The present invention relates to a mounting structure which is arranged at two abutting structural panels (1, 2) so that said structural panels are connected with each other, comprising two pairs of clamping plates, with one of said pairs of clamping plates being fixed to one structural panel (1), and the other pair of clamping plates being fixed to the other structural panel (2). The two pairs of clamping plates abut against each other with one of their clamping plates (3, 4), and the two abutting clamping plates (3, 4) are provided with mutually aligned, undercut longitudinal slots (5) which receive a connecting plate (6) connecting the abutting two clamping plates (3, 4) with each other, and being fixed to the two clamping plates (3, 4) by means of fasteners (7) which extend through said connecting plate (6). Thus, a mounting structure is provided whose manufacture is relatively easy and cost-efficient.

The present invention relates to a mounting structure for two abutting structural panels, in particular glass panels, by which said two panels may be connected with each other.
In a prior art, two laterally abutting structural panels are connected with each other by pairs of clamping plates comprising two plane clamping plates between which the two adjacent lateral edges of the two structural panels are clamped so that the two panels are fixed to each other.
In another prior art, two abutting structural panels are connected by two L-shaped planar clamping plates which are arranged opposite each other, with each of the structural panels being arranged and clamped between one pair of opposing legs of the L-shaped clamping plates.
Two angularly arranged structural panels are conventionally connected by clamping said panels between two angularly formed clamping plates. Said clamping plates are formed by joining two clamping plate portions at a predetermined angle by welding so that an angular clamping plate is formed which defines two clamping planes. Thus, it is necessary to prepare clamping plates having the required angle, and to provide them at the site of assembly.
It is an object of the present invention to provide a mounting structure of the initially described type whose manufacture is relatively easy and inexpensive. Preferably, the mounting structure of the present invention is to be used for structural panels, and in particular glass panels, which are arranged at an angle.
According to the present invention, a mounting structure which may be used for connecting two abutting structural panels, in particular glass panels, with each other comprises two pairs of clamping plates, with one pair of said clamping plates being fixed to one of the structural panels, and the other pair of clamping plates being fixed to the other structural panel, so that each of the two structural panels is clamped between the two clamping plates of the respective pair of clamping plates, with the two pairs of clamping plates abutting against each other with one of their clamping plates, and the two abutting clamping plates being provided with mutually aligned, undercut longitudinal slots which receive a connecting plate connecting the abutting clamping plates with each other and being fixed to the two clamping plates by means of fasteners which extend through said connecting plate.
Preferably, all individual clamping plates of the pairs of clamping plates are of identical cross-sectional shape so that they may be arbitrarily used and interchanged with each other, with their lengths differing in accordance with the particular application. The clamping plates which have an undercut longitudinal slot formed in their surface facing away from the clamping surface are formed as extruded sections, or rolled profiles. The clamping plates may be cut from the sections or profiles to any appropriate lenght. Each of the structural panels and clamping plates comprises at least one through opening through which a locking screw may be inserted so that a clamping connection is established between the two clamping plates and the structural panel arranged therebetween. In the clamping plates, said through openings are preferably formed within the undercut longitudinal slot, and are designed as longitudinal openings so that possible dimensional deviations of the openings in the structural panels may be compensated for during assembly of the clamping plates with the panel. Thus, it may be ensured that the outer edges of the clamping plates and the respective structural panel are flush with each other, even if the opening in the panel was not manufactured with sufficient accuracy. The head of the locking screw and the associated nut are formed such that they are flush with the respective outer surface of the clamping plate, and that their top surfaces do not protrude from the outer surfaces of the opposing clamping plates. After a pair of clamping plates has been mounted on each structural panel, the panels may be connected with each other by inserting one end of a connecting plate into the undercut longitudinal slot of one of the two clamping plates, after which said end is fixed in this slot, so that the other, free end of the connecting plate protrudes from said slot and thus from the edge of the structural panel. Then, the second structural panel may be abuttingly connected with the first panel by inserting the free, protruding end of the connecting plate into the longitudinal slot of one clamping plate of the second panel so that the two clamping plates abut against each other. The two abutting structural panels are connected with each other when the connecting plates in both abutting clamping plates are fixed by means of fasteners extending through said connecting plates. The mounting structure according to the present invention comprising the pairs of clamping plates with mutually aligned longitudinal slots may be easily and cost-effectively manufactured, and may furthermore provide for a simpler assembly of abutting structural panels.
According to an embodiment of the present invention, the two abutting clamping plates are each provided with at least two mutually aligned longitudinal slots so that the two abutting clamping plates, and thus structural panels, may be connected by means of two connecting plates to provide a more stable connection of the two structural panels, if necessary. The clamping plates may also each be provided with three longitudinal slots to be mutually aligned. In this case, a connecting plate connecting the clamping plate with the respective structural panel may for example be inserted in the uppermost and lowermost pair of mutually aligned slots, whereas the intermediate pair of slots comprises the through openings enabling the clamping connection of the pairs of clamping plates with the respective structural panel. Depending on the size of the abutting structural panels, two or more pairs of adjacently arranged clamping plates may be provided at the structural panels.
According to a further embodiment of the present invention, the two pairs of clamping plates are arranged such that a lateral end wall of each clamping plate of each pair abuts against a lateral end wall of a clamping plate of the other pair, and both clamping plates of each pair are provided with undercut longitudinal slots to be aligned with the slots of the abutting clamping plate and wherein connecting plates are fixed by means of fasteners.
According to another embodiment of the mounting structure of the present invention, the abutting clamping plates are arranged such that their longitudinal slots are in transverse or longitudinal alignment with each other, with an angle being included between them, and the connecting plates are formed accordingly to have an angular shape. By means of the mounting structure comprising said clamping plates, it is possible to connect abutting structural panels at any desired angle so that the structural panels received between the clamping plates may be assembled at different planes, which preferably include an angle in the range between 30xc2x0 and 160xc2x0. The structural panels are connected with each other as described above, with only the connecting plates requiring an angular shape. The connecting plates may be bent to the required angular shape directly at the assembly site so that welding operations as required by prior art clamping plates are no longer necessary.
According to another embodiment of the present invention, both clamping plates of one pair of clamping plates abut against one and the same clamping plate of the other pair of clamping plates. In this embodiment, the first pair of clamping plates may for example be arranged at the centre of the lower end wall of a structural panel, and the two clamping plates of the second pair may for example be arranged in perpendicular alignment with one of the clamping plates of the first pair, with the longitudinal slots of the abuttingly aligned clamping plates being in transverse alignment with each other. The two clamping plates of the second pair are each connected with the clamping plate of the first pair by means of a rectangularly formed connecting plate. This clamping plate arrangement enables the connection with each other of two perpendicularly arranged structural panels. Further, a third pair of clamping plates may be arranged in perpendicular alignment with the other clamping plate of the first pair of clamping plates, so that a third structural panel may be connected perpendicularly to the first structural panel. This embodiment is particularly advantageous for four-wing revolving doors, for example. It is further possible to arrange several pairs of clamping plates so that they abut against and are perpendicular to one and the same clamping plate of the first pair of clamping plates. The mounting structure according to the present invention having pairs of clamping plates with mutually aligned longitudinal slots may be used for numerous combinations of abutting structural panels. Another advantage of the mounting structure according to the present invention consists in the fact that it enables the connection with each other of structural panels of different widths, since the connecting plates may be aligned with each other during assembly in accordance with the particular widths of the structural panels to be connected.
According to another embodiment of the mounting structure of the present invention, two pairs of clamping plates are arranged such that an end wall of one clamping plate of the first pair abuts against an end wall of one clamping plate of the second pair, whereas the other clamping plate of each pair abuts against one of the clamping plates of a third pair of clamping plates fixed on both sides of a further structural panel, with said third pair of clamping plates being provided with longitudinal slots in which connecting plates may be fixed so that the third pair of clamping plates may be connected with the two other pairs of clamping plates by means of said connecting plates. This arrangement is particularly advantageous for the assembly of three-wing revolving doors, for example, wherein any two structural panels are arranged at the same angle.
In contrast with the conventional mounting structure comprising preformed angular clamping plates, all the above described embodiments of the present invention may be easily adjusted to the particular case of need by bending the connecting plates to the required shape at the site of the assembly. The plane clamping plates may be provided as sections of several lengths, with the through openings for the locking screws being formed during the cutting of the sections. In all above described embodiments, connecting plates of one and the same shape may be used which merely have to be bent to the required angle.
According to still another embodiment of the present invention, an angularly shaped connecting plate is provided with two recesses in its portion protruding from the undercut longitudinal slot of its associated clamping plate, in which recesses the two shoulders of the longitudinal slot of the other clamping plate may be received. The connecting plates may either be preformed with said recesses, or the recesses may be cut at the site of the assembly.
According to still another embodiment of the present invention, the longitudinal slot of the clamping plate of the first pair of clamping plates against which the two clamping plates of a second pair are to be abutted is provided with recesses in its shoulders through which the leg of a corresponding angular connecting plate may protrude so that it engages said longitudinal slot. In this embodiment, one of the legs of a connecting plate is first inserted through said recesses into the longitudinal slot, and then longitudinally displaced within said slot to a position within the slot at which its entire length is covered by the shoulders of the slot, or at which the other leg of the connecting plate, which protrudes from said slot, abuts against the shoulders of the slot at the edge of the recess. Subsequently, one of the legs of a second connecting plate may be inserted through the recess into said slot, and longitudinally displaced within said slot in an opposite direction as compared to the first displacement, so that the two legs of the two connecting plates protruding from the slot, which were first adjacent to each other, may be arranged at a distance as required for the insertion of a pair of clamping plates having a structural panel clamped between them. The size of the recesses to be provided in the slots depends on the length of the legs of the connecting plates to be inserted, and the recess is designed such that two legs may be inserted through it, and that at least the major part of the length of the leg of the second connecting plate to be inserted will be covered by the shoulder of the slot. Preferably, said recesses are cut out from the shoulders as required at the assembly site.
However, it is also possible to provide clamping plates with mutually aligned longitudinal slots of different widths.
According to this embodiment, the legs of the angular connecting plates are also of different widths so that they match the width of the respective longitudinal slot. This is particularly advantageous for arrangements with transversely aligned longitudinal slots, since it obviates recesses in the shoulders of the slots and in the connecting plates.
The connecting plates are preferably clamped against the shoulders of the respective undercut slot by means of locking screws such as grub screws so that the free ends of the locking screws do not protrude from the outer surface of the clamping plate. However, it is also possible to provide the clamping plates with tap holes into which screws protruding from the connecting plate may be threaded so that the respective connecting plate is screw-fitted with the clamping plate.
According to yet another embodiment of the present invention, the undercut longitudinal slots of at least one of the clamping plates of a pair of clamping plates are provided with mounting inserts, inserted supporting elements for the structural panels, hinges or the like.


An aircraft landing gear steering system comprising a turning member that is operably coupled to a landing gear leg through a harmonic drive mechanism. The landing gear steering system may be electrically driven. Additionally, the landing gear system has various advantages, including the provision of a safe failure mode should the harmonic drive mechanism fail.

1. Field of the Invention
The field of the invention relates generally to aircraft landing gear, and more particularly to improved aircraft landing gear steering systems.
2. Description of Related Art
Most aircraft, and particularly those that are heavier than air, are provided with some type of landing gear. Often such landing gear takes the form of one or more sets of freely rotateable wheels provided on respective wheel train units, which may each be independently retractable into a respective landing gear bay within the fuselage of the aircraft so as to reduce induced drag during flight. Usually, one or more of the wheel train units will also be steerable in order that a pilot can direct the aircraft on the ground. For example, it is fairly common with a tricycle-type undercarriage arrangement that the nose-wheel wheel train unit can be independently rotated relative to the aircraft fuselage in order to steer the aircraft.
Various steering arrangements for aircraft landing gear are known. One common type uses a hydraulically driven mechanical arrangement to steer aircraft [1-7]. However, the hydraulic pipes and actuators needed for such steering arrangements tend to be heavy and bulky, thereby taking up a relatively large amount of space in a landing gear bay. Additionally, hydraulic fluid is used and any leaks from such systems are problematic in the aircraft.
As an alternative to hydraulically driven arrangements, various electrically driven aircraft steering systems have also been developed [8-11]. However, these tend to be used mainly on various light aircraft because they generally have poor mechanical failure characteristics which can, for example, lead to a locking of the steering mechanism should the steering system fail. Such failure modes can be dangerous, and this is one reason why electrical steering systems have not generally been adopted for larger aircraft, such as, for example, those used for commercial air transport applications.
Additionally, certain conventional aircraft landing gear steering systems may also have poor mechanical vibration characteristics. For example, nose wheels of conventional systems can have a tendency to shimmy, or oscillate uncontrollably from side-to-side, when the aircraft touches down. This characteristic is undesirable, and may be reduced for hydraulically driven systems, for example, by providing a hydraulic accumulator and valves to increase hydraulic fluid pressure in the steering system during touch-down. Such a hydraulic accumulator and valves, however, not only add to the weight and complexity of certain conventional aircraft steering systems, but also increase the likelihood that hydraulic fluid leaks will occur.
Various aspects and embodiments of the present invention have therefore been developed whilst bearing the aforementioned disadvantages of conventional aircraft landing gear steering systems in mind.


A method and device for controlling an electric motor, in particular a machine tool drive, wherein during a sensorless open-loop control mode of operation of the electric motor the speed and the torque are determined from the motor current and the motor voltage, and the moment of inertia of the electric motor torque are determined from the determined motor current and the determined motor voltage, wherefrom then a control torque is determined, which is then associated with an open-loop torque control value and supplied as the torque setpoint value to a control element for setting the motor current and/or the motor voltage in the open-loop mode of operation. As long as the speed is below a minimum speed, the control element receives as input variable a control or pilot control torque generated from a predefined moment of inertia for a sensorless closed-loop control mode of operation of the electric motor.

The present invention relates to a method and a device for controlling a sensorless electric motor, in particular a machine tool drive. The method and device find applications in technical fields in which machine tools are driven by an electric motor.
The following discussion of related art is provided to assist the reader in understanding the advantages of the invention, and is not to be construed as an admission that this related art is prior art to this invention.
Sensorless operation of an electric motor, in other words operation of an electric motor without a rotational speed sensor, is of considerable importance in many applications for driving machine tools. Reasons for this are firstly cost savings and secondly the reliability of the drives, since without speed sensors no failures induced thereby can be caused either.
A sensorless electric motor that is used within a drive, in particular a machine tool drive, is driven in a open-loop control mode of operation in the lower speed range, for example within a speed range of approximately 10% of the rated speed. The reason for this is that in this range the motor model cannot provide an actual value for the speed, which value is required in order to regulate the electric motor. If the electric motor is accelerated or decelerated during sensorless operation with an excessively high change in frequency or an excessively high speed stroke, there is a risk that the electric motor will "buck". The term "bucking" of an electric motor means in this context that the electric motor is unable to follow the change in frequency or the required speed stroke and as a result has reached a maximum permitted slip value, for which reason the torque of the electric motor collapses abruptly. The consequence of this is that the electric motor no longer accelerates or no longer delivers a torque required for the drive.
If, on the other hand, the electric motor is accelerated or decelerated with a correspondingly low change in frequency or a correspondingly low speed stroke, time available for accelerating and decelerating would not be used.
It would therefore be desirable and advantageous to obviate prior art shortcomings and to provide an improved to method for controlling an electric motor which is used in particular in a machine tool drive and which enables the electric motor to accelerate or decelerate in a maximally time-saving manner. A further object is to disclose a corresponding device for performing the method.

Method and device for controlling an electric motor


A cutting tool to be utilized in the resection or removal of bone tissue from patients includes a handle that tensions a wire or cable-like cutting member with a small diameter between at least two features on the handle to present a thin cutting profile. The design of the cutting tool includes features that protect against soft tissue damage and minimize the incision size necessary to utilize the tool. Some embodiments feature details of the cutting tool that interface with a surgical cutting guide system. Other embodiments describe a cutting tool with a selectively changeable length of the cutting profile of the wire cutting member. In one embodiment, the wire cutting member of the cutting tool is energized by mechanical energy in the form of a unidirectional rotation of the cutting member, a mechanical vibration of the cutting member, or an oscillating movement of the wire cutting member.

1. Field of the Invention
This invention generally relates to methods and apparatus for bone resection to allow for the interconnection or attachment of various prosthetic devices with respect to the patient. More particularly, the present invention relates to the use of a wireplasty bone resection technique in which wires or cables act as bone cutting tools.
2. Background Art
Different methods and apparatus have been developed in the past to enable a surgeon to remove bony material to create specifically shaped surfaces in or on a bone for various reasons including to allow for attachment of various devices or objects to the bone. Keeping in mind that the ultimate goal of any surgical procedure is to restore the body to normal function, it is critical that the quality and orientation of the cut, as well as the quality of fixation, and the location and orientation of objects or devices attached to the bone, is sufficient to ensure proper healing of the body, as well as appropriate mechanical function of the musculoskeletal structure.
In total knee replacements, for example, a series of planar and/or curvilinear surfaces, or "resections," are created to allow for the attachment of prosthetic or other devices to the femur, tibia and/or patella. In the case of the femur, it is common to use the central axis of the femur, the posterior and distal femoral condyles, and/or the anterior distal femoral cortex as guides to determine the location and orientation of distal femoral resections. The location and orientation of these resections are critical in that they dictate the final location and orientation of the distal femoral implant. It is commonly thought that the location and orientation of the distal femoral implant are critical factors in the success or failure of the artificial knee joint. Additionally, with any surgical procedure, time is critical, and methods and apparatus that can save operating room time, are valuable. Past efforts have not been successful in consistently and/or properly locating and orienting distal femoral resections in a quick and efficient manner.
The use of oscillating saw blade based resection systems has been the standard in total knee replacement and other forms of bone resection for over 30 years. Unfortunately, present approaches to using such planar saw blade instrumentation systems all possess certain limitations and liabilities.
Perhaps the most critical factor in the clinical success of any bone resection for the purpose of creating an implant surface on the bone is the accuracy of the implant's placement. This can be described by the degrees of freedom associated with each implant. In the case of a total knee arthroplasty (TKA), for example, for the femoral component these include location and orientation that may be described as Varus-Valgus Alignment, Rotational Alignment, Flexion-Extension Alignment, A-P location, Distal Resection Depth Location, and Mediolateral Location. Conventional instrumentation very often relies on the placement of ⅛ or 3/16 inch diameter pin or drill placement in the anterior or distal faces of the femur for placement of cutting guides. In the case of posterior referencing systems for TKA, the distal resection cutting guide is positioned by drilling two long drill bits into the anterior cortex along the longitudinal axis of the bone. As these long drills contact the oblique surface of the femur they very often deflect, following the path of least resistance into the bone. As the alignment guides are disconnected from these cutting guides, the drill pins will "spring" to whatever position was dictated by their deflected course thus changing their designated, desired alignment to something less predictable and/or desirable. This kind of error is further compounded by the "tolerance stacking," inherent in the use of multiple alignment guides and cutting guides.
Another error inherent in these systems further adding to mal-alignment is deflection of the oscillating saw blade during the cutting process. The use of an oscillating saw blade is very skill intensive as the blade will also follow the path of least resistance through the bone and deflect in a manner creating variations in the cut surfaces which further contribute to prosthesis mal-alignment as well as poor fit between the prosthesis and the resection surfaces. Despite the fact that the oscillating saw has been used in TKA and other bone resection procedures for more than 30 years, there are still reports of incidences where poor cuts result in significant gaps in the fit between the implant and the bone. The safety of these saws is also questionable as minor incidences of misuse can result in serious harm and disability.
While oscillating saws have been the preferred tools for performing bone resections as part of an implantation procedure, other forms of bone saws and cutting instruments have also been used to cut bones. Generally, the problems of precision, accuracy and safety of these other cutting instruments are even greater than with an oscillating saw. U.S. Pat. No. 5,725,530 describes a planar surgical saw that utilizes a dual chain saw arrangement with guards along the outer sides of the chain saw blades. A surgeon's gigli saw, for example, has a cutting wire with a handle on each end that is wrapped around a bone to be cut. The surgeon alternates pulling each handle to run the cutting wire back and forth around the bone to cut the bone. U.S. Pat. No. 4,709,699 describes an improved cutting wire for a surgeon's gigli saw. U.S. Pat. No. 6,368,353 describes the use of a gigli saw for resecting the neck of the humerous bone as part of an implant procedure for a shoulder prosthesis. Although conventional chain saws and gigli saws can be very efficient general purpose cutting tools, these saws have little ability to be guided and aligned so as to make the precise and accurate resection cuts required for effective implants.
Improvements in the precision, accuracy, and safety of tools for resecting bone surfaces are desired in order to increase the efficacy of orthopedic procedures and enable the surgeon to better achieve the benefits of a standard, less invasive, and more efficacious joint reconstruction.

Method and apparatus for wireplasty bone resection


A hand held, manually operated paper folding device, made out of thin, high density material, divided into four sections by specially introduced flexible joints. Three of the sections are similar and together equal the size of a standard paper sheet which is placed on top of these sections prior to the folding process. The fourth section is about 1/8" narrower, which allows it to be folded on top of the adjacent third section, providing means to accommodate, align and hold paper sheets between the third and the forth sections, while also permitting the following folding of all three equal sections in a zig zag fashion, generating within one motion, buckling, formation of two sharp creases and the uniform triple folding of all inserted paper sheets. The inherent springiness of the folded paper sheets and the paper sheet folding device itself assures the release of all paper sheets after the completion of the folding process and release of the paper sheet folding device.

A variety of automatic, semi-automatic and manually operated mechanisms have been introduced to simplify, accelerate and standardize the process of paper sheets and document folding, thereby expediting their insertion into envelopes.
The most popular triple folding method, if performed manually, requires substantial skill or time and is tiring and unkempt when large volumes of mail have to be handled.
Heretofore two main types of paper sheets folding mechanisms have been evaluated.
Automatic paper sheets folding mechanisms with a complex feeding, holding and buckling actions are described in various sources and patents. The most typical representation of these mechanisms is offered in U.S. Pat. No. 5,000,432 by Marek Krasuski, et al. or U.S. Pat. No. 5,114,395, by Richard J. Abramson. These devices are developed in order to handle large volumes of identical sheets of mail and have restrictions as to the number of sheets in the stack as well as their orientation and alignment. They can be described as complex, power driven mechanisms with multiple rollers and an elaborate sequence of motions, providing a fast folding process for the properly inserted sheets of paper. Both price and maintenance of automatic folding mechanisms can be prohibitive either for private or business office use.
Suggested manual folding mechanisms are rare, bulky, inefficient and too expensive to justify either their widespread production or utilization. One of the manually operated folding guides, described in U.S. Pat. No. 4,421,500 by Samuel C. Smith, consists of a table top horizontal surface with two side flaps, which, when folded sequentially on top of the main horizontal surface, generates two creases on the paper sheet, located on top of the device. This unit requires careful orientation, positioning and insertion of the paper under the specially provided side holding tabs before the start of the folding process. The device is complex in use and in production, equipped with additional resilient flap opening elements, occupies substantial working space and requires a sequence of multiple operations, including the insertion of paper sheets, location of said paper under special guides or retainers, closing and opening of said flaps, as well as the following steps of removal of the creased but unfolded document.
It would be highly desirable, therefore, to have a manually operated, hand held paper folding device, which will have no mechanical or electrical components, will assure the aligning and uniform triple folding of multiple sheets of paper in one motion, will assure easy insertion and extraction of those sheets in folded condition, will be light, user friendly, affordable and portable.


Apparatus and methods are described for solids deposition study. One apparatus embodiment of the invention comprises an internal and an external cylinder positioned between first and second end portions, at least one of the cylinders being rotatable and thus forming a Couette-Taylor cell, the internal cylinder having an exterior surface, the external cylinder having an internal surface, an annular sample flow-through chamber or cell formed between the surfaces, optionally the chamber having an adaptable flow-through chamber geometry, the device having a sample inlet and outlet; and a non-intrusive probe for detecting solids deposition on at least one of the surfaces during sample flow through the apparatus. Apparatus described may be used to studying solids deposition from heavy hydrocarbon oils, hydrates, and other high viscosity compositions. This abstract complies with rules requiring an abstract. It should not be used to limit the scope or meaning of the claims.

1. Field of Invention
The present invention relates generally to the field of solids deposition on surfaces, and more particularly to apparatus and methods for producing layers of solids deposits under continuous flow conditions as a function of influencing variables including, but not limited to flow rate, temperature, pressure, shear, surface type, surface roughness, chemical inhibitors and chemical inducers. The apparatus and methods are useful for predicting solids deposition from fluids including, but not limited to reservoir hydrocarbon and aqueous based fluids, drilling muds, frac fluids, emulsions, and the like, which may have multiple phases (solid, liquid, gas, and combinations thereof).
2. Related Art
Oil fields flow assurance characterizes the operability and reliability of oil and/or gas production systems. Organic and inorganic solids (wax, asphaltenes, hydrates, scale, and the like) precipitation, deposition, emulsion, foaming, corrosion, erosion, inhibition, rheology, and complex multi-phase flow are some of the key issues related to flow assurance. Many flow problems are due to hydrates, wax, asphaltene and scale precipitation, which may lead to deposition on internal pipe and other equipment surfaces, causing pressure reduction, slower production, and ultimately plugging. Moreover, elevated viscosity at low temperatures (gelling) represents potential rheological problems, which may lead to slugging.
One aspect of "flow assurance" is managing the precipitation and deposition formation of these solids: wax, asphaltene, scales, hydrates, among many others. Even though solids precipitation is a prelude to solids deposition, their presence can be passive if proper measures are taken to avoid their adhesiveness to surfaces. It is now proven that any solids deposition occurrence can be a function of any of the following parameters: composition, viscosity, production rate, system pressure, system temperatures, and presence of water, deposition surface type and deposition surface roughness. Solutions to remediate the deposition problem vary from mechanical design to chemical injection. The economic implication, if wrong assessments are made, can be very serious and lead to significant losses due to slow production or shut down. Even though the subject of oil production has been well investigated, the tools to predict and conceptually design the production system, including pipelines, based on reliable experimental measurements and evaluation are very few. So far, very limited and unreliable experimental predictive methods and approaches are available to assess and quantify the wax deposition process, especially under various actual pipeline conditions and/or reservoir conditions. Most available methods fall short in mimicking the actual pipeline turbulent conditions in general, especially at relatively high Reynolds number and high shear. For the asphaltene deposition process, only one known tool, known under the trade designation OSDC (discussed below) is available to trigger and measure deposition under real pipelines conditions of shear, pressure and temperature. There are no known tools or devices available to evaluate, predict, measure or produce scale and hydrates deposits under transport conditions whether at steady state or transient.
Schlumberger has used the system known as the Organic Solids Deposition and Control system (OSDC), described more fully in U.S. Pat. Nos. 6,959,588 and 7,150,183, to identify, produce and control both wax and asphaltene deposits at very realistic reservoir as well as transport conditions. The experimental results using the system known as OSDC were benchmarked against field data and were found to be conservative, yet superior when compared to any other methods such as flow loops, cold finger and stirring tanks. Feedback from major oil companies was very encouraging. The experimental data from live oils, which are expensive to sample, are invaluable.
Despite success of the apparatus known under the trade designation OSDC, the system has numerous limitations in terms of being capable to meet the fast-growing and continuously evolving market. The high cost of the live oil sample collection and its uniqueness make it challenging and crucial for the industry to minimize the risks of not only losing the sample, but most importantly to extract the maximum information possible from it. Better controllability, more powerful hardware, improved design and enhanced geometry are desired to achieve ideal data quality and greater profitability.

Apparatus and methods for solids deposition and analysis


A rapidly heating curling iron with a handle, a hollow barrel secured to the handle, and a heating element positioned within the barrel, the heating element being an electrical insulating board wound with electrical wire. A pair of heat transmission members are positioned with one on each side of the heating element, but with electrical insulation between the heating element and the heat transmission members. The heat transmission member are shaped and dimensioned such that they fit between the electrical insulation and the inner surface of the barrel and press against a substantial portion of the inner surface, a temperature sensor positioned to sense the temperature of the barrel, and a control circuit allows the heating element to be energized only during one half cycle of supplied AC power, and adjusts the portion of the half cycle which is used in accordance with the sensed temperature.

Many curling irons are heated by having rope heaters within their barrels. These normally operate at about ten to thirty watts and may require as long as five minutes to heat the barrel to working temperature. Efforts to increase this heating time by increasing the wattage can cause excessive internal temperature which can break down the rope heater and cause a shock hazard.
The present invention is a structure which provides for rapid heating without the possibility of breakdown.

Fast heating curling iron and control circuit therefor


A method of forming a corrosion resistant neutron absorbing coating comprising the steps of spray or deposition or sputtering or welding processing to form a composite material made of a spray or deposition or sputtering or welding material, and a neutron absorbing material. Also a corrosion resistant neutron absorbing coating comprising a composite material made of a spray or deposition or sputtering or welding material, and a neutron absorbing material.

1. Field of Endeavor
The present invention relates to corrosion resistant materials and more particularly to corrosion resistant neutron absorbing materials and methods of forming corrosion resistant neutron absorbing materials and coatings. These coatings may include either homogeneous metallic alloys, or metal-ceramic composites, where the metallic alloy or the binder in the metal-ceramic composite could be a boron-containing iron-based amorphous metal, engineered for outstanding corrosion resistance.
2. State of Technology
U.S. Pat. No. 5,744,254 for composite materials including metallic matrix composite reinforcements issued Apr. 28, 1998 to Stephen L. Kampe and Leontios Christodoulou provides the following state of technology information, "Metal matrix composites comprising discontinuous ceramic reinforcements are under consideration for an increasing number of applications. Such composites have been highly touted as efficient material alternatives to conventional ferrous and nickel-base alloys presently incorporated in high performance, high temperature applications. Prominent among those who have invested heavily in the field are the automotive and aerospace industries, in efforts to improve fuel efficiency and performance. Other industries with interest in metal matrix composites include heavy equipment manufacturers and tooling industries such as drilling, mining and the like."
U.S. Pat. No. 6,767,419 for methods of forming hardened surfaces issued Jul. 27, 2004 to Daniel J. Branagan provides the following state of technology information, "Steel is a metallic alloy which can have exceptional strength characteristics, and which is accordingly commonly utilized in structures where strength is required or advantageous. Steel can be utilized, for example, in the skeletal supports of building structures, tools, engine components, and protective shielding of modern armaments."
United States Patent Application No. 2005/0117687 by George Carver et al for container and method for storing or transporting spent nuclear fuel, published Jun. 2, 2005, provides the following state of technology information: "Typically, spent nuclear fuel discharged from fission reactors is stored in deep pools filled with water to dissipate heat and to attenuate the gamma and neutron radiation generated by the fuel. This is called a wet storage system. An alternative method to storing the spent nuclear fuel is a dry storage system that uses a horizontal or vertical configuration having either a heavy wall protected vessel referred to as a cask or over-pack, or a thin walled vessel called a canister. Dry storage systems can also be used to transport spent fuel between storage locations. For dry storage system, the canister can be separately placed into the cask or over-pack. The structure that provides support for the spent nuclear fuel for dry storage and transportation systems is referred to as a fuel basket. The fuel baskets are designed to meet the compressive loads criteria contained within regulations, codes, and standards, particularly conditions for storing and transporting nuclear spent fuel. Dry storage and transportation basket designs include a tube and disk flux trap configuration, an egg crate interlocking plate configuration, a developed cell configuration and a stacked tube configuration."
The article "Corrosion Characterization of Iron-Based High-Performance Amorphous-Metal Thermal-Spray Coatings" by J. C. Farmer et al, ASME Pressure Vessels & Piping Division Conference, Denver, Colo., Jul. 17, 2005 through Jul. 21, 2005 provides the following state of technology information, "New corrosion-resistant, iron-based amorphous metals have been identified from published data or developed through combinatorial synthesis, and tested to determine their relative corrosion resistance. Many of these materials can be applied as coatings with advanced thermal spray technology . . . . Such materials could also be used to coat the entire outer surface of containers for the transportation and long-term storage of spent nuclear fuel, or to protect welds and heat affected zones, thereby preventing exposure to environments that might cause stress corrosion cracking."
The article "Corrosion Resistance of Iron-based Amorphous Metal Coatings" by J. C. Farmer et al, Pressure Vessels & Piping Division, Conference, Vancouver, Canada, Jul. 23, 2006 through Jul. 27, 2006 provides the following state of technology information, "New amorphous-metal thermal-spray coatings have been developed recently that may provide a viable coating option for spent nuclear fuel & high level waste repositories."

Corrosion resistant neutron absorbing coatings

Lawrence Livermore National Security, LLC

The United States of America as Represented by the Secretary of the Army


A novel serial data communication interface architecture is provided having two modes of operation that are accessed through a chip select signal in combination with a successive approximation registers signal (SARS). Once the internal data conversion begins, the chip select signal may change to any signal state without interrupting the conversion process. Serial interface data output and SARS lines are tri-stated during conversion, while the chip select signal is high. This allows data input, data output, and SARS lines to serve other purposes during conversion. If chip select signal is high at the falling edge of SARS, converted data DO bits are then provided to an internal output register. However, DO data are not immediately routed to the output. Clocking of the output data does not resume until at the first transition to low of chip select signal after the falling edge of SARS. The next conversion is not initiated until the second transition of chip select back to low after the falling edge of SARS signaling the end of conversion.

It is known to use a plurality of lines in a bus to transmit a plurality of data bits simultaneously, thereby achieving high data transmission rates. However, certain devices, are designed to transmit and receive data in a serial format, thereby sacrificing data rate to minimize the number of interface lines.
Two prior art serial communication interface configurations are known and commonly implemented with A/D converters. These two types of configurations are known as the nonregistered configuration and the registered configuration. FIG. 1b illustrates an example of a timing diagram corresponding to a nonregistered type serial interface shown in FIG. 1a, and FIG. 2b shows a timing diagram corresponding to a registered type serial interface of FIG. 2a. In both configurations, conversion begins when the Not Chip Select ("/CS") signal transitions from a logic "one" (high) to a logic "zero" (low). During the first five system clock cycles ("CLK"), the first five data input ("DI") bits provided are latched. These include the start bit, a single-ended or differential mode bit, a sign bit, and two bits for channel selection. After a predefined acquisition period T.sub.acq following the falling edge of the fifth CLK cycle, Successive Approximation Registers ("SARS") signal transitions from low to high, indicating the beginning of data conversion, i.e. such as A/D conversion.
FIG. 1b shows a prior art nonregistered format serial communication interface process which invokes conversion of DI bits upon detecting the signal state of /CS signal as being asserted, i.e. low, and Successive Approximation Register Signal (SARS) as being high. Prior art nonregistered configuration serial interfaces output converted data output ("DO") bits during the data conversion. Converted data DO are therefore not stored internally, but are provided serially at a data output signal port (not shown) as each successive DO bit becomes available. As shown in FIG. 1b converted data bit DO of nonregistered type serial interface is available upon the serial interface detecting the rising edge of SARS, with the most significant bit (MSB) DO bit provided first at the output port. However, the nonregistered approach as shown in FIG. 1b is not always practical beyond 12 bits due to induced noise from the output buffer.
FIG. 2b illustrates a registered configuration serial interface. In the registered format, the converted bits are available at the data output only after the entire conversion process has been completed. During conversion, converted data, DO bits, are temporarily stored in an internal register until conversion of data DI is completed. When SARS transitions from high to low, the falling edge of SARS is used to indicate the end of data conversion. Upon the next rising edge of CLK, DO bits are provided to the data output port (not shown) with the Least Significant Bit (LSB) first. Thus, in the registered type serial interface, the LSB of DO is first routed to the data output signal port followed by the subsequent bits.
In both the registered and the nonregistered configuration the system microprocessor must continuously monitor the status of the conversion, i.e. the changing state of SARS to detect the falling edge of SARS, which is additional overhead for a system microprocessor. Moreover, during this conversion process, /CS must be low for the selected chip to remain active. Since /CS is asserted during a conversion, other chips which share the same input or output ("I/O") signal lines, such as SARS, DO, and DI, cannot be selected during the conversion process. Thus, prior art registered or nonregistered format serial interfaces do not efficiently accommodate systems having multiple A/D converters, or multiple I/O devices.
Another prior art serial interface uses a modified registered output configuration such as the registered type A/D serial interface ADC0819 ("the ADC0819") provided by National Semiconductor Corporation. The modified registered serial interface of the ADC0819 implements two clock signals for serial interface operation. The first clock (CLK1) is a system operation clock, and the second clock (CLK2) is an I/O interfacing clock. FIGS. 3 and 4 illustrate two alternative modes of operation available with the modified registered serial interface configurations provided by the ADC0819. FIG. 3 shows a first operation mode of ADC0819, where data conversion is invoked with the rising edge of /CS. Since no SARS is provided in the ADC0189, /CS remains high during data conversion. After data conversion is completed, and on the falling edge of /CS, converted data DO bits are provided at a data output port.
FIG. 4 shows a second operation mode of the modified registered output configuration provided by ADC0819. Clock signal CLK2 is used to control the output of converted data DO to the data output port. When the last converted data DO bit is transferred to an output data shift register, CLK2 is inhibited thereby preventing clocking out of DO. After a prescribed time (a minimum of 16 .mu.sec for the ADC0819), CLK2 is restarted and converted data DO is provided serially to the output port, The modified registered serial interface of ADC0819 not only requires an extra clock signal, but also requires additional overhead control circuitry.
Thus, with prior art registered type serial interface architecture, such as the one exemplified in FIG. 1b, microprocessor overhead exists to continuously monitor for the falling edge of SARS to detect the end of data conversion. Alternatively, in most applications of serial interfaces where data is not needed immediately after conversion, delays to providing the output data DO may be achieved by the modified registered type serial interface ADC0819 (FIGS. 3 and 4). However, such delayed output is achieved at a cost of requiring an additional clock signal. Moreover, inhibiting data output requires precise clock signal edge detection, which is cumbersome to implement and consumes system microprocessor overhead. Although the nonregistered configuration serial interface (shown in FIG. 2b) is faster than registered configuration, the nonregistered configuration serial interface is more sensitive to internal noise. Thus, there is a need for an efficient serial communication interface architecture that provides controllable delay to data output, while minimizing additional circuitry and system overhead.

Serial data communication interface architecture


Provided is a method for controlling a laser oscillator. Such a laser oscillator is applicable to a laser processing machine and includes a plurality of oscillator modules each adapted to be driven to oscillate a laser beam. Also, such a laser oscillator is configured to collect laser beams oscillated by driven modules for output. The method includes determining the number of modules to be driven, of the plurality of oscillator modules.

A laser oscillator for laser processing application may include a couple of oscillator modules each operable to oscillate a laser beam, so that the laser beams oscillated by these oscillator modules can be collected for output. Each of such oscillator modules by itself can adequately provide for a laser oscillator, as well. Such oscillator modules are often combined to provide for a laser oscillator of a significant output that cannot be achieved with a single oscillator module, and a number of the oscillator modules may be employed according to the required output power of the laser oscillator. In sheet metals cutting application, for example, a large number of oscillator modules are associated with a laser processing machine to meet the demand for a greater cutting capability.
Conventionally, to adjust the output power of a laser oscillator that includes a plurality of oscillator modules, control is applied such that all of the oscillator modules are adjusted by the same proportions. For example, to adjust the output power of a laser oscillator to 50% of its maximum rated output, control is applied such that all of the output powers of the oscillator modules are regulated to 50% of their maximum rated output (see JP Laid-open Patent Publication No. 2003-037316).
When the output power of a laser oscillator is set low relative to its maximum rated output, a laser processing operation becomes unstable. Normally this is due to poor control resolution of the output of a laser oscillator; for example, control of a laser oscillator within the range of less than 10% of its maximum rated output is very difficult. This, in turn, makes it difficult to perform fine adjustment of its output in response to changes in the designated value for the output power that occur during a laser processing operation. In this way, considerable output fluctuations may occur during the processing operation. As such, fine adjustment is difficult and stable processing quality cannot be achieved. This also applies to a laser oscillator including oscillator modules whose output powers can be designated to select levels. A laser processing operation stabilizes when the designation is to a higher output power (e.g., 40% of the maximum rated output), better than when the designation is to a lower output power (e.g., 10% of the maximum rated output).
In laser cutting of a sheet metal, a correct curve shape requires the movement of a laser beam at a speed lower than when cutting a linear shape. When moving a laser beam at a lower speed, it may be necessary to reduce the laser output power because otherwise the heat input from the laser beam into a material undesirably increases. However, the aforementioned limit on the fine adjustment capability does not allow for regulation of the laser output power to a proper level. The resulting overheating or inadequate heat input jeopardizes a stable processing operation.


A method for creating word models for a large vocabulary, natural language dictation system. A user with limited typing skills can create documents with little or no advance training of word models. As the user is dictating, the user speaks a word which may or may not already be in the active vocabulary. The system displays a list of the words in the active vocabulary which best match the spoken word. By keyboard or voice command, the user may choose the correct word from the list or may choose to edit a similar word if the correct word is not on the list. Alternately, the user may type or speak the initial letters of the word. Then the recognition algorithm is called again satisfying the initial letters, and the choices displayed again. A word list is then also displayed from a large backup vocabulary. The best words to display from the backup vocabulary are chosen using a statistical language model and optionally word models derived from a phonemic dictionary. When the correct word is chosen by the user, the speech sample is used to create or update an acoustic model for the word, without further intervention by the user. As the system is used, it also constantly updates its statistical language model. The system gets more and more word models and keeps improving its performance the more it is used. The system may be used for connected speech as well as for discrete utterances.

In recent years, increasingly powerful speech recognition systems have begun to appear. For example, the assignee of the present invention markets a speech recognition system capable of recognizing active vocabularies up to 5,000 words in real-time on a personal computer. To get the best possible performance on difficult tasks such as recognition of a vocabulary of 5,000 words or more, it is desirable to train the system to the voice of each individual user. It is also desirable to customize the vocabulary to the particular subject matter and to the vocabulary usage of the individual user. To get the best results in recognizing unconstrained natural text, it is desirable to use higher-level linguistic knowledge that predicts which words are most probable, based on the context.
However, to make it possible to train the system to the voice of the individual user, it has been necessary in prior art speech recognition systems for the user to record the entire vocabulary, or else to separately record a special training or enrollment vocabulary before any words can be recognized. To customize the vocabulary and the higher-level linguistic knowledge, it has been necessary for the user to supply large amounts of sample text from which the statistical linguistic characteristics can be derived. There is a significant amount of time, effort, and expense that is necessary before such a large vocabulary, natural language recognition system is ready to be used by a new speaker or in a new area of subject matter.
Among the techniques in prior art speech recognition to limit or reduce the training and customization time is the use of speaker-independent acoustic models. Unfortunately, speaker-independent acoustic models must allow for the total amount of variability in the way a given word can be pronounced by many different speakers. This tends to result in fuzzy, or poorly defined, word models. With this variability, or fuzziness, there will be a greater amount of overlap between the region of acoustic parameter space that represents a given sound and the region which represents a different, but similar sound. Thus, other things being equal, there will be a higher error rate in a speech recognition system using speaker-independent acoustic models than in a speech recognition system using speaker-dependent acoustic models. For large vocabulary, natural language speech recognition tasks, it is important to get the highest possible performance in the acoustic recognition, because the overall recognition task is very difficult.
To get the best possible performance, therefore, the acoustic models and the linguistic model should be customized. The disadvantage of the customization, however, is the cost in time of the customization, and the delay before the speech recognition system can be used for productive work.

Method for interactive speech recognition and training


A composition comprising a dye of Formula (I) and a dye of Formula (II) or salts thereof, and use of the composition in ink jet printing

This invention relates to dye compositions and to their use in ink jet printing (xe2x80x9cIJPxe2x80x9d). IJP is a non-impact printing technique in which droplets of coloured liquids are ejected through a fine nozzle onto a substrate without bringing the nozzle into contact with the substrate.
There are many demanding performance requirements for dyes and inks used in IJP. For example they desirably provide sharp, non-feathered images having good water-fastness, light-fastness, chroma, and optical density. The inks are often required to dry quickly when applied to a substrate to prevent smudging, but they should not form a crust over the tip of an ink jet nozzle because this will stop the printer from working. The inks should also be stable to storage over time without decomposing or forming a precipitate which could block the fine nozzle. Thermal and piezoelectric ink jet printers are widely used, thus there is a need for inks, suitable for use in both types of printers, having high colour strength and giving images having good light fastness when printed on a typical substrate, especially plain paper.
Inks containing dyes are known for example from U.S. Pat. No. 5,622,550 which discloses a yellow ink composition comprising a mixture of a triazine linked carboxylated azo benzenoid dye with a triazine linked sulphonated azo benzenoid dye or a pyrazolone linked sulphonated dye.
EP 763 576 discloses the use of yellow dye mixtures comprising dyes containing carboxy groups with dyes containing a SO3H group.
We have found that a combination of a triazine linked azo benzenoid dyes with a pyridone dye provides an improved balance of lightfastness, chroma and dye solubility.
According to a first aspect of the present invention there is provided a composition comprising a dye of Formula (I) and a dye of Formula (II) or salts thereof:
wherein
Ar1, Ar2, Ar3, Ar4 and Ar5 are each independently optionally substituted aryl;
R1 is alkyl, alkenyl, alkynyl, pyridinium or aryl, each of which is substituted or unsubstituted, or H;
R2 is alkyl, alkenyl, alkynyl, pyridinium or aryl, each of which is substituted or unsubstituted, H, C(O)OH, CN, NR5R6 or C(O)NR5R6; and
R3, R4, R5 and R6each independently are alkyl, alkenyl, alkynyl or aryl, each of which is substituted or unsubstituted, or H;
L is H or L and R4 together with the N atom to which they are attached form an optionally substituted 5- or 6-membered ring.
Preferably the dye of Formula (I) is of the formula:
wherein:
R7 is alkyl, alkoxy, alkenyl, alkynyl or aryl, each of which is substituted or unsubstituted, H, SO3H, C(O)OH, PO3H, NR5R6 or C(O)NR5R6;
p is 0, 1, 2or 3; and
R1, R2, R3, R5 and R6 are as defined above.
Preferably the dye of Formula (II) is of the formula:
wherein
each R8 independently is alkyl, alkenyl, alkynyl or aryl, each of which is substituted or unsubstituted, H, NHC(O)R5 or NHC(O)NR5R6;
each R9 independently is alkyl, alkenyl, alkynyl, or aryl, each of which is substituted or unsubstituted, H, SO3H, PO3H or NH3+;
each m independently is 0, 1, 2 or 3; and
L, R4, R5, R6, Ar3 and Ar5 are as defined above.
Preferably L is H.
Preferably R1 is C1-C25alkyl, C2-C25alkenyl, C2-25alkynyl, pyridinium or aryl, each of which is substituted or unsubstituted, or H; more preferably R1 is H or optionally substituted C1-C15alkyl; most preferably R1 is C1-C10alkyl or xe2x80x94SO3H substituted C1-C10alkyl;
Preferably R2 is C1-C25alkyl, C2-C25alkenyl, C2-C25alkynyl, pyridinium or aryl, each of which is substituted or unsubstituted, H, C(O)OH, CN, NR5R6 or C(O)NR5R6; more preferably R2 is pyridinium or C1-C15alkyl each of which is substituted or unsubstituted, H, C(O)OH, CN, NR5R6 or C(O)NR5R6; most preferably R2 is pyridinium or C1-C10alkyl, each of which is substituted or unsubstituted H, C(O)OH, CN, NR5R6 or C(O)NR5R6.
Preferably R3, R4, R5 and R6 each independently are C1-C25alkyl, C2-C25alkyenyl, C2-C25alkynyl or aryl, each of which is substituted or unsubstituted, or H; more preferably R3, R4, R5 and R 6 each independently are C1-C20alkyl, C2-C20alkyenyl, C2-C20alkynyl or aryl, each of which is substituted or unsubstituted, or H; most preferably R3, R4, R5 and R6 each independently are H or optionally substituted C1-C10alkyl.
Preferably R7 is C1-C25alkyl, C1-C25alkoxy, C2-C25alkenyl, C2-C25alkynyl or aryl, each of which is substituted or unsubstituted, H, SO3H, C(O)OH, PO3H, NR5R6 or C(O)NR5R6; more preferably R7 is C1-C15alkyl or aryl, each of which is substituted or unsubstituted, H, SO3H, C(O)OH, PO3H, NR5R6 or C(O)NR5R6; most preferably R7 is C1-C10alkyl or aryl, each of which is substituted or unsubstituted, H, SO3H, C(O)OH, PO3H, NR5R6 or C(O)NR5R6.
Preferably each R8 independently is C1-C25alkyl, C2-C25alkyenyl, C2-C25alkynyl or aryl, each of which is substituted or unsubstituted, H, NHC(O)R5 or NHC(O)NR5R6; more preferably each R8 independently is optionally substituted C1-C10alkyl, H, NHC(O)R5 or NHC(O)NR5R6; most preferably each R8 independently is H, optionally substituted C1-C5alkyl, NHC(O)R5 or NHC(O)R5R6.
Preferably each R9 independently is C1-C25alkyl, C2-C25alkyenyl, C2-C25alkynyl or aryl, each of which is substituted or unsubstituted, H, SO3H, PO3H or NH3+; more preferably each R9 independently is optionally substituted C1-C10alkyl, H, SO3H, PO3H, or NH3+; most preferably each R9 independently is H or SO3H.
Preferably Ar1, Ar2, Ar3, Ar4 and Ar5 each independently are phenyl or napthyl; more preferably Ar1, Ar2 and Ar4 each independently are phenyl; and more preferably Ar3 and Ar5 each independently are napthyl.
Preferably each m independently is 1, 2 or 3.
In a particularly preferred embodiment of the present invention R1 is C1-C10alkyl or xe2x80x94SO3H substituted C1-C10alkyl; R2 is CN, optionally substituted pyridinium or optionally substituted C1-C10alkyl; R3, R4, R5 and R6 each independently are H or optionally substituted C1-C10alkyl; R7 is SO3H, C(O)OH or optionally substituted C1-C10alkyl; each R8 is independently H, C1-C5alkyl, NHC(O)R5, NHC(O)NR5R6; each R9 independently is SO3H; Ar1, Ar2 and Ar4 are phenyl; Ar3 and Ar5 are napthyl; and each m independently is 1 or 2.
When R1, R2, R3, R4, R5, R6, R7, R8, R9 or the 5- or 6-membered ring formed by L and R4 together with the N atom to which they are attached are optionally substituted the optional substituents include but are not limited to xe2x80x94Sxe2x80x94; xe2x80x94Oxe2x80x94; hydroxy; cyano; carboxyl; sulpho; nitro; ureido; C1-C4alkyl, for example methyl, ethyl propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl or iso-butyl; halogen, for example fluorine, chlorine or bromine; C1-C4alkoxy, for example methoxy, ethoxy, propoxy or butoxy; C1 to C4 alkoxycarbonyl, for example methoxy carbonyl or ethoxy carbonyl; xe2x80x94NHC(O)R10, xe2x80x94NR10R11, xe2x80x94C(O)NR10R11, xe2x80x94CHR10R11 where R10 and R11 each independently are H or C1-C6alkyl or where R10 and R11 together with the atom to which they are attached form an optionally substituted 5- or 6-membered ring, preferably an optionally substituted pyrrolidino, morpholino, piperidino or tetrahydrofuran ring.
When L and R4 together with the N atom to which they are attached form an optionally substituted 5- or 6-membered ring, the ring preferably comprises 3, 4 or 5 carbon atoms and optionally sulphur, oxygen and/or nitrogen atom(s). In a preferred embodiment L and R4 form an optionally substituted pyrrolidino, morpholino, piperidino or tetrahydrofuran ring, most preferably a morpholino ring.
Preferably the weight ratio of the dye of Formula (I) to the dye of Formula (II) is from 1:10 to 10:1, more preferably 1:5 to 5:1, especially 1:3 to 3:1, more especially 1:2 to 1:2, particularly 1.5:1. The preferences arise from a finding of an improved balance of chroma, optical density, wet-fastness, light-fastness and humidity-fastness properties.
Preferably the dyes of Formula (I) and Formula (II) are in the form of salts. Preferred salts are alkali metal salts, especially lithium, sodium and potassium salts, ammonium and substituted ammonium salts. Especially preferred salts are salts with ammonia, an organic amine or a quaternary amine (e.g.(CH3)4N+). The dyes may be converted into a salt using known techniques. For example, an alkali metal salt of a dye may be converted into a salt with ammonia or an amine by dissolving an alkali metal salt of the dye in water, acidifying with a mineral acid and adjusting the pH of the solution to pH 9 to 9.5 with ammonia or the amine and removing the alkali metal cations by dialysis.
The dyes may exist in tautomeric forms other than those shown in this specification. These tautomers are included within the scope of the present claims.
According to a second aspect of the present invention there is provided an ink comprising:
(a) from 0.1 to 20 parts of a composition according to the first aspect of the present invention;
(b) from 80 to 99.9 parts of a liquid medium; wherein all parts are by weight and the number of parts of (a)+(b) add up to 100.
The number of parts of (a) is preferably from 0.1 to 15, more preferably from 0.5 to 10, and especially from 1 to 5 parts. The number of parts of (b) is preferably from 99.9 to 85, more preferably from 99.5 to 90, especially from 99 to 95 parts.
The preferred weight ratio of the dye of Formula (I) and dye of Formula (II) is as described in relation to the first aspect of the present invention.
A preferred liquid medium includes water, a mixture of water and an organic solvent and an organic solvent free from water.
When the liquid medium comprises a mixture of water and an organic solvent, the weight ratio of water to organic solvent is preferably from 99:1 to 1:99, more preferably from 99:1 to 50:50 and especially from 95:5 to 70:30.
Preferably the liquid medium comprises:
(i) from 30 to 95 parts of water;
(ii) from 10 to 70 parts of organic solvent;
(iii) from 0 to 40 parts of a water dissipatable polymer; and
(iv) from 0 to 10 parts of a surfactant;
wherein all parts are by weight and the total number of parts of (i), (ii), (iii) and (iv) add up to 100.
Preferably the organic solvent present in the mixture of water and organic solvent is a water-miscible organic solvent or a mixture of water-miscible organic solvent and water-immiscible organic solvents.
Preferred water-miscible organic solvents include C1-6-alkanols, preferably methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, cyclopentanol and cyclohexanol; linear amides, preferably dimethylformamide or dimethylacetamide; ketones and ketone-alcohols, preferably acetone, methyl ether ketone, cyclohexanone and diacetone alcohol; water-miscible ethers, preferably tetrahydrofuran and dioxane; diols, preferably diols having from 2 to 12 carbon atoms, for example pentane-1,5-diol; C2-C6alkylene glycols preferably ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol and thiodiglycol and oligo- and poly-alkyleneglycols, preferably diethylene glycol, triethylene glycol, polyethylene glycol and polypropylene glycol; triols, preferably glycerol and 1,2,6-hexanetriol; mono-C1-4-alkyl ethers of diols, preferably mono-C1-4-alkyl ethers of diols having 2 to 12 carbon atoms, especially 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-[2-(2-methoxyethoxy)ethoxy]ethanol, 2-[2-(2-ethoxyethoxy)-ethoxy]ethanol, 2-butoxyethanol, 2-(2-butoxyethoxy)ethanol and ethyleneglycol monoallylether; cyclic amides, including optionally substituted oxazolidones, pyrrolidones preferably 2-pyrrolidone; optionally substituted pyrrolidones preferably N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, caprolactam and 1,3-dimethylimidazolidone; cyclic esters, preferably caprolactone; sulphoxides, preferably dimethyl sulphoxide and sulpholane. Preferably the liquid medium comprises water and 2 or more, especially from 2 to 8, water-miscible organic solvents.
Examples of further suitable liquid media comprising a mixture of water and one or more organic solvents are described in U.S. Pat. No. 4,963,189, U.S. Pat. No. 4,703,113, U.S. Pat. No. 4,626,284 and EP 425150A.
Suitable water-immiscible organic solvents include aromatic hydrocarbons, e.g. toluene, xylene, naphthalene, tetrahydronaphthalene and methyl naphthalene; chlorinated aromatic hydrocabons, e.g. chlorobenzene, fluorobenzene, chloronapthalene and bromonaphthalene; esters, e.g. butyl acetate, ethyl acetate, methyl benzoate, benzl benzoate, butyl benzoate, phenylethyl acetate, butyl lactate, benzyl lactate, diethyleneglycol dipropionate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di (2-ethylhexyl)phthalate, alcohols having six or more carbon atoms, e.g. hexanol, octanol, benzyl alcohol, phenyl ethanol, phenoxy ethanol, phenoxy propanol and phenoxy butanol; ethers having at least 4 carbon atoms, preferably C5-14 ethers, e.g. anisole and phenetole; nitrocellulose, cellulose ether, cellulose acetate; low odour petroleum distillates; turpentine; white spirits; naphtha; isopropylbiphenyl; terpene; vegetable oil; mineral oil; essential oil; and natural oil; and mixtures of any two or more thereof. Benzyl alcohol and phenoxy ethanol are especially preferred.
When the liquid medium comprises an organic solvent free from water, (i.e. less than 1% water by weight) the solvent preferably has a boiling point of from 30xc2x0 C. to 200xc2x0 C., more preferably of from 40xc2x0 C. to 150xc2x0 C., especially from 50xc2x0 C. to 125xc2x0 C. The organic solvent may be water-immiscible, water-miscible or a mixture-of such solvents. Preferred water-miscible organic solvents are any of the hereinbefore described water-miscible organic solvents and mixtures thereof. Preferred water-immiscible organic solvents include any of the hereinbefore described water-immiscible organic solvents and mixtures thereof.
When the liquid medium comprises a water-immiscible organic solvent, preferably a polar solvent is included because this enhances solubility of the dye in the liquid medium. Examples of polar solvents include C1-4-alcohols.
According to the second aspect of the invention an ink is provided comprising optionally a water-dissipatable polymer as part of the liquid medium. A water-dissipatable polymer, on dissipation in water or an aqueous solution may form a solution, dispersion, emulsion or suspension, depending on the nature of the water-dissipatable polymer. Preferably the water-dissipatable polymer is soluble in water although a minor amount may be insoluble in water and exist as dispersed particles in aqueous media or water. Preferably the proportion of insoluble polymer is less than 50%, preferably less than 40% and more preferably less than 30% by weight relative to the total weight of the water-dissipatable polymer.
The water-dissipatable polymer preferably bears water-dispersing groups, for example ionised carboxy and/or sulphonate groups, especially ionised sulphonate groups, as these assist water-dissipatability of the polymer. Such groups can be chain pendant and/or terminal. The water-dissipatable polymer may optionally have hydrophilic non-ionic segments, for example polyethylene oxide chains, which may be within the polymer backbone (i.e. in-chain incorporation) or as chain pendant and/or terminal groups.
The water-dissipatable polymer is preferably a water-dissipatable polyvinyl, polyurethane or polyester, more preferably a water-dissipatable polyester.
Water-dissipatable polymers may be prepared as known in the art and as described in WO 98/14524 page 1 line 25 to page 9 line 25, incorporated herein by reference, or for example water-dissipatable polyesters may be purchased from Eastman Kodak Limited or Avecia Limited. Examples include Eastman AQ 29D and Aq 55W.
Preferably the dyes of Formula (I) and (II) are purified by reverse osmosis, ultrafiltration, ion exchange or a combination thereof, either before or after they are incorporated in the ink according to the second aspect of the present invention.
In the ink according to the second aspect of the present invention the composition according to the first aspect of the present invention is preferably soluble in the liquid medium. Preferably the composition is soluble in the liquid medium at 20xc2x0 C. at a concentration of at least 5% by weight of the ink, preferably at least 6% by weight of the ink, and more preferably at least 7.5% by weight of the ink. This allows the preparation of concentrates which may be used to prepare more dilute inks and reduces the chance of the composition precipitating if evaporation of the liquid medium occurs during storage.
The ink may also contain additional components conventionally used in ink jet printing inks, for example dyes, pigments, viscosity and surface tension modifiers, corrosion inhibitors, light fastness enhancing additives, water fastness enhancing additives, ozone fastness enhancing additives, biocides (e.g. Proxel from Avecia), kogation reducing additives and surfactants which may be ionic or non-ionic. If the ink contains a surfactant, it is preferably a surfactant having a sulpho or sulphate group, a non-ionic surfactant free from carbon-carbon triple bonds, or a mixture thereof.
Inks may be prepared by mixing the composition according to the first aspect of the invention and the liquid medium in any order. Conveniently the composition is mixed with the liquid medium followed by addition of a surfactant and heating and/or stirring and/or sonication of the mixture to dissolve the composition, and the optional water-dissipatable polymer is then mixed in and stirred until homogeneous, to give the ink.
Preferably the ink has been filtered through a filter having a mean pore size xe2x89xa610 xcexcm, more preferably xe2x89xa65 xcexcm, especially xe2x89xa62 xcexcm, more especially xe2x89xa61 xcexcm. In this way particulate matter is removed which could otherwise block the fine nozzles used in ink jet printers.
Preferably the ink has a viscosity of xe2x89xa620 mPa.s, more preferably xe2x89xa610 mPa.s, especially xe2x89xa65 mPa.s, at 20xc2x0 C.
The surface tension of a liquid may be described as the attractive force exerted by molecules below the surface upon the molecules at the surface/air interface and its strength depends on the chemical nature of the liquid. Polar liquids such as water have a higher surface tension when compared with less polar liquids such as ethanol.
The surface tension of ink jet inks is a suitable feature for the evaluation of the usefulness of ink jet inks. Ink jet printer heads used in thermal or piezo ink jet printing are designed to work with inks having specific surface tension, typically in the range of from 25 to 55 dynes cmxe2x88x921. The surface tension of a liquid may easily be lowered by for example the addition of surfactants, however it is not easily raised and thus the surface tension should be at least as high as the value required for the ink jet printer head to work effectively. Too low a surface tension results in poor print quality and or early failure of the ink jet print head. The preferred static surface tension for ink jet inks used with piezo ink jet printing heads is in the range of from 25 to 40 dynes cmxe2x88x921 and for use with thermal ink jet printing heads in the range of from 25 to 50 dynes cmxe2x88x921, measured using the DuNouy Ring method on a Kruss K10 instrument.
Preferably the ink when printed on paper using an ink jet printer gives a solid area coverage with an optical density xe2x89xa71.0, preferably xe2x89xa71.1 and more preferably xe2x89xa71.2.
Preferably the ink has a total concentration of divalent and trivalent metal cations and halide anions below 1000, more preferably below 20, more especially below 10 parts per million by weight relative to the total weight of the ink. Inks of this purity may be prepared by purifying an impure ink, or the components which go into the ink, using standard purification techniques. Suitable techniques include reverse osmosis ultra filtration, ion exchange and combinations thereof.
Preferably the ink is yellow.
The inks of the second aspect of present invention are surprisingly superior to inks containing only one of the dyes of Formula (I) or Formula (II). In particular, the use of the composition according to the first aspect of the invention in ink jet printing inks results in improved storage stability, optical density, solubility, light-fastness and chroma. Image durability, print quality improvements and good wet-fastness of prints are also observed which are of particular value in wide format ink jet printing field.
The inks of the second aspect of the present invention have the advantage that they are suitable not only for the use of piezoelectric ink jet printers but also for the use in thermal, continuous, electrostatic and microelectromechanical ink jet printers.
A third aspect of the invention provides a process for printing an image on a substrate comprising applying thereto an ink according to the second aspect of the present invention by means of an ink jet printer.
The ink jet printer preferably applies the ink to the substrate in the form of droplets which are ejected through a small orifice onto the substrate. Preferred ink jet printers are piezoelectric ink jet printers and thermal ink jet printers. In thermal ink jet printers, programmed pulses of heat are applied to the ink in a reservoir by means of a resistor adjacent to the orifice, thereby causing the ink to be ejected in the form of small droplets directed towards the substrate during relative movement between the substrate and the orifice. In piezoelectric ink jet printers the oscillation of a small crystal causes ejection of the ink from the orifice. Microelectromechanical technology is described for example in WO 00/48938 and WO 00/55089 where ink is ejected from an ink ejection nozzle chamber utilising an electromechcnical actuator connected to a paddle or plunger which moves towards the ejection nozzle of the chamber for the ejection of drops of ink from the ejection nozzle chamber and also in U.S. Pat. No. 6,042,208 (microfluidic ink jet printing).
The substrate is preferably paper, plastic, a textile, metal or glass, more preferably paper, an overhead projector slide or a textile material, especially paper.
Preferred papers are plain or treated papers which may have an acid, alkaline or neutral character.
A further aspect of the present invention provides a paper, an overhead projector slide or a textile material printed with an ink as hereinbefore defined.
A still further aspect of the invention provides an ink jet printer cartridge comprising a chamber, optionally refillable, containing an ink according to the second aspect of the present invention in the chamber.
The invention is further illustrated by the following Examples in which all parts, percentages and ratios are by weight unless otherwise stated.
Dye 1 was prepared using stages 1a and 1b described below:
Stage 1a
Preparation of a Pyridone Component
4-Chloroethylacetoacetate (115 g, 0.70 mol) was added dropwise to a suspension of sodium sulphite (88.2 g, 0.70 mol) in water (70 cm3) at 60-70xc2x0 C. The reaction mixture was stirred for 2 hours at 60-70xc2x0 C. and then ethyl cyanoacetamide (78.4 g, 0.70 mol) (prepared by the reaction of ethylamine with ethyl cyanoacetate) was added, followed by the dropwise addition of ethylene diamine (24 cm3, 0.36 mol). The reaction mixture was heated at 95xc2x0 C. for 2 hours and then heated at reflux for 24 hours.
The reaction mixture was cooled to xe2x88x925xc2x0 C., acidified to pH=1 with conc. HCl and left to stand for 1 hour at 0xc2x0 C. The resulting product was isolated by filtration, dispersed in acetone (500 cm3), re-filtered and dried to give the pyridone coupling component (79.8 g).
Stage 1b
3-Hexylaniline (19.3 g, 0.1 mol) was added portionwise with stirring to 2M hydrochloric acid (500 cm3) at 0-5xc2x0 C. After the reaction mixture was allowed to stir for 10 minutes, sodium nitrite solution (40% w/w, 17.5 cm3, 0.1 mol) was added over 5 minutes and the reaction mixture than allowed to stir for a further 10 minutes. The excess nitrous acid was destroyed using sulphamic acid.
The pyridone component from Stage 1a (27.4 g, 0.1 mol) was added to the reaction mixture and the resultant yellow precipitate was stirred at 0-5xc2x0 C. for 30 minutes. The pH was raised to 4.5 with sodium acetate and the reaction mixture then stirred for a further 2 hours whilst rising to room temperature. The product was collected by filtration, washed with water and dried to give a yellow dye (Dye 1) (yield=38.6 g, 83%).
Dye (2) was prepared using stages 2a to 2c described below:
Stage 2a
4-Nitrobenzoylchloride (55.7 g) in CH2Cl2 (100 cm3) was added dropwise to a mixture of 2-(2-methoxyethoxy)ethanol (36 g) and pyridine (32 cm3) in CH2Cl2 (200 cm3) keeping the temperature below 10xc2x0 C. After isolation the resultant nitro compound was converted to the corresponding amino compound using H2 gas and a palladium catalyst in ethanol.
Ethyl acetoacetate (65.07 g) was added dropwise over 30 minutes to a stirred mixture of tetrahydrofurfurylamine (122.92 g) and water (18 g) at room temperature. Ethyl cyanoacetate (56.6 g) was then added. After heating to 90xc2x0 C. for 20 hours the solution was cooled and poured onto ice (150 g) and acidified by addition of concentrated hydrochloric acid. The resulting product was filtered-off, washed with water and dried at 45xc2x0 C. under reduced pressure.
Stage 2c
The amino compound from Stage 2a (11.9 g) was added to a mixture of water (30 cm3) and hydrochloric acid (12.3 cm3) and the solution cooled to 0-5xc2x0 C. A solution of sodium nitrite (3.46 g) in the minimum of water was then added dropwise keeping the temperature at 0-5xc2x0 C. After stirring for a further 20 minutes the excess nitrous acid was destroyed by the addition of sulphamic acid. The resulting diazonium salt solution was slowly added to a solution of the product from stage 2b (11.61 g) in methanol (200 cm3) keeping the temperature below 10xc2x0 C. After stirring for a further 30 minutes the yellow suspension was diluted with water (200 cm3) and the product filtered-off and recrystallised from methanol to give 15.8 g of Dye 2 having a xcexmax at 434 nm.
Dye (3) was prepared as the sodium salt using stages 3a to 3d as described below:
Intermediate (A)
Chloroacetamide (339.4 g at 98% strength) was added to N,N-dimethylformamide (DMF) (2 L). To the resulting solution was added nicotinic acid (466.4 g at 98% strength) followed by further DMF (800 cm3) whilst warming the mixture to 90xc2x0 C. The mixture was stirred at this temperature for 2xc2xd hours and allowed to cool to room temperature. The resulting precipitate was filtered-off, washed with acetone and dried under vacuum at 50xc2x0 C. to give Intermediate (A). (Yield=478 g).
Intermediate (B)
Intermediate (A) (450 g) was added to ethylacetoacetate (277.2 g) and methylated spirit740 P (1.25 L). To this was added sodium hydroxide pellets (188.5 g in total dissolved in methylated spirit 740 P (800 cm3) and water (840 cm3)). The mixture was then heated to reflux for total of 17 hours and then cooled to room temperature. The resulting solid was filtered-off, washed with methylated spirit 740 P and dried under vacuum 40xc2x0 C. to give Intermediate (B). (Yield=102.2 g at 33% strength).
Stage 3c: Diazotisation and Coupling
2-Carboxy-4-sulphoaniline (60.75 g at 89% strength) was dissolved in water (600 cm3) at pH 7-8 by addition of 2N NaOH (aq) and sodium nitrite (19.0 g). This solution was then added to a mixture of conc. HCl (162 cm3) in water (200 cm3). The resultant solution was stirred at for 2 hours whilst maintaining the temperature below 10xc2x0 C. Excess nitrous acid in the solution was then destroyed by addition of sulphamic acid.
To the resultant solution was added a solution of Intermediate (B) (76.8 g at 33% strength) in water (800 cm3). The resultant mixture was diluted to 7 L with de-ionised water and was adjusted to pH 7 by addition of 2N NaOH. The mixture was stirred over night, salted to 15% w/v with NaCl and the pH adjusted to 5-6 by addition of conc. HCl. The resulting solid was filtered-off, washed and pulled dry in a filter.
Stage 3d
Purification
The solid product of stage 3c was re-dissolved in distilled water (approx. 4 L) at pH 9.5 and desalinated by reverse osmosis. The solution was then screened and the water evaporated to give Dye 3 in the form of its sodium salt. (Yield=117 g).
Dye 4 was prepared using stages 4a-c as described below:
Stage 4a
A solution of sodium nitrite (13.6 g) in water (20 cm3) was added dropwise with stirring to a suspension of 2-aminonaphthalene-4,8-disulphonic acid (82.5 g) in a mixture of concentrated hydrochloric acid (73 cm3) and water (380 cm3) at 0-5xc2x0 C. After the addition was complete, the reaction mixture was allowed to stir for 30 minutes to give a diazo solution and then the excess nitrous acid was destroyed using sulphamic acid.
A solution of m-toluidine (19.82 g) in acetone (75 cm3) was then added dropwise with stirring to the above solution, whilst maintaining the temperature at 0-5xc2x0 C. The reaction mixture was stirred for 30 minutes and then the pH was raised to 4.5 with sodium acetate. Sodium chloride was added to 10% w/v over 30 minutes and a red precipitate formed. The reaction mixture was allowed to rise to room temperature and stirred overnight. The precipitate was collected by filtration, washed with 15% w/v sodium chloride solution and dried under vacuum to give a monoazo intermediate (yield=135 g at 52% purity).
Stage 4b
The monoazo intermediate resulting from stage 4a (64.5 g) was placed in water (140 cm3) and dissolved by adjusting to pH 7 with 2M sodium hydroxide solution to give a monoazo solution.
Cyanuric chloride (7.4 g) was dissolved in acetone (100 cm3) and added dropwise with stirring to ice/water (1000 cm3) over 15 minutes. After the addition was complete, the resultant fine white suspension was stirred at 0-5xc2x0 C. for 15 minutes and then half of the monoazo solution was added over 30 minutes, whilst maintaining the pH at pH 4-5 (via addition of 1N sodium hydroxide solution) and the temperature at 0-5xc2x0 C. After stirring for a further 2 hours, the remainder of the monoazo solution was added. The reaction mixture was allowed to rise to room temperature and stirred overnight, whilst the pH was maintained at 7 with 1M sodium hydroxide solution. The addition of sodium chloride (15% w/v) resulted in the precipitation of a monochloro intermediate. After stirring for a further 2 hours, the precipitate was collected by filtration and dried under vacuum to give a yellow monochloro intermediate (yield=50 g).
Stage 4c
The monochloro intermediate from stage 4b was added to a mixture of water (200 cm3), hexylamine (12.1 g) and 1,4-diazabicyclo[2.2.2.]octane (1.5 g) and the reaction mixture was stirred at 70-75xc2x0 C. overnight. The reaction mixture was cooled to room temperature and the pH lowered to pH 7 with 2M hydrochloric acid. The resultant precipitate was collected by filtration, washed with water (1000 cm3) and dried to give a yellow dye, (Dye 4) (yield=15 g).
Dye 5 was prepared using stages 5a-5c as described below:
Stage 5a
2-Aminonapthalene-4,8-disulphonic acid (837.6 g) was dissolved in distilled water (4 L). Hydrochloric acid (728 cm3) was added slowly over 10 mins and the reaction mixture was cooled to below 5xc2x0 C. by both the addition of ice and external cooling. Sodium nitrite (130 g) dissolved in water (260 cm3) was added slowly over 30 min, keeping the temperature below 5xc2x0 C. The excess nitrous acid was destroyed using sulphamic acid and then a solution of aniline-xcfx89-methanesulphonate (482.2 g) in water (1 L) was added over 20 minutes, keeping the temperature below 10xc2x0 C. Sodium acetate (550 g) was added to raise the pH to 4.5 and the reaction mixture was stirred at below 10xc2x0 C. for 2 hours, then allowed to rise to room temperature overnight. The reaction mixture was salted to 10% w/v with sodium chloride, stirred for 30 minutes, collected by filtration and then washed with 15% brine to give a paste.
The paste was charged to a flask, to which water (4 L) was added. 46% sodium hydroxide liquor (1361 g) was added over 10 minutes and the mixture was then stirred at 70-80xc2x0 C. for 7 hours. The mixture was allowed to cool to 50xc2x0 C., salted to 10% w/v with sodium chloride, cooled to 40xc2x0 C. and filtered. The resulting product was washed with 15% brine and then dried. Yield=695 g.
Stage 5b
A solution of cyanuric chloride (36.9 g) dissolved in acetone(350 cm3) was added to a mixture of ice/water (2 L) over 20 minutes. After stirring for 15 minutes, a solution of the product from stage 5a (136.6 g) in water (4 L) was added over 30 minutes, keeping the temperature below 5xc2x0 C. and the pH between 4 and 5, by the addition of 2M sodium hydroxide solution. Once the addition was complete, the reaction mixture was stirred for 15 minutes and then adjusted to pH 6.5 with 2M sodium hydroxide and stirred for a further 2.5 hours whilst keeping the temperature below 5xc2x0 C.
A further solution of product from stage 5a (136.6 g in 4 L water) was added and the reaction mixture was allowed to warm to room temperature whilst stirring overnight at pH 7. The reaction mixture was heated to 50xc2x0 C. and salted to 7.5% w/v with sodium chloride. The stirred reaction mixture was cooled to 40xc2x0 C., filtered-off and dried to give a monochlorotriazinyl product (yield=282 g)
Stage 5c
The monochlorotriazinyl product from stage 5b (65 g) was dissolved in water (1.25 L) containing 4-(3-aminopropyl)morpholine (27.6 g), and the resultant mixture was heated with stirring at 70-80xc2x0 C. for 3 hours. The mixture was allowed to cool to 45xc2x0 C. and salted to 20% w/v with sodium chloride. The precipitate was collected by filtration and washed with 25% brine to give a paste. The paste was dissolved in distilled water, desalinated and then evaporated to dryness to give 65 g of Dye 5.
Dye 6
Dye 6 is Cl Direct Yellow 86 available from Orion Dyes.
Preparation of Compositions of the Invention


A thin film transistor, comprising a first N-type LDD (Lightly Doped Drain) and a second N-type LDD, is provided. The two N-type LDDs are formed in a semiconductor layer by tilted implantation with a gate electrode serving as a mask. The two N-type LDDs are adjacent to source/drain regions, respectively. The thin film transistor further comprises a third P-type LDD and a fourth P-type LDD. The two P-type LDDs are formed in a semiconductor layer by tilted implantation with a gate electrode serving as a mask. The source/drain regions and the two N-type LDDs are surrounded by the two P-type LDDs, respectively.

The present invention relates to a liquid crystal display device, and more particularly to a liquid crystal display device having lightly doped drains (LDDs).
To increase the aperture ratio of a low temperature liquid crystal display device, the channel length between the source/drain regions must be reduced. When channel length is reduced, however, short channels effect occurs. A hot electron effect also occurs when the device is driven by a voltage.
With a short channel, depletion regions between the source/drain regions become narrow when voltage is applied to the device. Meanwhile, leakage current between the source/drain electrodes occurs, and the punch-through effect intensifies. The electronic properties of a low temperature poly silicon liquid crystal display device are thus affected and the device may be unreliable.
In a typical process of fabricating a lightly doped drain, although the P-type LDDs surround the N-type LDDs, leakage current and punch-through effects still occur when a large voltage is applied to the device.
Accordingly, a liquid crystal display capable of ameliorating the described problems is desirable.