of imaging. In another specific embodiment, the printing apparatus employs an acoustic ink jet process, where the ink droplets are forced to be ejected in a pattern of acoustic beam imaging. Other methods may be employed, such as piezoelectric on demand drip inkjet printing, continuous flow inkjet printing, hot melt ink jet printing, or the like. Any suitable substrate or record sheet can be used, including flat papers, such as Xerox 4024 papers, Xerox Image Series papers, Courtland 4024 DP paper, regulated note pad paper, bond paper, silica coated papers, such as Sharp Company-coated paper, JuJo paper and the like, materials for transparencies, fabrics, textiles, plastics, polymeric films, inorganic substrates, such as metals and wood, and the like. In a preferred embodiment, the process involves printing on a porous or absorbent ink substrate, such as a flat paper. In the embodiments of the present invention, where special receiving sheets or substrates are used, it may be advantageous to use a paper coated with absorbent layers of specific dye couplers. As described in, for example, Japanese Patent Publication JP 9030107 A, when the coloring agents are located at a specific depth in the receiving sheet, improved color reproduction can be achieved because agents of different color tone do not they enter the same depth in the absorbent layer. In the specific embodiments of the present invention, which allow the production of gray level images, have hereinabove been illustrated in the specific context of photographic materials, including color photographic materials and the development processes. Those embodiments of the present invention, namely (1) provide a multiplicity of intensity or "gray" levels within a particular color by controlling the time between the point at which the developing composition, the oxidizing composition and the coloring composition are all together at the point at which the fixing composition is deposited; (2) provide a multiplicity of level intensities or "gray" within a particular color, dripping fixed amounts of one of (a) the developer composition, (b) the dye composition, or (c) the oxidizing composition on the substrate in combination with varying amounts of the other two compositions, with the limited composition being present in amounts that limit the reaction with respect to the other two compositions; and (3) dripping the developer composition, the coloring composition and the oxidizing composition in an image-forming pattern, so that the superposition of the droplets of those compositions is controlled, thereby modulating the size of the pixel to produce sizes of Variable stain, can also be made by a multiplicity of other specific chemistries. In some of these modalities, no fixative is necessary; in other embodiments, only two liquid color forming compositions are used instead of three. One embodiment of the present invention is directed to a process which comprises (a) incorporating an ink jet recording apparatus (1) a color forming composition comprising a liquid carrier and at least one color forming agent; and (2) a reactive composition comprising a vehicle and at least one material capable of reacting with the color forming agent to cause the desired color to be formed; (b) causing droplets of the color forming composition to be ejected or ejected in a pattern of imaging on the substrate; and (c) causing the drops of the reactive composition to be ejected in a pattern of imaging on the substrate; where the process results in at least some portions of the substrate containing images comprising both of the color-forming composition and the reactive composition, such portions form a printed image, where at time Ti, the color-forming composition has formed an image on the substrate, at time T2, the reactive composition is deposited on a first portion Pi of the image, and at time "T3, the reactive composition is deposited on a second portion P2 of the image, where the period of time Ti to T2 is less than the period of time Ti to T3, thereby resulting in a second portion P2 having a color intensity different from that of the first portion P_. Another embodiment of the present invention is directed to a process, the which comprises (a) incorporating in an ink jet recording apparatus (1) a color forming composition comprising a liquid carrier and at least one color forming agent; Reactive composition comprising a liquid carrier and at least one material capable of reacting with the color forming agent to cause the desired color to be formed; (b) causing droplets of the color forming composition to be ejected in a pattern of imaging on the substrate; and (c) causing the drops of the reactive composition to be ejected in a pattern of imaging on the substrate; where the process results in at least some portions of the substrate containing images comprising the color-forming composition and the reactive composition, such portions form a printed image, wherein one of (i) the color-forming composition and (ii) the Reactive composition, are applied to the substrate in fixed volumes per pixel, and the other of (i) and (ii) is applied to the substrate in variable volumes per pixel, thereby varying the intensity of the color of the printed image. Yet another embodiment of the present invention is directed to a process which comprises (a) incorporating in an ink jet recording apparatus (1) a color forming composition comprising a liquid carrier and at least one color forming agent; and (2) a reactive composition comprising a liquid carrier and at least one material capable of reacting with the color forming agent to cause the desired color to be formed; (b) causing droplets of the color forming composition to be ejected in a pattern of imaging on the substrate; and (c) causing the drops of the reactive composition to be ejected in a pattern of imaging on the substrate; where the process results in at least some portions of the substrate containing images comprising both of the color-forming composition and the reactive composition, such portions form a printed image, wherein the drops of the color-forming composition and the drops of the The reactive composition is applied to the substrate in an image-forming pattern, so that the droplets of the color-forming composition and the reactive composition are superimposed in a controlled pattern, thereby forming stags of varying sizes on the substrate, such stains. they form in areas where the droplets of the color-forming composition and the reactive composition overlap. For example, the present invention includes embodiments wherein more than one color forming agent is combined into a single "ink" or liquid composition for printing. For example, the color developer and the dye coupler can be included in a single "ink" or liquid composition, thereby eliminating the need for a separate developer composition and the need for a separate printhead or cartridge to print the revealing composition. In this embodiment, the use of quinone color developers may be preferred over the diamine color developers, in view of the greater reactivity (and potential instability in this embodiment) of the diamines.

In addition, dye developer molecules, commonly used in instant photography, can be used in place of different color developer and dye coupler molecules. In this embodiment, the color developer and the dye coupler are covalently linked in a single molecule. Otherwise, the process is analogous to that described here above with respect to the materials commonly used in conventional photography. Additional information on dye developer molecules and processes for the use thereof are described in, for example, "Color Photography, Instant", by Vivian K. Walworth and Stanley H. Mervis in The Encyclopedia of Chemical Technology, 4a Edition, Vol. 6, pp. 1003-1048, John Wiley & Sons, New York (1993); U.S. Patent No. 3,443,940; U.S. Patent No. 2,983,606; U.S. Patent No. 3,255,001; U.S. Patent No. 3,201,384; U.S. Patent No. 3,246,985; U.S. Patent No. 3,857,855; U.S. Patent No. 4,264,701; M. Idelson, I. R. Karday, B. H. Mark, D. O. Richter, and V. H. Hooper, Inorg. Chem. 6, 450 (1967); E. M. Idelson, Dyes and Pigments 3, 191 (1982); and H.

G. Rogers, E. M. Idelson, R. F. W. Cieciuh, and S. M. Bloom, J. Photogr. Sci. 22, 138 (1974); the descriptions of each of which are fully incorporated here as a reference.

In addition, leuco or vat dye may be used, which are typically colorless at least and until they react with an oxidizing agent or a pH-altering agent, in combination with oxidizing reagents or reagents that alter the pH to visualize them. In this mode, no fixative is necessary. In other circumstances, the process is analogous to that described here above with reference to the materials commonly used in conventional photography. Additional information on leuco and vat dyes and processes for their use is described in, for example, IBM Technical Disclosure Bulletin, Vol. 23, No. 4, p. 1387 (September 1980); U.S. Patent No. 1,055,115; British Patent 15055/12; and German Patent 257,167, the descriptions of each of which are fully incorporated herein by reference. Additionally, metal vanadates and polyphenolic compounds, such as gallic acid, tangentic acid, dihydroxybenzene carboxylic acids or dihydroxynaphthalene carboxylic acids can be used to create durable black images. In other circumstances, the process is analogous to that described here above with respect to the materials commonly used in conventional photography. Additional information on metal and polyphenylate vanadates and processes for using same, is described in, for example, Japanese Patent Publication JP 77049366 B, British Patent Publication GB 1398334, and German Patent Publication DE 2505077, the descriptions of each of which are fully incorporated here as a reference. Now, the specific embodiments of the invention will be described in detail. It is intended that those examples be illustrative, and the invention is not limited to the materials, conditions or process parameters set forth in that form. All parts and percentages are by weight, unless otherwise indicated.

EXAMPLE I A developer composition was prepared by mixing 5 parts by weight of CD-3 regulator (4- (N-ethyl-N-2-methanesulfonylaminoethyl) -2-methyl-phenylenediamine sesquisulfate monohydrate, obtained from Eastman Kodak Co., , Rochester, NY), 70 parts by weight of deionized water, 11 parts by weight of tripropylene glycol of monomethyl ether (DOWANOL TPM, obtained from Dow Chemical Co.), 10 parts by weight of dipropylene glycol, 0.05 parts by weight of oxide of polyethylene (adduct of poly (ethylene glycol) -bisphenol A diglycidyl ether, with a molecular weight of 18,500, obtained from the Polysciences), and 3 parts by weight of potassium carbonate.

An oxidizing composition was prepared by mixing 74 parts by weight of deionized water, 11 parts by weight of tripropylene glycol monomethyl ether (DOWANOL® TPM, obtained from Dow Chemical, Co.), 10 parts by weight of dipropylene glycol, 0.05 parts by weight of polyethylene oxide (adduct of poly (ethylene glycol) -bisphenol) A diglycidyl ether, with a molecular weight of 18,500, obtained from Polysciences), 3 parts by weight of potassium carbonate and 3 parts by weight of potassium peroxydisulfate (K2S2Os). A cyan color composition was prepared by mixing 74 parts by weight of deionized water, 11 parts by weight of tripropylene glycol monomethyl ether (DOWANOL® TPM, obtained from Dow Chemical, Co.), 10 parts by weight of dipropylene glycol, 0.05 parts by weight of polyethylene oxide (adduct of poly (ethylene glycol) -bisphenol A diglycidyl ether, with a molecular weight of 18,500, obtained from Polysciences), and 5 parts by weight of cyan dye coupler of α-naphthol (N- (2-acetamidophenethyl) -l-hydroxy- 2-naphthamide, obtained from Fisher Scientific (ACROS ORGANICS), Pittsburgh, PA). A magenta colored composition was produced by the same process except that the dye coupler used was 5 parts by weight of a magenta dye coupler of pyrazolinone (1- (2,4,6-trichlorophenyl) -3- (p- nitroanilino) -2-pyrazolin-5-one, obtained from Fisher Scientific (ACROS ORGANICS), Pittsburgh, PA). A yellow composition was produced by the same process except that the dye coupler used was 5 parts by weight of a β-ketocarboxamide yellow dye coupler (2-benzoylacetanilide, obtained from Fisher Scientific (ACROS ORGANICS), Pittsburgh, PA ). A fixative composition was prepared by mixing 70 parts by weight of deionized water, 11 parts by weight of tripropylene glycol monomethyl ether (DOWANOL® TPM, obtained from Dow Chemical, Co.), 10 parts by weight of dipropylene glycol, 0.05 parts by weight. of polyethylene oxide (adduct of poly (ethylene glycol) bisphenol A diglycidyl ether, with a molecular weight of 18,500, obtained from Polysciences), 5 parts by weight of poly (methyl vinyl ether / maleic acid) (GANTREZ MS-955 , obtained from GAF Corp., Wayne, NJ), and 4 parts by weight of sodium sulfite (Na2S03) A syringe in the order of microliters was then used to deposit controlled volumes of the developer composition on Xpressions® Color XEROX® paper. Then stoichiometric amounts of the oxidizing composition and the cyan color composition directly deposited onto spots containing the developer composition were deposited to produce intensely colored cyan stains.

The process was repeated with several volumes of oxidizing composition to give cyan-colored spots of varying intensity. The process was repeated so that the drops of developer composition, oxidizing composition and coloring composition did not overlap completely. Strongly colored cyan stains of fractional size (compared to those obtained with superposition of 100 percent droplets) were obtained only in those areas where the droplets of developer composition, oxidizing composition and coloring composition were superimposed. The reactions were inhibited by deposition of a stoichiometric excess of the fixing composition on the revealed spots. Other embodiments and modifications of the present invention may occur to those skilled in the art after reviewing the information presented herein; those embodiments and modifications, as well as the equivalents thereof, are also included within the scope of this invention.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (25)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property.

1. A process, characterized in that it comprises (a) incorporating into a printing apparatus by. ink jet (1) a developer composition comprising a liquid carrier and a color developer; (2) an oxidizing composition comprising a liquid vehicle and an oxidizing agent; (3) a coloring composition comprising a liquid vehicle and a dye coupler; and (4) a fixing composition comprising a liquid vehicle and a fixative; (b) causing the drops of the developer composition to be ejected or ejected in a pattern of imaging on the substrate; (c) causing droplets of the oxidizing composition to be ejected or ejected in a pattern of imaging on the substrate; (d) causing droplets of the dye composition to be ejected or ejected in a pattern of imaging on the substrate; and (e) causing droplets of the setting composition to be ejected or ejected in a pattern of imaging on the substrate; wherein the process results in at least some portions of the substrate containing images, comprising all four of the developer composition, the oxidizing composition, the coloring composition and the fixing composition, the portions forming a printed image.

The process according to claim 1, characterized in that the first, second and third coloring compositions are incorporated into the printing apparatus and caused to be ejected or ejected onto the substrate, wherein the first coloring composition comprises a liquid carrier and a cyan dye coupler, the second dye composition comprises a liquid vehicle and a magenta dye coupler, and the third dye composition comprises a liquid vehicle and a yellow dye coupler.

3. The process according to claim 1, characterized in that the printing apparatus employs a thermal ink jet process, wherein the ink in the nozzles is selectively heated in an image forming pattern, thereby causing the Drops of ink are ejected or ejected in an image-forming pattern.

The process according to claim 1, characterized in that the printing apparatus employs an acoustic ink jet process, wherein the droplets of the ink are forced to be ejected or ejected in a pattern of imaging by means of acoustic beams The process according to claim 1, characterized in that two of (i) the developer composition, (ii) the dye composition and (iii) the oxidizing composition are applied to the substrate in fixed volumes per pixel, and the remaining composition of (i), (ii) and

(iii) it is applied to the substrate in a variable volume per pixel, thereby varying the intensity of the color of the printed image.

The process according to claim 5, characterized in that the remaining composition is applied to the substrate through a printhead having a plurality of ink channels, where the drops of the remaining composition of at least two different volumes are they form by dripping the remaining composition from the ink channels.

7. The process according to claim 5, characterized in that the number of drops of the remaining composition applied per pixel is variable.

8. The process according to claim 5, characterized in that the remaining composition is the oxidizing composition.

9. The process according to claim 1, characterized in that the drops of the developer composition, the drops of the dye composition and the drops of the oxidizing composition are applied to the substrate in a pattern of imaging, so that the drops of the developer composition, the coloring composition and the oxidizing composition, they overlap in a controlled pattern, thus forming patches of varying sizes on the substrate, such spots are formed in areas where the droplets of the developer composition, the coloring composition and the oxidizing composition overlap.

10. The process according to claim 1, characterized in that the time Ti, the developer composition, the oxidizing composition and the dye composition have been superimposed on the substrate to react and form an image, at time T2, the fixing composition is deposited on a first portion Pi of the image, and at time T3, the fixing composition is deposited on a second portion P2 of the image, where the period of time xa to T2 is smaller than the period of time Ti to T3, resulting in therefore, a second portion P2 having a color intensity different from that of the first portion Pi.

A process, characterized in that it comprises (a) incorporating an ink jet recording apparatus (1) a color forming composition comprising a liquid carrier and at least one color forming agent; and (2) a reactive composition comprising a liquid carrier and at least one material capable of reacting with the color forming agent to cause the desired color to be formed; (b) causing droplets of the color forming composition to be ejected or ejected in a pattern of imaging on the substrate; and (c) causing the drops of the reactive composition to be ejected or ejected in a pattern of imaging on the substrate; where the process results in at least some portions of the substrate containing images comprising both of the color-forming composition and the reactive composition, such portions form a printed image, where at time Ti, the color-forming composition has formed an image on the substrate, at time T2, the reactive composition is deposited on a first portion Pi of the image, and at time T3, the reactive composition is deposited on a second portion P2 of the image, where the period of time Ti to T2 is less than the period of time Ti to T3, whereby a second portion P2 having a color intensity different from that of the first portion Px is obtained as a result.

12. The process according to claim 11, characterized in that the color-forming composition comprises a color developing molecule and the reactive composition comprises an oxidizing agent.

13. The process according to claim 11, characterized in that the color-forming composition comprises a leuco dye or vat dye and the reactive composition comprises an oxidizing agent or an agent that alters the pH.

The process according to claim 11, characterized in that the color forming composition comprises a metal vanadate and the reactive composition comprises a polyphenolic compound.

15. The process according to claim 11, characterized in that the color-forming composition comprises - a mixture of two of (i) a developer composition, (ii) a dye composition and (iii) an oxidizing composition, and the reactive composition it comprises the remaining composition of (i), (ii) and (iii).

16. A process, characterized in that it comprises (a) incorporating in an ink jet pressure apparatus (1) a color forming composition comprising a liquid carrier and at least? a color-forming agent; and (2) a reactive composition comprising a liquid carrier and at least one material capable of reacting with the color forming agent to cause the desired color to be formed; (b) causing droplets of the color forming composition to be ejected or ejected in a pattern of imaging on the substrate; and (c) causing the drops of the reactive composition to be ejected in a pattern of imaging on the substrate; where the process results in that at least some portions of the substrate contain images comprising both of the color-forming composition and the reactive composition, such portions form a printed image, wherein one of (i) the color-forming composition and (ii) ) the reactive composition, are applied to the substrate in fixed volumes per pixel, and the other of (i) and

(ii) it is applied to the substrate in variable volumes per pixel, thereby varying the intensity of the color of the printed image.

17. The process according to claim 16, characterized in that the color forming composition comprises a color developing molecule and the reactive composition comprises an oxidizing agent.

18. The process according to claim 16, characterized in that the color-forming composition comprises a leuco dye or vat dye and the reactive composition comprises an oxidizing agent or an agent that alters the pH.

19. The process according to claim 16, characterized in that the color forming composition comprises a metal vanadate and the reactive composition comprises a polyphenolic compound.

20. The process according to claim 16, characterized in that the color-forming composition comprises a mixture of two of (i) a developer composition, (ii) a dye composition and (iii) an oxidizing composition, and the reactive composition comprises the composition remaining of (i), (ii) and (iii).

21. A process, characterized in that it comprises (a) incorporating in an ink jet pressure apparatus (1) a color forming composition comprising a liquid carrier and at least one color forming agent; and (2) a reactive composition comprising a liquid carrier and at least one material capable of reacting with the color forming agent to cause the desired color to be formed; (b) causing droplets of the color forming composition to be ejected or ejected in a pattern of imaging on the substrate; and (c) causing the drops of the reactive composition to be ejected in a pattern of imaging on the substrate; where the process results in that at least some portions of the substrate contain images comprising both of the color-forming composition and the reactive composition, such portions form a printed image, wherein the drops of the color-forming composition and the drops of the The reactive composition is applied to the substrate in an image-forming pattern, so that the droplets of the color-forming composition and the reactive composition are superimposed on a controlled pattern., thus forming patches of varying sizes on the substrate, such spots are formed in areas where the droplets of the color forming composition and the reactive composition overlap.

22. The process according to claim 21, characterized in that the color forming composition comprises a color developer molecule and the reactive composition comprises an oxidizing agent.

23. The process according to claim 21, characterized in that the color-forming composition comprises a leuco dye or vat dye and the reactive composition comprises an oxidizing agent or an agent that alters the pH.

24. The process according to claim 21, characterized in that the color forming composition comprises a metal vanadate and the reactive composition comprises a polyphenolic compound.

25. The process according to claim 21, characterized in that the color-forming composition comprises a mixture of two of (i) a developer composition, (ii) a dye composition and (iii) an oxidizing composition, and the reactive composition comprises the remaining composition of (i), (ii) and (iii).

SUMMARY OF THE INVENTION

A process, characterized in that it comprises (a) incorporating in an ink jet recording apparatus (1) a developing composition comprising a liquid carrier and a color developer; (2) an oxidizing composition comprising a liquid vehicle and an oxidizing agent; (3) a coloring composition comprising a liquid vehicle and a dye coupler; and (4) a fixing composition comprising a liquid vehicle and a fixative; (b) causing the drops of the developer composition to be ejected or ejected in a pattern of imaging on the substrate; (c) causing droplets of the oxidizing composition to be ejected or ejected in a pattern of imaging on the substrate; (d) causing droplets of the dye composition to be ejected or ejected in a pattern of imaging on the substrate; and (e) causing droplets of the setting composition to be ejected or ejected in a pattern of imaging on the substrate; wherein the process results in at least some portions of the substrate containing images, comprising all four of the developer composition, the oxidizing composition, the coloring composition and the fixing composition, the portions forming a printed image. The specific embodiments of the present invention are directed to the realization of continuous shades and gray scales in images by (1) the control of the time at which the color-forming reactions are inhibited by controlling the period of time between the deposition of the color forming liquids and the deposition of the fixing liquid; (2) controlling the degree of color-forming reactions by limiting the amount of one of the color-forming liquids; or (3) controlling the pixel size by controlling the placement of the drop over the superimposed areas of droplets of color-forming liquids.