EP0772526A2 - Placement des buses dans les tetes monolithiques d'impression fonctionnant en goutte-a-la-demande - Google Patents
Placement des buses dans les tetes monolithiques d'impression fonctionnant en goutte-a-la-demandeInfo
- Publication number
- EP0772526A2 EP0772526A2 EP96911653A EP96911653A EP0772526A2 EP 0772526 A2 EP0772526 A2 EP 0772526A2 EP 96911653 A EP96911653 A EP 96911653A EP 96911653 A EP96911653 A EP 96911653A EP 0772526 A2 EP0772526 A2 EP 0772526A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- ink
- nozzles
- drop
- printing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/14—Structure thereof only for on-demand ink jet heads
- B41J2/14451—Structure of ink jet print heads discharging by lowering surface tension of meniscus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/14—Structure thereof only for on-demand ink jet heads
- B41J2/1433—Structure of nozzle plates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/145—Arrangement thereof
- B41J2/155—Arrangement thereof for line printing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/14—Structure thereof only for on-demand ink jet heads
- B41J2002/14475—Structure thereof only for on-demand ink jet heads characterised by nozzle shapes or number of orifices per chamber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2202/00—Embodiments of or processes related to ink-jet or thermal heads
- B41J2202/01—Embodiments of or processes related to ink-jet heads
- B41J2202/11—Embodiments of or processes related to ink-jet heads characterised by specific geometrical characteristics
Definitions
- the present invention is in the field of computer controlled printing devices.
- the field is nozzle configurations for thermally activated drop on demand (DOD) printing heads which integrate multiple nozzles on a single substrate.
- DOD drop on demand
- Inkjet printing has become recognized as a prominent contender in the digitally controlled, electronic printing arena because, e.g., of its non-impact, low-noise characteristics, its use of plain paper and its avoidance of toner transfers and fixing.
- ink jet printing mechanisms have been invented. These can be categorized as either continuous ink jet (CIJ) or drop on demand (DOD) ink jet.
- Continuous ink jet printing dates back to at least 1929: Hansell, US Pat. No. 1,941,001.
- Sweet et al US Pat. No. 3,373,437, 1967 discloses an array of continuous ink jet nozzles where ink drops to be printed are selectively charged and deflected towards the recording medium. This technique is known as binary deflection CU, and is used by several manufacturers, including Elmjet and Scitex. Hertz et al US Pat. No.
- 3,416,153, 1966 discloses a method of achieving variable optical density of printed spots in CU printing using the electrostatic dispersion of a charged drop stream to modulate the number of droplets which pass through a small aperture.
- This technique is used in ink jet printers manufactured by Iris Graphics.
- Kyser et al US Pat. No. 3,946,398, 1970 discloses a DOD ink jet printer which applies a high voltage to a piezoelectric crystal, causing the crystal to bend, applying pressure on an ink reservoir and jetting drops on demand.
- Many types of piezoelectric drop on demand printers have subsequently been invented, which utilize piezoelectric crystals in bend mode, push mode, shear mode, and squeeze mode.
- Piezoelectric DOD printers have achieved commercial success using hot melt inks (for example, Tektronix and Dataproducts printers), and at image resolutions up to 720 dpi for home and office printers (Seiko Epson). Piezoelectric DOD printers have an advantage in being able to use a wide range of inks. However, piezoelectric printing mechanisms usually require complex high voltage drive circuitry and bulky piezoelectric crystal arrays, which are disadvantageous in regard to manufacturability and performance.
- Endo et al GB Pat. No. 2,007,162, 1979 discloses an electrothermal DOD ink jet printer which applies a power pulse to an electrothermal transducer (heater) which is in thermal contact with ink in a nozzle.
- the heater rapidly heats water based ink to a high temperature, whereupon a small quantity of ink rapidly evaporates, forming a bubble.
- the formation of these bubbles results in a pressure wave which cause drops of ink to be ejected from small apertures along the edge of the heater substrate.
- BubblejetTM trademark of Canon K.K. of Japan
- Thermal Ink Jet printing typically requires approximately 20 ⁇ J over a period of approximately 2 ⁇ s to eject each drop.
- the 10 Watt active power consumption of each heater is disadvantageous in itself and also necessitates special inks, complicates the driver electronics and precipitates deterioration of heater elements.
- U.S. Patent No. 4,275,290 discloses a system wherein the coincident address of predetermined print head nozzles with heat pulses and hydrostatic pressure, allows ink to flow freely to spacer-separated paper, passing beneath the print head.
- U.S. Patent Nos. 4,737,803; 4,737,803 and 4,748,458 disclose ink jet recording systems wherein the coincident address of ink in print head nozzles with heat pulses and an electrostatically attractive field cause ejection of ink drops to a print sheet
- one object of the present invention is to provide means for improving the mechanical strength of drop on demand print heads where the nozzles are formed as holes which communicate between the back surface of the print head wafer and the front surface of the wafer.
- the wafer may become significantly weakened along the line of those holes. This is especially true when the holes are formed at the bottom of a slot which is formed in the wafer, and where the slot is formed most of the way through the wafer.
- the strength of the wafer along the line of nozzles may be as little as 1 % of the normal wafer strength. This can create a severe problem for wafer handling, and may also result in mechanical failure when used with pressurized ink.
- the present invention provides an improvement for this problem, and maintains wafer strength along the line of nozzles at approximately 50% of the normal wafer strength. This is achieved by dividing each row of nozzles into segments, and by displacing some of those segments (preferably every alternate segment) in the print direction. Displacement of the segment of nozzles is in the print direction so that the nozzles can still print the same pixels to the recording medium, simply by altering the time that the nozzles are provided with the particular information to be printed. The distance that the displaced segments are displaced is preferably slightly more than the width of the slot (or ink channel) in which the nozzles in the appropriate segment are formed.
- the invention constitutes a drop on demand printing head comprising a substrate having a plurality of nozzles formed as holes communicating between the back surface of said substrate and the front surface of said substrate, said nozzles being formed in one or more row regions which are generally perpendicular to a print direction, each of said regions being divided into a plurality of multi-nozzle groups at least some of said groups within the regions being displaced in the print direction from other of said groups in the same row region.
- a further preferred aspect of the invention is that the substrate is composed of single crystal silicon.
- a further preferred aspect of the invention is that the substrate is a single crystal silicon wafer of (100) crystallographic orientation.
- a alternative further preferred aspect of the invention is that the substrate is a single crystal silicon wafer of (110) crystallographic orientation.
- a further preferred aspect of the invention is that the group of the segments which are displaced from the other segments in each row is each alternate segment.
- a further preferred aspect of the invention is that the distance that the segments are displaced from the other segments in each row is greater than or equal to the width of the ink channel formed in the substrate wherein the width is measured at the back surface of the substrate, and the width is measured in the print direction.
- Figure 1 shows a simplified block schematic diagram of one exemplary printing apparatus according to the present invention.
- Figure 1(b) shows a cross section of one variety of nozzle tip in accordance with the invention.
- Figures 2(a) to 2(f) show fluid dynamic simulations of drop selection.
- Figure 3(a) shows a finite element fluid dynamic simulation of a nozzle in operation according to an embodiment ofthe invention.
- Figure 3(b) shows successive meniscus positions during drop selection and separation.
- Figure 3(c) shows the temperatures at various points during a drop selection cycle.
- Figure 3(d) shows measured surface tension versus temperature curves for various ink additives.
- Figure 3(e) shows the power pulses which are applied to the nozzle heater to generate the temperature curves of figure 3(c)
- Figure 4 shows a block schematic diagram of print head drive circuitry for practice of the invention.
- Figure 5 shows projected manufacturing yields for an A4 page width color print head embodying features of the invention, with and without fault tolerance.
- Figure 6 shows a generalized block diagram of a printing system using a print head
- Figure 7 shows a single silicon substrate with a multitude of nozzles etched in it.
- Figure 8 shows an arrangement of nozzles for an 800 dpi color print head which are closely packed, and which exhibits several problems solved by the present invention.
- Figure 9 shows an arrangement of nozzles for an 800 dpi color print head which are further spaced, but which still exhibit several problems solved by the present invention.
- Figure 10 shows an arrangement of nozzles for an 800 dpi color print head which are divided into groups of rows for each ink color, but which still exhibit a problem solved by the present invention.
- Figure 11 shows an arrangement of nozzles for an 800 dpi color print head fabricated on a (100) silicon wafer, with alternate segments displaced.
- Figure 12 shows an arrangement of nozzles for an 800 dpi color print head fabricated on a (110) silicon wafer, with alternate segments displaced.
- the invention constitutes a drop-on-demand printing mechanism wherein the means of selecting drops to be printed produces a difference in position between selected drops and drops which are not selected, but which is insufficient to cause the ink drops to overcome the ink surface tension and separate from the body of ink, and wherein an alternative means is provided to cause separation of the selected drops from the body of ink.
- the separation of drop selection means from drop separation means significantly reduces the energy required to select which ink drops are to be printed. Only the drop selection means must be driven by individual signals to each nozzle.
- the drop separation means can be a field or condition applied simultaneously to all nozzles.
- the drop selection means may be chosen from, but is not limited to, the following list:
- the drop separation means may be chosen from, but is not limited to, the following list: 1) Proximity (recording medium in close proximity to print head)
- DOD printing technology targets shows some desirable characteristics of drop on demand printing technology.
- the table also lists some methods by which some embodiments described herein, or in other of my related applications, provide improvements over the prior art.
- TU thermal ink jet
- piezoelectric ink jet systems a drop velocity of approximately 10 meters per second is preferred to ensure that the selected ink drops overcome ink surface tension, separate from the body of the ink, and strike the recording medium.
- These systems have a very low efficiency of conversion of electrical energy into drop kinetic energy.
- the efficiency of TI J systems is approximately 0.02%).
- the drive circuits for piezoelectric ink jet heads must either switch high voltages, or drive highly capacitive loads.
- the total power consumption of pagewidth ⁇ J printheads is also very high.
- An 800 dpi A4 full color pagewidth ⁇ J print head printing a four color black image in one second would consume approximately 6 kW of electrical power, most of which is converted to waste heat. The difficulties of removal of this amount of heat precludes the production of low cost, high speed, high resolution compact pagewidth TU systems.
- One important feature of embodiments of the invention is a means of significantly reducing the energy required to select which ink drops are to be printed. This is achieved by separating the means for selecting ink drops from the means for ensuring that selected drops separate from the body of ink and form dots on the recording medium. Only the drop selection means must be driven by individual signals to each nozzle. The drop separation means can be a field or condition applied simultaneously to all nozzles.
- Drop selection means shows some of the possible means for selecting drops in accordance with the invention.
- the drop selection means is only required to create sufficient change in the position of selected drops that the drop separation means can discriminate between selected and imselected drops.
- the preferred drop selection means for water based inks is method 1 : "Electrothermal reduction of surface tension of pressurized ink”. This drop selection means provides many advantages over other systems, including; low power operation (approximately 1% of TU), compatibility with CMOS VLSI chip fabrication, low voltage operation (approx. 10 V), high nozzle density, low temperature operation, and wide range of suitable ink formulations. The ink must exhibit a reduction in surface tension with increasing temperature.
- the preferred drop selection means for hot melt or oil based inks is method 2: "Electrothermal reduction of ink viscosity, combined with oscillating ink pressure”.
- This drop selection means is particularly suited for use with inks which exhibit a large reduction of viscosity with increasing temperature, but only a small reduction in surface tension. This occurs particularly with non-polar ink carriers with relatively high molecular weight This is especially applicable to hot melt and oil based inks.
- the table “Drop separation means” shows some of the possible methods for separating selected drops from the body of ink, and ensuring that the selected drops form dots on the printing medium.
- the drop separation means discriminates between selected drops and imselected drops to ensure that imselected drops do not form dots on the printing medium.
- drop separation means may also be used.
- the preferred drop separation means depends upon the intended use. For most applications, method 1: “Electrostatic attraction”, or method 2: “AC electric field” are most appropriate. For applications where smooth coated paper or film is used, and very high speed is not essential, method 3: “Proximity” may be appropriate. For high speed, high quality systems, method 4: 'Transfer proximity” can be used. Method 6: “Magnetic attraction” is appropriate for portable printing systems where the print medium is too rough for proximity printing, and the high voltages required for electrostatic drop separation are undesirable. There is no clear 'best' drop separation means which is applicable to all circumstances.
- FIG. 1 A simplified schematic diagram of one preferred printing system according to the invention appears in Figure 1(a).
- An image source 52 may be raster image data from a scanner or computer, or outline image data in the form of a page description language (PDL), or other forms of digital image representation.
- This image data is converted to a pixel-mapped page image by the image processing system 53.
- This may be a raster image processor (RIP) in the case of PDL image data, or may be pixel image manipulation in the case of raster image data.
- Continuous tone data produced by the image processing unit 53 is halftoned.
- Halftoning is performed by the Digital Halftoning unit 54.
- Halftoned bitmap image data is stored in the image memory 72.
- the image memory 72 may be a full page memory, or a band memory.
- Heater control circuits 71 read data from the image memory 72 and apply time- varying electrical pulses to the nozzle heaters (103 in figure 1(b)) that are part of the print head 50. These pulses are applied at an appropriate time, and to the appropriate nozzle, so that selected drops will form spots on the recording medium 51 in the appropriate position designated by the data in the image memory 72.
- the recording medium 51 is moved relative to the head 50 by a paper transport system 65, which is electronically controlled by a paper transport control system 66, which in turn is controlled by a microcontroller 315.
- the paper transport system shown in figure 1(a) is schematic only, and many different mechanical configurations are possible. In the case of pagewidth print heads, it is most convenient to move the recording medium 51 past a stationary head 50. However, in the case of scanning print systems, it is usually most convenient to move the head 50 along one axis (the sub-scanning direction) and the recording medium 51 along the orthogonal axis (the main scanning direction), in a relative raster motion.
- the microcontroller 315 may also control the ink pressure regulator
- ink is contained in an ink reservoir 64 under pressure.
- the ink pressure is insufficient to overcome the ink surface tension and eject a drop.
- a constant ink pressure can be achieved by applying pressure to the ink reservoir 64 under the control of an ink pressure regulator 63.
- the ink pressure can be very accurately generated and controUed by situating the top surface of the ink in the reservoir 64 an appropriate distance above the head 50.
- This ink level can be regulated by a simple float valve (not shown).
- ink is contained in an ink reservoir 64 under pressure, and the ink pressure is caused to oscillate.
- the means of producing this oscillation may be a piezoelectric actuator mounted in the ink channels (not shown).
- the ink is distributed to the back surface of the head 50 by an ink channel device 75.
- the ink preferably flows through slots and/or holes etched through the silicon substrate of the head 50 to the front surface, where the nozzles and actuators are situated.
- the nozzle actuators are electrothermal heaters.
- an external field 74 is required to ensure that the selected drop separates from the body of the ink and moves towards the recording medium 51.
- a convenient external field 74 is a constant electric field, as the ink is easily made to be electrically conductive.
- the paper guide or platen 67 can be made of electrically conductive material and used as one electrode generating the electric field.
- the other electrode can be the head 50 itself.
- Another embodiment uses proximity of the print medium as a means of discriminating between selected drops and imselected drops. For small drop sizes gravitational force on the ink drop is very small; approximately 10 "4 of the surface tension forces, so gravity can be ignored in most cases. This allows the print head 50 and recording medium 51 to be oriented in any direction in relation to the local gravitational field. This is an important requirement for portable printers.
- Figure 1 (b) is a detail enlargement of a cross section of a single microscopic nozzle tip embodiment of the invention, fabricated using a modified
- CMOS process The nozzle is etched in a substrate 101, which may be silicon, glass, metal, or any other suitable material. If substrates which are not semiconductor materials are used, a semiconducting material (such as amorphous silicon) may be deposited on the substrate, and integrated drive transistors and data distribution circuitry may be formed in the surface semiconducting layer.
- a semiconducting material such as amorphous silicon
- SCS substrates have several advantages, including:
- Print heads can be fabricated in existing facilities (fabs) using standard VLSI processing equipment;
- SCS has high mechanical strength and rigidity
- SCS has a high thermal conductivity.
- the nozzle is of cylindrical form, with the heater 103 forming an annulus.
- the nozzle tip 104 is formed from silicon dioxide layers 102 deposited during the fabrication of the CMOS drive circuitry.
- the nozzle tip is passivated with silicon nitride.
- the protruding nozzle tip controls the contact point of the pressurized ink 100 on the print head surface.
- the print head surface is also hydrophobized to prevent accidental spread of ink across the front of the print head.
- Many other configurations of nozzles are possible, and nozzle embodiments of the invention may vary in shape, dimensions, and materials used.
- Monolithic nozzles etched from the substrate upon which the heater and drive electronics are formed have the advantage of not requiring an orifice plate.
- the elimination of the orifice plate has significant cost savings in manufacture and assembly.
- Recent methods for eliminating orifice plates include the use of 'vortex' actuators such as those described in Domoto et al US Pat. No.4,580,158, 1986, assigned to Xerox, and Miller et al US Pat. No. 5,371,527, 1994 assigned to
- the preferred method for elimination of orifice plates for print heads of the invention is incorporation of the orifice into the actuator substrate.
- This type of nozzle may be used for print heads using various techniques for drop separation.
- Figure 2 shows the results of energy transport and fluid dynamic simulations performed using FIDAP, a commercial fluid dynamic simulation software package available from Fluid Dynamics Inc., of Illinois, USA.
- FIDAP Fluid Dynamics Inc.
- This simulation is of a thermal drop selection nozzle embodiment with a diameter of 8 ⁇ m, at an ambient temperature of 30°C.
- the total energy applied to the heater is 276 nJ, applied as 69 pulses of 4 nJ each.
- the ink pressure is 10 kPa above ambient air pressure, and the ink viscosity at 30°C is 1.84 cPs.
- the ink is water based, and includes a sol of 0.1% palmitic acid to achieve an enhanced decrease in surface tension with increasing temperature.
- FIG. 1 A cross section of the nozzle tip from the central axis of the nozzle to a radial distance of 40 ⁇ m is shown.
- Heat flow in the various materials of the nozzle including silicon, silicon nitride, amorphous silicon dioxide, crystalline silicon dioxide, and water based ink are simulated using the respective densities, heat capacities, and thermal conductivities of the materials.
- the time step of the simulation is 0.1 ⁇ s.
- Figure 2(a) shows a quiescent state, just before the heater is actuated. An equilibrium is created whereby no ink escapes the nozzle in the quiescent state by ensuring that the ink pressure plus external electrostatic field is insufficient to overcome the surface tension of the ink at the ambient temperature. In the quiescent state, the meniscus of the ink does not protrude significantly from the print head surface, so the electrostatic field is not significantly concentrated at the meniscus.
- Figure 2(b) shows thermal contours at 5°C intervals 5 ⁇ s after the start of the heater energizing pulse.
- the heater When the heater is energized, the ink in contact with the nozzle tip is rapidly heated. The reduction in surface tension causes the heated portion ofthe meniscus to rapidly expand relative to the cool ink meniscus.
- Figure 2(c) shows thermal contours at 5°C intervals 10 ⁇ s after the start of the heater energizing pulse.
- the increase in temperature causes a decrease in surface tension, disturbing the equilibrium of forces. As the entire meniscus has been heated, the ink begins to flow.
- Figure 2(d) shows thermal contours at 5°C intervals 20 ⁇ s after the start of the heater energizing pulse.
- the ink pressure has caused the ink to flow to a new meniscus position, which protrudes from the print head.
- the electrostatic field becomes concentrated by the protruding conductive ink drop.
- Figure 2(e) shows thermal contours at 5°C intervals 30 ⁇ s after the start of the heater energizing pulse, which is also 6 ⁇ s after the end of the heater pulse, as the heater pulse duration is 24 ⁇ s.
- the nozzle tip has rapidly cooled due to conduction through the oxide layers, and conduction into the flowing ink.
- the nozzle tip is effectively 'water cooled' by the ink. Electrostatic attraction causes the ink drop to begin to accelerate towards the recording medium. Were the heater pulse significantly shorter (less than 16 ⁇ s in this case) the ink would not accelerate towards the print medium, but would instead return to the nozzle.
- Figure 2(f) shows thermal contours at 5°C intervals 26 ⁇ s after the end of the heater pulse.
- the temperature at the nozzle tip is now less than 5°C above ambient temperature. This causes an increase in surface tension around the nozzle tip.
- the rate at which the ink is drawn from the nozzle exceeds the viscously limited rate of ink flow through the nozzle, the ink in the region of the nozzle tip 'necks', and the selected drop separates from the body of ink.
- the selected drop then travels to the recording medium under the influence of the external electrostatic field.
- the meniscus of the ink at the nozzle tip then returns to its quiescent position, ready for the next heat pulse to select the next ink drop.
- Figure 3(a) shows successive meniscus positions during the drop selection cycle at 5 ⁇ s intervals, starting at the beginning of the heater energizing pulse.
- Figure 3(b) is a graph of meniscus position versus time, showing the movement of the point at the centre of the meniscus.
- the heater pulse starts 10 ⁇ s into the simulation.
- Figure 3(c) shows the resultant curve of temperature with respect to time at various points in the nozzle.
- the vertical axis of the graph is temperature, in units of 100°C.
- the horizontal axis of the graph is time, in units of 10 ⁇ s.
- the temperature curve shown in figure 3(b) was calculated by FIDAP, using 0.1 ⁇ s time steps.
- the local ambient temperature is 30 degrees C. Temperature histories at three points are shown:
- a - Nozzle tip This shows the temperature history at the circle of contact between the passivation layer, the ink, and air.
- C - Chip surface This is at a point on the print head surface 20 ⁇ m from the centre of the nozzle. The temperature only rises a few degrees. This indicates that active circuitry can be located very close to the nozzles without experiencing performance or lifetime degradation due to elevated temperatures.
- Figure 3(e) shows the power applied to the heater. Optimum operation requires a sharp rise in temperature at the start of the heater pulse, a maintenance of the temperature a little below the boiling point of the ink for the duration of the pulse, and a rapid fall in temperature at the end of the pulse. To achieve this, the average energy applied to the heater is varied over the duration of the pulse. In this case, the variation is achieved by pulse frequency modulation of 0.1 ⁇ s sub-pulses, each with an energy of 4 nJ.
- the peak power applied to the heater is 40 mW, and the average power over the duration of the heater pulse is 11.5 mW.
- the sub-pulse frequency in this case is 5 Mhz. This can readily be varied without significantly affecting the operation of the print head. A higher sub-pulse frequency allows finer control over the power applied to the heater.
- a sub-pulse frequency of 13.5 Mhz is suitable, as this frequency is also suitable for minimizing the effect of radio frequency interference (RFI).
- RFID radio frequency interference
- ⁇ r is the surface tension at temperature T
- k is a constant
- T c is the critical temperature of the liquid
- M is the molar mass of the liquid
- x is the degree of association of the liquid
- p is the density of the liquid.
- surfactant is important.
- water based ink for thermal ink jet printers often contains isopropyl alcohol (2-propanol) to reduce the surface tension and promote rapid drying.
- Isopropyl alcohol has a boiling point of 82.4°G, lower than that of water.
- a surfactant such as 1-Hexanol (b.p. 158°C) can be used to reverse this effect, and achieve a surface tension which decreases slightly with temperature.
- a relatively large decrease in surface tension with temperature is desirable to maximize operating latitude.
- a surface tension decrease of 20 mN/m over a 30°C temperature range is preferred to achieve large operating margins, while as little as lOmN/m can be used to achieve operation of the print head according to the present invention.
- the ink may contain a low concentration sol of a surfactant which is solid at ambient temperatures, but melts at a threshold temperature. Particle sizes less than 1,000 A are desirable. Suitable surfactant melting points for a water based ink are between 50°C and 90°C, and preferably between 60°C and 80°C.
- the ink may contain an oil/water microemulsion with a phase inversion temperature (PIT) which is above the maximum ambient temperature, but below the boiling point of the ink.
- PIT phase inversion temperature
- the PIT of the microemulsion is preferably 20°C or more above the maximum non-operating temperature encountered by the ink. A PIT of approximately 80°C is suitable.
- Inks can be prepared as a sol of small particles of a surfactant which melts in the desired operating temperature range.
- surfactants include carboxylic acids with between 14 and 30 carbon atoms, such as:
- the melting point of sols with a small particle size is usually slightly less than of the bulk material, it is preferable to choose a carboxylic acid with a melting point slightly above the desired drop selection temperature.
- a good example is Arachidic acid.
- carboxylic acids are available in high purity and at low cost.
- the amount of surfactant required is very small, so the cost of adding them to the ink is insignificant
- a mixture of carboxylic acids with slightly varying chain lengths can be used to spread the melting points over a range of temperatures. Such mixtures will typically cost less than the pure acid.
- surfactant it is not necessary to restrict the choice of surfactant to simple unbranched carboxylic acids.
- Surfactants with branched chains or phenyl groups, or other hydrophobic moieties can be used. It is also not necessary to use a carboxylic acid.
- Many highly polar moieties are suitable for the hydrophilic end of the surfactant. It is desirable that the polar end be ionizable in water, so that the surface of the surfactant particles can be charged to aid dispersion and prevent flocculation. In the case of carboxylic acids, this can be achieved by adding an alkali such as sodium hydroxide or potassium hydroxide. Prenaration of Inks with Surfactant Sols
- the surfactant sol can be prepared separately at high concentration, and added to the ink in the required concentration.
- An example process for creating the surfactant sol is as follows: 1) Add the carboxylic acid to purified water in an oxygen free atmosphere.
- the ink preparation w ⁇ l also contain either dye(s) or pigment(s), bactericidal agents, agents to enhance the electrical conductivity of the ink if electrostatic drop separation is used, humectants, and other agents as required. Anti-foaming agents will generally not be required, as there is no bubble formation during the drop ejection process.
- Inks made with anionic surfactant sols are generally unsuitable for use with cationic dyes or pigments. This is because the cationic dye or pigment may precipitate or flocculate with the anionic surfactant. To allow the use of cationic dyes and pigments, a cationic surfactant sol is required. The family of alkylamines is suitable for this purpose.
- the method of preparation of cationic surfactant sols is essentially similar to that of anionic surfactant sols, except that an acid instead of an alkali is used to adjust the pH balance and increase the charge on the surfactant particles.
- a pH of 6 using HCl is suitable.
- a microemulsion is chosen with a phase inversion temperature (PIT) around the desired ejection threshold temperature. Below the PIT, the microemulsion is oil in water (OAV), and above the PIT the microemulsion is water in oil (W/O). At low temperatures, the surfactant forming the microemulsion prefers a high curvature surface around oil, and at temperatures significantly above the PIT, the surfactant prefers a high curvature surface around water. At temperatures close to the PIT, the microemulsion forms a continuous 'sponge' of topologically connected water and oil.
- PIT phase inversion temperature
- the surfactant prefers surfaces with very low curvature.
- surfactant molecules migrate to the ink/air interface, which has a curvature which is much less than the curvature of the oil emulsion. This lowers the surface tension of the water.
- the microemulsion changes from O W to W/O, and therefore the ink/air interface changes from water/air to oil/air.
- the oil/air interface has a lower surface tension.
- microemulsion based inks There is a wide range of possibilities for the preparation of microemulsion based inks. For fast drop ejection, it is preferable to chose a low viscosity oil.
- water is a suitable polar solvent
- polar solvents with a high surface tension should be chosen, so that a large decrease in surface tension is achievable.
- the surfactant can be chosen to result in a phase inversion temperature in the desired range.
- surfactants of the group poly(oxyethylene)alkylphenyl ether ethoxylated alkyl phenols, general formula: C n H 2n+ ⁇ C H6(CH 2 CH 2 O) m OH
- the hydrophilicity of the surfactant can be increased by increasing m, and the hydrophobicity can be increased by increasing n. Values of m of approximately 10, and n of approximately 8 are suitable.
- ethoxylated alkyl phenols include those listed in the following table:
- Microemulsions are thermodynamically stable, and will not separate. Therefore, the storage time can be very long. This is especially significant for office and portable printers, which may be used sporadically.
- microemulsion will form spontaneously with a particular drop size, and does not require extensive stirring, centrifuging, or filtering to ensure a particular range of emulsified oil drop sizes.
- the amount of oil contained in the ink can be quite high, so dyes which are soluble in oil or soluble in water, or both, can be used. It is also possible to use a mixture of dyes, one soluble in water, and the other soluble in oil, to obtain specific colors.
- Oil miscible pigments are prevented from flocculating, as they are trapped in the oil microdroplets.
- the use of a microemulsion can reduce the mixing of different dye colors on the surface of the print medium.
- T e requirement for humectants can be reduced or eliminated.
- Oil in water mixtures can have high oil contents - as high as 40% - and still form O/W microemulsions. This allows a high dye or pigment loading.
- the ninth combination is useful for printing transparent coatings, UV ink, and selective gloss highlights.
- dyes are amphiphilic, large quantities of dyes can also be solubilized in the oil-water boundary layer as this layer has a very large surface area. It is also possible to have multiple dyes or pigments in each phase, and to have a mixture of dyes and pigments in each phase.
- the color of the ink may be different on different substrates. If a dye and a pigment are used in combination, the color of the dye will tend to have a smaller contribution to the printed ink color on more abso ⁇ tive papers, as the dye will be absorbed into the paper, while the pigment will tend to 'sit on top' of the paper. This may be used as an advantage in some circumstances.
- This factor can be used to achieve an increased reduction in surface tension with increasing temperature. At ambient temperatures, only a portion of the surfactant is in solution. When the nozzle heater is turned on, the temperature rises, and more of the surfactant goes into solution, decreasing the surface tension.
- a surfactant should be chosen with a Krafft point which is near the top of the range of temperatures to which the ink is raised. This gives a maximum margin between the concentration of surfactant in solution at ambient temperatures, and the concentration of surfactant in solution at the drop selection temperature.
- the concentration of surfactant should be approximately equal to the CMC at the Krafft point. In this manner, the surface tension is reduced to the maximum amount at elevated temperatures, and is reduced to a minimum amount at ambient temperatures.
- Non-ionic surfactants using polyoxyethylene (POE) chains can be used to create an ink where the surface tension falls with increasing temperature.
- the POE chain is hydrophilic, and maintains the surfactant in solution.
- the structured water around the POE section of the molecule is disrupted, and the POE section becomes hydrophobic.
- the surfactant is increasingly rejected by the water at higher temperatures, resulting in increasing concentration of surfactant at the air/ink interface, thereby lowering surface tension.
- the temperature at which the POE section of a nonionic surfactant becomes hydrophilic is related to the cloud point of that surfactant POE chains by themselves are not particularly suitable, as the cloud point is generally above 100°C
- Polyoxypropylene (POP) can be combined with POE in POE/POP block copolymers to lower the cloud point of POE chains without introducing a strong hydrophobicity at low temperatures.
- POP Polyoxypropylene
- Two main configurations of symmetrical POE POP block copolymers are available. These are:
- Desirable characteristics are a room temperature surface tension which is as high as possible, and a cloud point between 40°C and 100°C, and preferably between 60°C and 80°C.
- Meroxapol [HO(CHCH 3 CH 2 O) x (CH 2 CH 2 O) y (CHCH 3 CH 2 O) z OH] varieties where the average x and z are approximately 4, and the average y is approximately 15 may be suitable.
- the cloud point of POE surfactants is increased by ions that disrupt water structure (such as I " ), as this makes more water molecules available to form hydrogen bonds with the POE oxygen lone pairs.
- the cloud point of POE surfactants is decreased by ions that form water structure (such as Cl “ , OH " ), as fewer water molecules are available to form hydrogen bonds. Bromide ions have relatively little effect
- the ink composition can be 'tuned' for a desired temperature range by altering the lengths of POE and POP chains in a block copolymer surfactant, and by changing the choice of salts (e.g Cl ' to Br ' to I " ) that are added to increase electrical conductivity. NaCl is likely to be the best choice of salts to increase ink conductivity, due to low cost and non-toxicity. NaCl slightly lowers the cloud point of nonionic surfactants.
- Hot Melt Inks The ink need not be in a liquid state at room temperature.
- Solid 'hot melt' inks can be used by heating the printing head and ink reservoir above the melting point of the ink.
- the hot melt ink must be formulated so that the surface tension of the molten ink decreases with temperature. A decrease of approximately 2 mN/m will be typical of many such preparations using waxes and other substances. However, a reduction in surface tension of approximately 20 mN/m is desirable in order to achieve good operating margins when relying on a reduction in surface tension rather than a reduction in viscosity.
- the temperature difference between quiescent temperature and drop selection temperature may be greater for a hot melt ink than for a water based ink, as water based inks are constrained by the boiling point of the water.
- the ink must be liquid at the quiescent temperature.
- the quiescent temperature should be higher than the highest ambient temperature likely to be encountered by the printed page. T he quiescent temperature should also be as low as practical, to reduce the power needed to heat the print head, and to provide a maximum margin between the quiescent and the drop ejection temperatures.
- a quiescent temperature between 60°C and 90°C is generally suitable, though other temperatures may be used.
- a drop ejection temperature of between 160°C and 200°C is generally suitable.
- a dispersion of microfine particles of a surfactant with a melting point substantially above the quiescent temperature, but substantially below the drop ejection temperature, can be added to the hot melt ink while in the liquid phase.
- the hot melt ink carrier have a relatively large surface tension
- Suitable materials will generally have a strong intermolecular attraction, which may be achieved by multiple hydrogen bonds, for example, polyols, such as Hexanetetrol, which has a melting point of 88°C.
- Figure 3(d) shows the measured effect of temperature on the surface tension of various aqueous preparations containing the following additives:
- operation of an embodiment using thermal reduction of viscosity and proximity drop separation, in combination with hot melt ink is as follows.
- solid ink Prior to operation of the printer, solid ink is melted in the reservoir 64.
- the reservoir, ink passage to the print head, ink channels 75, and print head 50 are maintained at a temperature at which the ink 100 is liquid, but exhibits a relatively high viscosity (for example, approximately 100 cP).
- the Ink 100 is retained in the nozzle by the surface tension of the ink.
- the ink 100 is formulated so that the viscosity ofthe ink reduces with increasing temperature.
- the ink pressure oscillates at a frequency which is an integral multiple of the drop ejection frequency from the nozzle.
- the ink pressure oscillation causes oscillations of the ink meniscus at the nozzle tips, but this oscillation is small due to the high ink viscosity. At the normal operating temperature, these oscillations are of insufficient amplitude to result in drop separation.
- the heater 103 When the heater 103 is energized, the ink forming the selected drop is heated, causing a reduction in viscosity to a value which is preferably less than 5 cP. The reduced viscosity results in the ink meniscus moving further during the high pressure part of the ink pressure cycle.
- the recording medium 51 is arranged sufficiently close to the print head 50 so that the selected drops contact the recording medium 51, but sufficiently far away that the imselected drops do not contact the recording medium 51.
- part of the selected drop freezes, and attaches to the recording medium.
- ink pressure falls, ink begins to move back into the nozzle.
- the body of ink separates from the ink which is frozen onto the recording medium.
- the meniscus of the ink 100 at the nozzle tip then returns to low amplitude oscillation.
- the viscosity of the ink increases to its quiescent level as remaining heat is dissipated to the bulk ink and print head.
- One ink drop is selected, separated and forms a spot on the recording medium 51 for each heat pulse. As the heat pulses are electrically controlled, drop on demand ink jet operation can be achieved.
- An objective of printing systems according to the invention is to attain a print quality which is equal to that which people are accustomed to in quality color publications printed using offset printing. This can be achieved using a print resolution of approximately 1,600 dpi. However, 1,600 dpi printing is difficult and expensive to achieve. Similar results can be achieved using 800 dpi printing, with 2 bits per pixel for cyan and magenta, and one bit per pixel for yellow and black. This color model is herein called CC'MM'YK. Where high quality monochrome image printing is also required, two bits per pixel can also be used for black. This color model is herein called CC'MM' YKK'. Color models, halftoning, data compression, and real-time expansion systems suitable for use in systems of this invention and other printing systems are described in the following Australian patent specifications filed on 12 April 1995, the disclosure of which are hereby inco ⁇ orated by reference:
- Printing apparatus and methods of this invention are suitable for a wide range of applications, including (but not limited to) the following: color and monochrome office printing, short run digital printing, high speed digital printing, process color printing, spot color printing, offset press supplemental printing, low cost printers using scanning print heads, high speed printers using pagewidth print heads, portable color and monochrome printers, color and monochrome copiers, color and monochrome facsimile machines, combined printer, facsimile and copying machines, label printing, large format plotters, photographic duplication, printers for digital photographic processing, portable printers inco ⁇ orated into digital 'instant' cameras, video printing, printing of PhotoCD images, portable printers for 'Personal Digital Assistants', wallpaper printing, indoor sign printing, billboard printing, and fabric printing.
- drop on demand printing systems have consistent and predictable ink drop size and position. Unwanted variation in ink drop size and position causes variations in the optical density of the resultant print, reducing the perceived print quahty. These variations should be kept to a small proportion of the nominal ink drop volume and pixel spacing respectively. Many environmental variables can be compensated to reduce their effect to insignificant levels. Active compensation of some factors can be achieved by varying the power applied to the nozzle heaters.
- An optimum temperature profile for one print head embodiment involves an instantaneous raising of the active region of the nozzle tip to the ejection temperature, maintenance of this region at the ejection temperature for the duration of the pulse, and instantaneous cooling of the region to the ambient temperature.
- One way to achieve this is by 'broadcasting' a variety of different digital pulse trains across the print head chip, and selecting the appropriate pulse train for each nozzle using multiplexing circuits.
- Figure 4 is a block schematic diagram showing electronic operation of an example head driver circuit in accordance with this invention.
- This control circuit uses analog modulation of the power supply voltage applied to the print head to achieve heater power modulation, and does not have individual control of the power applied to each nozzle.
- Figure 4 shows a block diagram for a system using an 800 dpi pagewidth print head which prints process color using the CC'MM' YK color model.
- the print head 50 has a total of 79,488 nozzles, with 39,744 main nozzles and 39,744 redundant nozzles.
- the main and redundant nozzles are divided into six colors, and each color is divided into 8 drive phases.
- Each drive phase has a shift register which converts the serial data from a head control ASIC 400 into parallel data for enabling heater drive circuits.
- Each shift register is composed of 828 shift register stages 217, the outputs of which are logically anded with phase enable signal by a nand gate 215.
- the output of the nand gate 215 drives an inverting buffer 216, which in turn controls the drive transistor 201.
- the drive transistor 201 actuates the electrothermal heater 200, which may be a heater 103 as shown in figure 1(b).
- the clock to the shift register is stopped the enable pulse is active by a clock stopper 218, which is shown as a single gate for clarity, but is preferably any of a range of well known glitch free clock control circuits. Stopping the clock of the shift register removes the requirement for a parallel data latch in the print head, but adds some complexity to the control circuits in the Head Control ASIC 400. Data is routed to either the main nozzles or the redundant nozzles by the data router 219 depending on the state of the appropriate signal of the fault status bus.
- the print head shown in figure 4 is simplified, and does not show various means of improving manufacturing yield, such as block fault tolerance.
- Drive circuits for different configurations of print head can readily be derived from the apparatus disclosed herein.
- Digital information representing patterns of dots to be printed on the recording medium is stored in the Page or Band memory 1513, which may be the same as the Image memory 72 in figure 1(a).
- Data in 32 bit words representing dots of one color is read from the Page or Band memory 1513 using addresses selected by the address mux 417 and control signals generated by the Memory Interface 418. These addresses are generated by Address generators 411, which forms part of the 'Per color circuits' 410, for which there is one for each of the six color components. The addresses are generated based on the positions ofthe nozzles in relation to the print medium.
- the Address generators 411 are preferably made programmable.
- the Address generators 411 normally generate the address corresponding to the position ofthe main nozzles. However, when faulty nozzles are present, locations of blocks of nozzles containing faults can be marked in the Fault Map RAM 412.
- the Fault Map RAM 412 is read as the page is printed. If the memory indicates a fault in the block of nozzles, the address is altered so that the Address generators 411 generate the address corresponding to the position of the redundant nozzles.
- Data read from the Page or Band memory 1513 is latched by the latch 413 and converted to four sequential bytes by the multiplexer 414.
- Timing of these bytes is adjusted to match that of data representing other colors by the FIFO 415.
- This data is then buffered by the buffer 430 to form the 48 bit main data bus to the print head 50.
- the data is buffered as the print head may be located a relatively long distance from the head control ASIC.
- Data from the Fault Map RAM 412 also forms the input to the FIFO 416. The timing of this data is matched to the data output of the FIFO
- the programmable power supply 320 provides power for the head 50.
- the voltage of the power supply 320 is controlled by the DAC 313, which is part of a RAM and DAC combination (RAMDAC) 316.
- the RAMDAC 316 contains a dual port RAM 317.
- the contents of the dual port RAM 317 are programmed by the Microcontroller 315. Temperature is compensated by changing the contents of the dual port RAM 317. These values are calculated by the microcontroller 315 based on temperature sensed by a thermal sensor 300.
- the thermal sensor 300 signal connects to the Analog to Digital Converter (ADC) 311.
- the ADC 311 is preferably inco ⁇ orated in the Microcontroller 315.
- the Head Control ASIC 400 contains control circuits for thermal lag compensation and print density.
- Thermal lag compensation requires that the power supply voltage to the head 50 is a rapidly time- varying voltage which is synchronized with the enable pulse for the heater. This is achieved by programming the programmable power supply 320 to produce this voltage.
- An analog time varying programming voltage is produced by the DAC 313 based upon data read from the dual port RAM 317. The data is read according to an address produced by the counter 403.
- the counter 403 produces one complete cycle of addresses during the period of one enable pulse. This synchronization is ensured, as the counter 403 is clocked by the system clock 408, and the top count of the counter 403 is used to clock the enable counter 404.
- the count from the enable counter 404 is then decoded by the decoder 405 and buffered by the buffer 432 to produce the enable pulses for the head 50.
- the counter 403 may include a prescaler if the number of states in the count is less than the number of clock periods in one enable pulse.
- Sixteen voltage states are adequate to accurately compensate for the heater thermal lag. These sixteen states can be specified by using a four bit connection between the counter 403 and the dual port RAM 317. However, these sixteen states may not be linearly spaced in time. To allow non-linear timing of these states the counter 403 may also include a ROM or other device which causes the counter 403 to count in a non-linear fashion. Alternatively, fewer than sixteen states may be used.
- the printing density is detected by counting the number of pixels to which a drop is to be printed ('on' pixels) in each enable period.
- the 'on' pixels are counted by the On pixel counters 402.
- the number of enable phases in a print head in accordance with the invention depend upon the specific design. Four, eight, and sixteen are convenient numbers, though there is no requirement that the number of enable phases is a power of two.
- the On Pixel Counters 402 can be composed of combinatorial logic pixel counters 420 which determine how many bits in a nibble of data are on. This number is then accumulated by the adder 421 and accumulator 422.
- a latch 423 holds the accumulated value valid for the duration of the enable pulse.
- the multiplexer 401 selects the output of the latch 423 which corresponds to the current enable phase, as determined by the enable counter 404.
- the output of the multiplexer 401 forms part of the address of the dual port RAM 317. An exact count of the number of 'on' pixels is not necessary, and the most significant four bits of this count are adequate.
- Combining the four bits of thermal lag compensation address and the four bits of print density compensation address means that the dual port RAM 317 has an 8 bit address. This means that the dual port RAM 317 contains 256 numbers, which are in a two dimensional array. These two dimensions are time (for thermal lag compensation) and print density. A third dimension - temperature - can be included.
- the microcontroller 315 has sufficient time to calculate a matrix of 256 numbers compensating for thermal lag and print density at the current temperature. Periodically (for example, a few times a second), the microcontroller senses the current head temperature and calculates this matrix.
- the clock to the print head 50 is generated from the system clock
- JTAG test circuits 499 may be included.
- the table "Comparison between Thermal ink jet and Present Invention” compares the aspects of printing in accordance with the present invention with thermal ink jet printing technology. A direct comparison is made between the present invention and thermal ink jet technology because both are drop on demand systems which operate using thermal actuators and liquid ink. Although they may appear similar, the two technologies operate on different principles.
- Thermal ink jet printers use the following fundamental operating principle.
- a thermal impulse caused by electrical resistance heating results in the explosive formation of a bubble in liquid ink. Rapid and consistent bubble formation can be achieved by superheating the ink, so that sufficient heat is transferred to the ink before bubble nucleation is complete.
- ink temperatures of approximately 280°C to 400°C are required.
- the bubble formation causes a pressure wave which forces a drop of ink from the aperture with high velocity. The bubble then collapses, drawing ink from the ink reservoir to re-fill the nozzle.
- Thermal ink jet printing has been highly successful commercially due to the high nozzle packing density and the use of well established integrated circuit manufacturing techniques.
- thermal ink jet printing technology faces significant technical problems including multi-part precision fabrication, device yield, image resolution, 'pepper' noise, printing speed, drive transistor power, waste power dissipation, satellite drop formation, thermal stress, differential thermal expansion, kogation, cavitation, rectified diffusion, and difficulties in ink formulation.
- Printing in accordance with the present invention has many of the advantages of thermal ink jet printing, and completely or substantially eliminates many of the inherent problems of thermal ink jet technology.
- yield The percentage of operational devices which are produced from a wafer run is known as the yield. Yield has a direct influence on manufacturing cost. A device with a yield of 5% is effectively ten times more expensive to manufacture than an identical device with a yield of 50%.
- Figure 5 is a graph of wafer sort yield versus defect density for a monolithic full width color A4 head embodiment ofthe invention.
- the head is 215 mm long by 5 mm wide.
- the non fault tolerant yield 198 is calculated according to Mu ⁇ hy's method, which is a widely used yield prediction method. With a defect density of one defect per square cm, Mu ⁇ hy's method predicts a yield less than 1 %. This means that more than 99% of heads fabricated would have to be discarded. This low yield is highly undesirable, as the print head manufacturing cost becomes unacceptably high.
- Figure 5 also includes a graph of non fault tolerant yield 197 which explicitly models the clustering of defects by introducing a defect clustering factor.
- the defect clustering factor is not a controllable parameter in manufacturing, but is a characteristic of the manufacturing process.
- the defect clustering factor for manufacturing processes can be expected to be approximately 2, in which case yield projections closely match Mu ⁇ hy's method.
- a solution to the problem of low yield is to inco ⁇ orate fault tolerance by including redundant functional units on the chip which are used to replace faulty functional units.
- redundant sub-units In memory chips and most Wafer Scale Integration (WSI) devices, the physical location of redundant sub-units on the chip is not important. However, in printing heads the redundant sub-unit may contain one or more printing actuators. These must have a fixed spatial relationship to the page being printed. To be able to print a dot in the same position as a faulty actuator, redundant actuators must not be displaced in the non-scan direction. However, faulty actuators can be replaced with redundant actuators which are displaced in the scan direction. To ensure that the redundant actuator prints the dot in the same position as the faulty actuator, the data timing to the redundant actuator can be altered to compensate for the displacement in the scan direction.
- the minimum physical dimensions of the head chip are determined by the width of the page being printed, the fragility of the head chip, and manufacturing constraints on fabrication of ink channels which supply ink to the back surface of the chip.
- the piinimiim practical size for a full width, full color head for printing A4 size paper is approximately 215 mm x 5 mm. This size allows the inclusion of 100% redundancy without significantly increasing chip area, when using 1.5 ⁇ m CMOS fabrication technology. Therefore, a high level of fault tolerance can be included without significantly decreasing primary yield.
- Figure 5 shows the fault tolerant sort yield 199 for a full width color A4 head which includes various forms of fault tolerance, the modeling of which has been included in the yield equation.
- This graph shows projected yield as a function of both defect density and defect clustering.
- the yield projection shown in figure 5 indicates that thoroughly implemented fault tolerance can increase wafer sort yield from under 1% to more than 90% under identical manufacturing conditions. This can reduce the manufacturing cost by a factor of 1 0.
- fault tolerance is highly recommended to improve yield and reliability of print heads containing thousands of printing nozzles, and thereby make pagewidth printing heads practical.
- fault tolerance is not to be taken as an essential part of the present invention.
- FIG. 6 A schematic diagram of a digital electronic printing system using a print head of this invention is shown in Figure 6.
- This shows a monolithic printing head 50 printing an image 60 composed of a multitude of ink drops onto a recording medium 51.
- This medium will typically be paper, but can also be overhead transparency film, cloth, or many other substantially flat surfaces which will accept ink drops.
- the image to be printed is provided by an image source 52, which may be any image type which can be converted into a two dimensional array of pixels.
- Typical image sources are image scanners, digitally stored images, images encoded in a page description language (PDL) such as Adobe Postscript, Adobe Postscript level 2, or Hewlett-Packard PCL 5, page images generated by a procedure-call based rasterizer, such as Apple QuickDraw, Apple Quickdraw GX, or Microsoft GDI, or text in an electronic form such as ASCII.
- PDL page description language
- This image data is then converted by an image processing system 53 into a two dimensional array of pixels suitable for the particular printing system. This may be color or monochrome, and the data will typically have between 1 and 32 bits per pixel, depending upon the image source and the specifications of the printing system.
- the image processing system may be a raster image processor (RIP) if the source image is a page description, or may be a two dimensional image processing system if the source image is from a scanner. If continuous tone images are required, then a halftoning system 54 is necessary. Suitable types of halftoning are based on dispersed dot ordered dither or error diffusion. Variations of these, commonly known as stochastic screening or frequency modulation screening are suitable. The halftoning system commonly used for offset printing - clustered dot ordered dither - is not recommended, as effective image resolution is unnecessarily wasted using this technique. The output of the halftoning system is a binary monochrome or color image at the resolution of the printing system according to the present invention.
- RIP raster image processor
- the binary image is processed by a data phasing circuit 55 (which may be inco ⁇ orated in a Head Control ASIC 400 as shown in figure 4) which provides the pixel data in the correct sequence to the data shift registers 56. Data sequencing is required to compensate for the nozzle arrangement and the movement of the paper.
- the driver circuits 57 When the data has been loaded into the shift registers 56, it is presented in parallel to the heater driver circuits 57. At the correct time, the driver circuits 57 will electronically connect the corresponding heaters 58 with the voltage pulse generated by the pulse shaper circuit 61 and the voltage regulator 62. The heaters 58 heat the tip of the nozzles 59, affecting the physical characteristics of the ink.
- Ink drops 60 escape from the nozzles in a pattern which corresponds to the digital impulses which have been applied to the heater driver circuits.
- the pressure of the ink in the ink reservoir 64 is regulated by the pressure regulator 63.
- Selected drops of ink drops 60 are separated from the body of ink by the chosen drop separation means, and contact the recording medium 51.
- the recording medium 51 is continually moved relative to the print head 50 by the paper transport system 65. If the print head 50 is the full width of the print region of the recording medium 51, it is only necessary to move the recording medium 51 in one direction, and the print head 50 can remain fixed. If a smaller print head 50 is used, it is necessary to implement a raster scan system. This is typically achieved by scanning the print head 50 along the short dimension of the recording medium 51, while moving the recording medium 51 along its long dimension.
- a printing speed of 60 A4 pages per minute (one page per second) will generally be adequate for many appUcations.
- achieving an electronically controlled print speed of 60 pages per minute is not simple.
- the minimum time taken to print a page is equal to the number of dot positions on the page times the time required to print a dot, divided by the number of dots of each color which can be printed simultaneously.
- the image quality that can be obtained is affected by the total number of ink dots which can be used to create an image.
- approximately 800 dots per inch (31.5 dots per mm) are required.
- the spacing between dots on the paper is
- a standard A4 page is 210 mm times 297 mm. At 31.5 dots per mm,
- 61,886,632 dots are required for a monochrome full bleed A4 page.
- High quality process color printing requires four colors - cyan, magenta, yellow, and black.
- the total number of dots required is 247,546,528. While this can be reduced somewhat by not allowing printing in a small margin at the edge of the paper, the total number of dots required is still very large. If the time taken to print a dot is 144 ms, and only one nozzle per color is provided, then it will take more than two hours to print a single page.
- printing heads with many small nozzles are preferred.
- the printing of a 800 dpi color A4 page in one second can be achieved if the printing head is the full width of the paper.
- the printing head can be stationary, and the paper can travel past it in the one second period.
- a four color 800 dpi printing head 210 mm wide requires 26,460 nozzles.
- Such a print head may contain 26,460 active nozzles, and 26,460 redundant (spare) nozzles, giving a total of 52,920 nozzles. There are 6,615 active nozzles for each of the cyan, magenta, yellow, and black process colors.
- Print heads with large numbers of nozzles can be manufactured at low cost This can be achieved by using semiconductor manufacturing processes to simultaneously fabricate many thousands of nozzles in a silicon wafer. To eliminate problems with mechanical alignment and differential thermal expansion that would occur if the print head were to be manufactured in several parts and assembled, the head can be manufactured from a single piece of silicon. Nozzles and ink channels are etched into the silicon. Heater elements are formed by evaporation of resistive materials, and subsequent photolithography using standard semiconductor manufacturing processes. To reduce the large number of connections that would be required on a print head with thousands of nozzles, data distribution circuits and drive circuits can also be integrated on the print head.
- Figure 7 is a simplified view of a portion of a print head, seen from the back surface of the chip, and cut through some of the nozzles.
- Nozzles 121 are fabricated in the substrate, e.g., by semiconductor photolithography and chemical wet etch or plasma etching processes. Ink enters the nozzle at the top surface of the head, passes through the substrate, and leaves via the nozzle tip 123. Planar fabrication of the heaters and the drive circuitry is on the underside of the wafer; that is, the print head is shown 'upside down' in relation the surface upon which active circuitry is fabricated.
- the substrate thickness 124 can be that of a standard silicon wafer, approximately 650 ⁇ m.
- the head width 125 is related to the number of colors, the arrangement of nozzles, the spacing between the nozzles, and the head area required for drive circuitry and interconnections.
- an appropriate width would be approximately 2 mm.
- an appropriate width would be approximately 5 mm.
- the appropriate head width is approximately 8 mm.
- the length of the head 126 depends upon the application. Very low cost applications may use short heads, which must be scanned over a page. High speed applications can use fixed page ⁇ width monolithic or multi-chip print heads. A typical range of lengths for print heads is between 1 cm and 21 cm, though print heads longer than 21 cm are appropriate for high volume paper or fabric printing.
- Nozzle placement in monolithic heads Figure 8 shows the closest nozzle placement desirable for a color monolithic drop on demand 800 dpi print head.
- the print head includes 8 rows of nozzles which are spaced one pixel width apart Each nozzle in each row is also spaced one pixel width apart The number of nozzles in each row is equal to the print width times the print resolution.
- 370 is the row of main nozzles which print cyan ink
- 371 is the row of redundant nozzles which print cyan ink
- 372 is the row of main nozzles which print magenta ink
- 373 is the row of redundant nozzles which print magenta ink
- 374 is the row of main nozzles which print yellow ink
- 375 is the row of redundant nozzles which print yellow ink
- 376 is the row of main nozzles which print black ink
- 377 is the row of redundant nozzles which print black ink
- the nozzle arrangement shown in figure 8 has an advantage of compactness, but has many disadvantages.
- One of these disadvantages is that the close packing may result in significant thermal and/or fluid dynamic crosstalk between nozzles.
- This problem can be alleviated by using the nozzle layout shown in figure 9.
- each of the rows 370 to 377 is replaced by two rows of nozzles, wherein the nozzles within each row print alternate pixels. This increases the distance between two nozzles in the same row to two pixel widths. In the case shown in figure 9, the minimum distance between nozzles is 2 times the pixel width.
- each row of nozzles in figure 8 can be replaced by an arbitrary number of rows of nozzles n, and each row may print every nth pixel.
- the spacing between nozzles in a row may then be n times the pixel width.
- the spacing between adjacent rows of nozzles need not be a pixel width, but can be considerably greater. This spacing need not even be a multiple of the pixel width, as the timing of actuation of the nozzles can be adjusted to make the ink drops form spots on the recording medium at the correct places to maintain image quality.
- the nozzle arrangements shown in figures 8 and 9 have a further disadvantage. Nozzles which are to be supplied with ink of one color are situated next to nozzles which are to supplied with ink of a different color. This results in difficulty in supplying different colors of ink to the print head without the inks mixing. This problem can be alleviated by using the nozzle layout shown in figure 10. In this case, all of the nozzles that are supplied with ink of one color are separated from nozzles which are to be supplied with different colored ink. The degree of separation required is highly dependent upon the method of supplying ink to the nozzles. If the nozzles are etched through the substrate, and ink is supplied to the nozzles via precision injection molded plastic ink channels, then a separation of approximately 1 mm is adequate. Separation significantly greater than 1 mm results in excessive width ofthe print head, with a subsequently lower primary yield.
- Separation significantly less than 1 mm results in difficulties in fabricating the ink channels and bonding them to the head. If the ink channels are fabricated from micromachined silicon or some other high precision fabrication technique, then the separation may be significantly reduced.
- the spacing between rows of nozzles of different colors also provides room for integrated drive electronics, such as drive transistors and data distribution circuits such as shift registers. Placing the drive transistors and shift registers corresponding to a row of nozzles adjacent to that row, and between that row and adjacent rows of nozzles which are supplied with ink of a different color, minimizes the difficulties of routing wires from the drive transistors to the nozzles. This is especially applicable to print heads, where the relatively low temperatures experienced in close proximity to the nozzles means that drive transistors and data distribution circuitry does not experience significant thermal degradation.
- the pattern of nozzles within color group in figure 10 is not constrained to the simple 'polka-dot' arrangement shown, and the distance between adjacent nozzles may be varied from that shown.
- the nozzle arrangements shown in figures 8, 9 and 10 are suitable for some fabrication processes, but still exhibit a problem when used in print heads where the nozzles are anisotropically etched through the substrate using wet etchants which etch some crystallographic directions in preference to others.
- This problem is that the substrate for the print head is excessively weakened along the rows of nozzles, and may not be strong enough to withstand handling or pressurized ink.
- This problem can be alleviated by dividing rows of nozzles into segments, and displacing alternate segments a certain distance in the print direction from the other segments. The distance that alternate segments should be displaced should be at least the width of the ink channel hole at the back surface of the wafer.
- a displacement less than this amount may preserve enough strength in the substrate, but complicates the process of masking the back face of the substrate for etching the ink channels.
- Figure 11 shows a nozzle arrangement which can be used for print heads which are fabricated on (100) silicon, and where ink channels are etched most of the way through the silicon substrate using a wet etch which etches slowly in ⁇ 111> crystallographic directions. This etching process will result in rectangular pyramidical pits with an angle of 54.74° to the (100) plane.
- the displacement in the print direction between adjacent segments is shown as n x 31.75 ⁇ m (31.75 ⁇ m being the pixel width in this example). It is preferable that n is an integer, to simplify timing of the enable pulses to the nozzle heaters. However, n can be non-integral with an appropriate timing correction.
- n can be calculated as (the width of the segment of nozzles plus 2 times the depth of the ink channels etched in the silicon substrate, plus any manufacturing margins required by the specific process used) divided by 31.75 ⁇ m.
- An appropriate value of n for an 800 dpi print head fabricated on a silicon wafer 650 ⁇ m thick using the nozzle arrangement shown would be 34.
- n is an integer, to simplify timing of the enable pulses to the nozzle heaters.
- the value of m may be the same as the value of n.
- the separation between segments in the print direction is not shown to scale in figure 11, and the typical separation required is much greater than that shown.
- the pattern of nozzles within each segment in figure 11 is not constrained to the simple 'polka-dot' arrangement shown, and the distance between adjacent nozzles may be varied from that shown. This manufacturing process has a disadvantage in that excessive silicon area is consumed. This increases manufacturing cost by reducing primary yield.
- the silicon area of the print head can be reduced by fabricating the ink channels on a (110) silicon wafer.
- (110) silicon wafers some of the ⁇ 111 ⁇ crystallographic planes are pe ⁇ endicular to the wafer surface. If the print head is fabricated with these planes normal to the print direction, it is possible to wet etch ink channels as narrow slots normal to the print direction.
- the nozzles can be formed at the bottom of these slots.
- Figure 12 shows a nozzle arrangement of an 800 dpi color print head suitable for fabrication using wet etching of (110) silicon wafers. Individual rows of nozzles are divided into segments. Each segment preferably contains a length of nozzles equal to or greater than four times the depth of the ink channels.
- each segment preferably contains 40 or more nozzles.
- the length of each segment is preferably not significantly greater than the minimum length allowed by other factors. A total of 40 nozzles per segment is therefore a suitable number.
- the distance that alternate segments are offset in the print direction from adjacent segments in the same row is shown in figure 12 to be 95.25 ⁇ m. This is three pixel widths at 800 dpi. It is not necessary for this distance to be an integral number of pixel widths.
- the preferred minimum offset in the print direction is sufficiently greater than the width of the ink channel to allow masking from the back surface of the wafer.
- the minimum width of the ink channels is the width of the nozzles. However, ink channels of greater width than this minimum are preferred to accommodate manufacturing tolerances and inaccuracies in the alignment of the wafer surface to the (110) crystallographic plane. Nozzle rows, and segments within rows, can be separated in the print direction by more than the minimum, but this leads to greater print head area, and therefore lower primary yield.
- the separation ion the print direction between nozzles which print different colors of ink is shown in figure 12 to be approximately 1 mm. This is to simplify the provision of ink to the etched silicon ink channels, and prevent mixing of different color inks.
- Figures 11 and 12 both show three segments in each row. This is to only simplify the drawing and the actual number of segments per row will preferably be the print length divided by the length of a segment
- a print head fabricated using wet etching on (110) silicon can use the nozzle arrangement shown in figure 11.
- the arrangement shown in figure 12 is preferable, as there is greater thermal and fluid dynamic isolation between nozzles, and the thin silicon and oxide membrane in the region of the nozzles at the bottom of the ink channels is narrower, and therefore stronger.
- the nozzles within each row or segment are shown to be in a straight line pe ⁇ endicular to the print direction. This is a simplification, as the nozzles are preferably offset by a small amount in the print direction, depending upon there actuation phase (that is, depending on the relative timing that each nozzle is activated).
- the amount that each nozzle is preferably offset in the print direction from the nominal line of nozzles is equal to the difference in activation time of that particular nozzle from the nominal activation time of the row of nozzles times the speed of the print head relative to the print medium. For example, if there are eight actuation phases which are evenly distributed over the nozzle repetition period, then the nozzles corresponding to each actuation phase are preferably offset in the print direction by a multiple of one eighth the pixel width.
Landscapes
- Particle Formation And Scattering Control In Inkjet Printers (AREA)
Abstract
Cette invention concerne une configuration de tête d'impression perfectionnée permettant de conserver la résistance de la microplaquette le long de la ligne des buses à un niveau approximativement égal à 50 % de la résistance normale de la microplaquette. A ces fins, on divise chaque rangée de buses en segments, et l'on déplace certains de ces segments (de préférence un segment sur deux) dans la direction d'impression. Le déplacement du segment de buses se fait suivant la direction d'impression de telle sorte que les buses puissent encore imprimer les mêmes pixels sur le milieu d'enregistrement grâce à une simple modification de l'instant auquel les buses disposent des informations particulières à imprimer. De préférence, les segments déplacés sont déplacés sur une distance légèrement supérieure à la largeur de la fente (ou du canal d'alimentation en encre) dans laquelle les buses du segment approprié sont formées.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AUPN2307A AUPN230795A0 (en) | 1995-04-12 | 1995-04-12 | Nozzle placement in monolithic drop-on-demand print heads |
AUPN2307/95 | 1995-04-12 | ||
PCT/US1996/004857 WO1996032281A2 (fr) | 1995-04-12 | 1996-04-09 | Placement des buses dans les tetes monolithiques d'impression fonctionnant en goutte-a-la-demande |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0772526A2 true EP0772526A2 (fr) | 1997-05-14 |
Family
ID=3786659
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96911653A Withdrawn EP0772526A2 (fr) | 1995-04-12 | 1996-04-09 | Placement des buses dans les tetes monolithiques d'impression fonctionnant en goutte-a-la-demande |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0772526A2 (fr) |
JP (1) | JPH10501767A (fr) |
AU (1) | AUPN230795A0 (fr) |
WO (1) | WO1996032281A2 (fr) |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7455879B2 (en) * | 1996-12-17 | 2008-11-25 | Toray Industries, Inc. | Method and apparatus for producing a plasma display |
US5923348A (en) * | 1997-02-26 | 1999-07-13 | Lexmark International, Inc. | Method of printing using a printhead having multiple rows of ink emitting orifices |
US6786420B1 (en) | 1997-07-15 | 2004-09-07 | Silverbrook Research Pty. Ltd. | Data distribution mechanism in the form of ink dots on cards |
US6618117B2 (en) | 1997-07-12 | 2003-09-09 | Silverbrook Research Pty Ltd | Image sensing apparatus including a microcontroller |
US6690419B1 (en) | 1997-07-15 | 2004-02-10 | Silverbrook Research Pty Ltd | Utilising eye detection methods for image processing in a digital image camera |
US6624848B1 (en) | 1997-07-15 | 2003-09-23 | Silverbrook Research Pty Ltd | Cascading image modification using multiple digital cameras incorporating image processing |
US20090273633A1 (en) * | 1997-07-15 | 2009-11-05 | Silverbrook Research Pty Ltd | Printhead Integrated Circuit With High Density Nozzle Array |
US20090273632A1 (en) * | 1997-07-15 | 2009-11-05 | Silverbrook Research Pty Ltd | Printhead Integrated Circuit With Large Nozzle Array |
US7110024B1 (en) | 1997-07-15 | 2006-09-19 | Silverbrook Research Pty Ltd | Digital camera system having motion deblurring means |
SG112833A1 (en) * | 1997-07-15 | 2005-07-28 | Silverbrook Res Pty Ltd | Re-writable optical card reader/writer unit using ink dots data storage |
US6948794B2 (en) | 1997-07-15 | 2005-09-27 | Silverbrook Reserach Pty Ltd | Printhead re-capping assembly for a print and demand digital camera system |
AUPO850597A0 (en) | 1997-08-11 | 1997-09-04 | Silverbrook Research Pty Ltd | Image processing method and apparatus (art01a) |
US6879341B1 (en) | 1997-07-15 | 2005-04-12 | Silverbrook Research Pty Ltd | Digital camera system containing a VLIW vector processor |
US6985207B2 (en) | 1997-07-15 | 2006-01-10 | Silverbrook Research Pty Ltd | Photographic prints having magnetically recordable media |
AUPP654398A0 (en) | 1998-10-16 | 1998-11-05 | Silverbrook Research Pty Ltd | Micromechanical device and method (ij46g) |
JP4028067B2 (ja) | 1998-02-26 | 2007-12-26 | 東芝テック株式会社 | 記録ヘッドの駆動方法 |
AUPP702098A0 (en) | 1998-11-09 | 1998-12-03 | Silverbrook Research Pty Ltd | Image creation method and apparatus (ART73) |
JP2002527272A (ja) | 1998-10-16 | 2002-08-27 | シルバーブルック リサーチ プロプライエタリイ、リミテッド | インクジェットプリンタに関する改良 |
US6575558B1 (en) | 1999-03-26 | 2003-06-10 | Spectra, Inc. | Single-pass inkjet printing |
US6592204B1 (en) * | 1999-03-26 | 2003-07-15 | Spectra, Inc. | Single-pass inkjet printing |
AUPQ056099A0 (en) | 1999-05-25 | 1999-06-17 | Silverbrook Research Pty Ltd | A method and apparatus (pprint01) |
US6536873B1 (en) | 2000-06-30 | 2003-03-25 | Eastman Kodak Company | Drop-on-demand ink jet printer capable of directional control of ink drop ejection and method of assembling the printer |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5840512B2 (ja) * | 1978-10-04 | 1983-09-06 | 株式会社リコー | インクジェット記録装置 |
US4164745A (en) * | 1978-05-08 | 1979-08-14 | Northern Telecom Limited | Printing by modulation of ink viscosity |
FR2448979B1 (fr) * | 1979-02-16 | 1986-05-23 | Havas Machines | Dispositif destine a deposer sur un support des gouttes d'encre |
US4752783A (en) * | 1986-03-27 | 1988-06-21 | Fuji Xerox Co., Ltd. | Thermal-electrostatic ink jet recording method and apparatus |
GB8912245D0 (en) * | 1989-05-26 | 1989-07-12 | Pa Consulting Services | Liquid jet recording process |
US5469199A (en) * | 1990-08-16 | 1995-11-21 | Hewlett-Packard Company | Wide inkjet printhead |
DE69209684T2 (de) * | 1991-01-30 | 1996-10-17 | Canon Information Syst Res | Düsenstrukturen für Tintenstrahldrucker |
US5278585A (en) * | 1992-05-28 | 1994-01-11 | Xerox Corporation | Ink jet printhead with ink flow directing valves |
JP3384597B2 (ja) * | 1992-11-30 | 2003-03-10 | ヒューレット・パッカード・カンパニー | インク転移印刷装置及び方法 |
JP3047661B2 (ja) * | 1993-02-16 | 2000-05-29 | ブラザー工業株式会社 | 液滴噴射装置 |
-
1995
- 1995-04-12 AU AUPN2307A patent/AUPN230795A0/en not_active Abandoned
-
1996
- 1996-04-09 WO PCT/US1996/004857 patent/WO1996032281A2/fr not_active Application Discontinuation
- 1996-04-09 EP EP96911653A patent/EP0772526A2/fr not_active Withdrawn
- 1996-04-09 JP JP8531106A patent/JPH10501767A/ja active Pending
Non-Patent Citations (1)
Title |
---|
See references of WO9632281A2 * |
Also Published As
Publication number | Publication date |
---|---|
WO1996032281A3 (fr) | 1996-11-14 |
WO1996032281A2 (fr) | 1996-10-17 |
JPH10501767A (ja) | 1998-02-17 |
AUPN230795A0 (en) | 1995-05-04 |
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