A device and a method for processing high data rate serial data includes circuitry for recovering or generating a clock based with varying amounts of phase noise or jitter based upon a particular application. To achieve the foregoing, regulated and unregulated power are selectively provided to the circuitry for recovering a clock, to the circuitry for generating a transmission clock, and to any other circuitry having different tolerance levels for jitter and phase noise. Each power regulator comprises a current supply module and voltage regulator module. The current supply module provides one of a plurality of selectable output current levels into an output node of the regulator. The voltage regulator module having selectable voltage divider ratios at a first input of a comparator regulates an amount of current the device sinks from the output node to adjust the output voltage.

1. Technical Field of the Invention
This invention relates generally to communication systems and more particularly to clock recovery circuits used therein.
2. Description of Related Art
Communication systems are known to transport large amounts of data between a plurality of end user devices, which, for example, include telephones, facsimile machines, computers, television sets, cellular telephones, personal digital assistants, etc. As is known, such communication systems may be local area networks (LANs) and/or wide area networks (WANs) that are stand-alone communication systems or interconnected to other LANs and/or WANs as part of a public switched telephone network (PSTN), packet switched data network (PSDN), integrated service digital network (ISDN), or Internet. As is further known, communication systems include a plurality of system equipment to facilitate the transporting of data. Such system equipment includes, but is not limited to, routers, switches, bridges, gateways, protocol converters, frame relays, and private branch exchanges.
The transportation of data within communication systems is governed by one or more standards that ensure the integrity of data conveyances and fairness of access for data conveyances. For example, there are a variety of Ethernet standards that govern serial transmissions within a communication system at data rates of 10 megabits-per-second, 100 megabits-per-second, 1 gigabit-per-second and beyond. Synchronous Optical NETwork (SONET), for example, currently provides for transmission of 10 gigabits-per-second. In accordance with such standards, many system components and end user devices of a communication system transport data via serial transmission paths. Internally, however, the system components and end user devices may process data in a parallel manner. As such, each system component and end user device must receive the serial data and convert the serial data into parallel data without loss of information. After processing the data, the parallel data must be converted back to serial data for transmission without loss.
Accurate recovery of information from high-speed serial transmissions typically requires transceiver components that operate at clock speeds equal to or higher than the received serial data rate. Higher clock speeds limit the usefulness of prior art clock recovery circuits that require precise alignment of signals to recover clock and/or data. Higher data rates require greater bandwidth for a feedback loop of the clock recovery circuits to operate correctly. Some prior art designs are bandwidth limited.
As the demand for data throughput increases, so do the demands on a high-speed serial transceiver. The increased throughput demands are pushing some current integrated circuit manufacturing processes to their operating limits, where integrated circuit processing limits (e.g., device parasitics, trace sizes, propagation delays, device sizes) and integrated circuit (IC) fabrication limits (e.g., IC layout, frequency response of the packaging, frequency response of bonding wires) limit the speed at which the high-speed serial transceiver may operate without excessive jitter performance and/or noise performance.
A further alternative for high-speed serial transceivers is to use an IC technology that inherently provides for greater speeds. For instance, switching from a CMOS process to a silicon germanium or gallium arsenide process would allow integrated circuit transceivers to systems, such alternate integrated circuit fabrication processes are too cost prohibitive for widespread use.
Modern communication systems, including high data rate communication systems, typically include a plurality of circuit boards that communicate with each other by way of signal traces, bundled data lines, back planes, etc. Accordingly, designers of high data rate communication transceiver devices often have conflicting design goals that relate to the performance of the particular device. For example, there are many different communication protocols specified for data rates that range from 2.48832 gigabits per second for OC48, to 9.95 gigabits per second for OC192. Other known standards define data rates of 2.5 gigabits per second (INFINIBAND) or 3.125 gigabits per second (XAUI). These different data rates affect the allowable rise and fall time of the signal, the peak amplitude of the signal and the response time from an idle state. For example, one protocol may specify a peak voltage range of 200-400 millivolts, while another standard specifies a mutually exclusive voltage range of 500-700 millivolts. Thus, a designer either cannot satisfy these mutually exclusive requirements (and therefore cannot support multiple protocols) or must design a high data rate transceiver device that can adapt according to the protocol being used for the communications.
Along these lines, field programmable gate array (FPGA) circuits are gaining in popularity for providing the required flexibility and adaptable performance described above for those designers that seek to build one device that can operate according to multiple protocols. Thus, while FPGA technology affords a designer an opportunity to develop flexible and configurable hardware circuits, specific designs that achieve the desired operations must still be developed.
One design challenge for serial data processing, especially for high data rate communications, relates to synchronization, and in particular to timing differences between a reference clock and high data rate serial stream. Such differences can lead to buffer overflows/underflows, unnecessary delays and other complications. The problem of synchronization mismatch become more acute in devices that conduct multi-gigabit serial data rates. For such systems, it is important to eliminate these mismatches because of the high volume of data being transported. In these systems especially, but more generally in all serial communication systems, even a mismatch of one percent can lead to buffer overflows/underflows and other problems. This problem of high data rate mismatch is a significant problem for any type of device or system that receives, processes or transmits high data rate serial data. A need exists, therefore, for a device and accompanying method with broad applicability that resolves high data rate mismatch between the data and a given clock used to operate upon or process the high serial rate data. Along these lines, sources of error often require attention to reduce phase noise and jitter in a clock used for transmission and/or data recovery. One common error source is the unregulated power supply. Thus, for some high data rate communications, a need exists to reduce jitter and/or phase noise that results from unregulated power supplies.

Programmable on chip regulators with bypass


In a gas turbine combustion chamber having an annular combustion space, the combustion chamber inlet is equipped with a plurality of burners, which are uniformly distributed in the peripheral direction and are fastened to a front plate. Scavenged Helmholtz resonators (21) consisting of supply tube (51), resonance volume (50) and damping tube (52) are arranged in the region of the burners. The damping tubes (52) are designed so as to be exchangeable, for which purpose the walls of the combustion space are provided with a manhole.

1. Field of the Invention
The invention relates to a gas turbine combustion chamber having an annular combustion space whose walls extend from the combustion chamber inlet to the inlet to the gas turbine, and in which the combustion chamber inlet is equipped with a plurality of burners evenly distributed in the peripheral direction, which burners are fastened to a front plate.
2. Discussion of Background
The so-called "weak premixing combustion" has, in the recent past, become general for the low-pollutant combustion of a gaseous or liquid fuel. In this, the fuel and the combustion air are premixed as evenly as possible and are only then supplied to the flame. If this is carried out with a large excess of air, as is usual in the case of gas turbine installations, relatively low flame temperatures occur and this in turn leads to the desired, low level of formation of nitrogen oxides.
Combustion chambers of the type mentioned at the beginning are known from EP-A1-387 532. In this, the front plate is formed by a single wall on which are arranged premixing burners of the double-cone type.
Modern highly-loaded gas turbines demand increasingly complex and effective cooling methods. In order to achieve low NO.sub.x emission, attempts are made to direct an increasing proportion of the air through the burners themselves. This necessity to reduce the cooling air flows is also, however, due to reasons associated with the increasing hot gas temperature at the inlet of a modern gas turbine. Because the cooling of the other installation parts such as blading, machine shaft, etc. must also meet increasingly stringent requirements and because the hot gas temperatures, which continue to be increased in the interest of a high thermal efficiency, also lead directly to a greatly increased thermal loading on the combustion chamber walls, it is necessary to be very economical with the combustion chamber cooling air. These requirements generally lead to multi-stage cooling techniques, in which the pressure loss coefficient, i.e. the overall pressure drop caused by the cooling divided by a stagnation pressure at the cooling air inlet into the combustion chamber, can be quite high.
Gas turbine combustion chambers with air-cooled flame tubes are likewise known, for example from U.S. Pat. Nos. 4,077,205 or 3,978,662. The flame tube is essentially constructed of wall parts overlapping in the axial direction of the turbine. On their side facing away from the combustion space, each of the wall parts has a plurality of inlet openings distributed over the periphery. These inlet openings are used to introduce air into a distribution space arranged in the flame tube and communicating with the combustion space. In the case of the cooling system in these specifications, the respective flame tube has a lip which extends over the slot through which the cooling air film emerges. This cooling air film is to adhere to the wall of the flame tube, in order to form a cooling barrier layer for the flame tube.
The known gas turbine combustion chambers mentioned above have the disadvantage that the air consumption for cooling purposes is much too high and that, because the cooling air is fed into the flame tube interior downstream of the flame, this air is not available for the actual combustion process. The combustion chamber cannot, in consequence, be operated with the high excess air ratio necessary.
In the case of conventional combustion chambers, the cooling generally plays an extremely important role in the noise damping of the combustion chamber. The reduction in the cooling air mass flow mentioned above, in association with a greatly increased pressure loss coefficient for the overall combustion chamber wall cooling, now leads to an almost complete suppression of the noise damping. This development has led to an increasing vibration level in modern low NO.sub.x combustion chambers.

Gas turbine combustion chamber with scavenged Helmholtz resonators


A dimension sensor is used in conjunction with a tube and includes a body member and at least one detector element. The body member has an inner surface defining an opening sized to receive the tube. The at least one detector element is connected to the body member and has a detector portion extending into the opening. When the tube is received in the opening, the detector portion is initially disposed apart from the tube. A method using the dimension sensor stops expansion of the tube expanding from a pre-expanded state to a desired expanded state. A pumping device is actuated to pressurize a fluid by an amount sufficient to cause the tube to expand from the pre-expanded state to the desired expanded state. When the tube expands to the desired expanded state, the pumping device deactivates thereby stopping expansion of the tube at the desired expanded state.

In the manufacture of a conventional heat exchanger, heat exchanger tubes are inserted through respective aligned holes in a plurality of spaced-apart plate fins. Initially, the heat exchanger tubes are rather loosely received in the holes of the plate fins. It is necessary to expand the heat exchanger tubes in the holes of the plate fins so that the heat exchanger tubes are in a close-fitting, interference contact with the plate fins.
A conventional system for constructing heat exchangers using fluidic expansion by employing a fluid expansion is disclosed in U.S. Pat. No. 5,765,284 to Ali et al. As shown in FIG. 1, a compressor 2 of a tube expansion system 3 compresses an expansion fluid, specifically, a compressible fluid, from an expansion fluid reservoir 4 through a high-pressure safety valve 6 to the heat exchanger 8 via pipes 10a and 10b. The expansion fluid under high-pressure enters a tubing circuit 12 of the heat exchanger 8 through a connector 14 which is sealed to an inlet of the tubing circuit 12. The tubing circuit 12 is a serpentine structure of connected heat exchanger tubes 16. The connector 14 is a high-pressure connector capable of remaining sealed while delivering the expansion fluid at several thousand pounds per square inch. Upon introduction of the high-pressure fluid into the tubing circuit 12, the heat exchanger tubes 16 of the serpentine structure 16 expand radially outwardly to form secure contact with plate fins 18 and tube sheets 20. A plug 22 seals an outlet of the tubing circuit 12.
As shown in FIG. 1, controls 24 govern the amount of pressure the compressor 2 supplies to the tubing circuit 12. The controls 24 also terminate compression of the compressor 2 when sufficient expansion of the heat exchanger tubes 16 has been achieved by shutting off a power supply 26 supplying power to the compressor 2 through the controls 24. The controls 24 are used in conjunction with a displacement sensor 28. The displacement sensor 28 physically measures the increase in tubing diameter of a portion of one heat exchanger tube 16 of the tubing circuit 12. The displacement sensor 28 provides feedback of the expansion progress of the heat exchanger tubes 16 to the controls 24. In this manner, the controls 24 are set to stop the expansion of the heat exchanger tubes 16 once the circuit reaches a certain diameter. Alternatively, the controls 24 can vary the pressure of the expansion fluid during the expansion process. The controls 24 are essentially a microprocessor programmed in such a manner as to perform the above-stated objectives.
Another conventional tube expansion system for constructing heat exchangers uses an incompressible fluid such as water as opposed to U.S. Pat. No. 5,765,284 that uses a compressible fluid. However, other than one system using an incompressible fluid while the other uses a compressible fluid, the conventional systems for expanding heat exchanger tubes to construct heat exchangers using a fluid are generally similar in structure and function.

Dimension sensor and method for stopping expansion of a tube


Improvements in a downhole submerged pump assembly having a plunger formed of a cast or machined cylindrical member includes seal ring grooves capable of receiving flat metallic seal rings formed of a plurality of segments which are interlocked in a manner wherein the segments can expand during the upstroke of the pump movement and retract during the downstroke.

This invention relates to improvements in oil well pumps and more particularly, but not by way of limitation, to a reciprocating subsurface oil well pump.
A typical submerged oil well plunger type pump of the displacement type consists of a plunger and travelling check valve that is reciprocatingly received within a stationary working barrel formed as a part of the oil well production tubing. The working barrel itself is provided with a standing valve and is submerged usually in well fluid.
In one embodiment, the pump is normally secured to the lowermost end of a sucker rod string, which extends longitudinally through production tubing situated in the well bore. A reciprocating device at the surface is usually a `horsehead` type which alternately raises and lowers the string of sucker rods in the well bore. Subsurface pumps have long presented problems in the lifting of the well fluid to the surface of the ground in that the plunger of the pump is usually several feet long and thus requires a relatively long stroke for operation of the pump. This results in substantially great friction and drag on the pump as the pump plunger reciprocates within the working barrel. As a result, the pump plunger may not move freely nor provide a full stroke, thus reducing the pumping efficiency. In addition, since most of the subsurface pumps are relatively long, it may require several strokes of the pump before a sufficient load is applied to the pump to start the pumping action. Also, many well fluids contain sand and other foreign particles which hinder the operation of the subsurface pump and frequently damage the working parts thereof.
Newer forms of pump systems utilize a reciprocating wire line mechanism. A wire line winch provided at the surface will replace the horsehead type apparatus. Such a system includes control means for rotating the winch in one direction for the upstroke and controllably releasing the winch in the reverse direction for the downstroke. In such a system a weighted oil well plunger type pump must be capable, during the upstroke, of providing adequate ring seals for producing the fluid, while on the downstroke, the seal rings must be capable of permitting substantial release of the plunger so that it will fall to its bottom dead center position for the repeat of the process.
Pump plungers of the prior art have been provided with the various means for affecting the necessary fluid seal between the plunger and the working barrel. Such devices are shown in the aforesaid patents cited above. See also U.S. Pat. No. 3,953,155. In many of the prior art plunger pumps, the seal means between the plunger and the working barrel are apt to lose their close tolerance fit because of wear and, therefore, must be pulled occasionally to replace the parts. The pulling operation causes down-time on the well and expense in making the necessary repairs.

Oil well pump with radially expandable interlocking seal ring


A sense amplifier includes a first PMOS transistor, a second PMOS transistor, a third PMOS transistor, a fourth PMOS transistor, a first NMOS transistor, a second NMOS transistor, a third NMOS transistor, and a fourth NMOS transistor. The first PMOS transistor, the second PMOS transistor, the first NMOS transistor, and the second NMOS transistor form cross coupled sensing pairs. The third PMOS and the fourth PMOS transistors serve as compensation transistors. The third NMOS and the fourth NMOS transistors serve as sensing enabling transistors.

A bit line sense amplifier in embedded Dynamic Random Access Memory (eDRAM) generally includes one or two cross-coupled transistor or device pairs. Ideally, each device parameter such as threshold voltage Vt, transconductance coefficient β, node capacitance, etc., of one transistor in the transistor pair is the same as that of the other transistor in the same transistor pair. Manufacturing process deviations, however, cause differences or offsets in parameters of different transistors. As a result, two transistors even though manufactured by the same process intrinsically have two threshold voltages Vt with two different values. Many techniques have been used to compensate for the difference in threshold voltages Vt. Most of the techniques, however, are not applicable for use in eDRAMs that are manufactured by advanced technology in the nano-scale and/or operate above 300 MHz.
Like reference symbols in the various drawings indicate like elements.

Taiwan Semiconductor Manufacturing Company, Ltd.


Various aspects of methods and apparatuses are described herein. Some methods may include receiving video content, receiving metadata including a hierarchical order of metadata fields, and performing an enhancement operation on at least a portion of the video content according to settings associated with at least one of the metadata fields. The enhancement operation may include a video processing operation configured to modify one or more visual characteristics of the video content. The settings associated with the metadata field(s) may be predefined in a device that receives the video content and the metadata. The enhancement operation may be performed at a time based on a time code in the video content. The enhancement operation may be performed on a bounded area of an object. The hierarchical order may correspond to a type of display technology. The hierarchical order may correspond to information associated with a manufacturer of a display.

In conventional systems, devices that display video content may receive various inputs from the user to adjust settings associated with the display of the video content. For example, the user may adjust settings of the device such that the brightness of the displayed video content is increased. As another example, the user may adjust settings of the device such that the contrast of the displayed video content is decreased. These settings typically affect all of the displayed video content and persist until these settings are changed by the user. These settings typically do not to affect a particular portion of the video content. In conventional systems, modifications to the displayed video content may be performed at a server that transmits the video content. For example, the server may embed those modifications into the video content and subsequently transmit that modified video content to the receiving device for display. However, embedding such modifications into the video content can substantially increase the data size of the transmitted video content. Additionally, not every receiving device is configured to properly decode, process, and display every modification embedded in the video content. Conventional systems can benefit from enhancements that overcome such limitations to provide an improved user experience.

Enhancing video content according to metadata

INTERDIGITAL MADISON PATENT HOLDINGS, SAS


This application relates to a cell (1200) or sub-module for a voltage source converter (1201). The cell includes an energy storage apparatus (101; 101a, 101b) and a plurality of dual-switch semiconductor packages (201), each having first and second semiconductor switches (202, 203) connected in series. The cell is operable in an active state in which an energy storage apparatus (101; 101a, 101b) is electrically connected in series between cell terminals (102a, 102b) and a bypass state in the cell terminals (102a, 102b) are electrically connected via a path that bypasses the first energy storage apparatus. The plurality of dual-switch semiconductor switch packages are configured to provide a first set of semiconductor switches (301; 401) connected between nodes of the cell that are electrically connected in the first active state and electrically disconnected in the first bypass state; and a second set of semiconductor switches (302a, 302b; 402a, 402b) is connected between nodes of the cell that are electrically disconnected in the first active state and electrically connected in the bypass state. The second set of switches comprises a greater number of switches in parallel than the first set of switches.

This application relates to modular apparatus for a voltage source converter and to methods and apparatus for controlling modular apparatus of a voltage source converter, and especially to a modular apparatus that can be used as a cell of a chain-link circuit of a voltage source converter for use in high voltage power transmission.
High-voltage direct current (HVDC) electrical power transmission uses direct current for the transmission of electrical power. This is an alternative to alternating current electrical power transmission which is more common. There are a number of benefits to using HVDC electrical power transmission.
In order to use HVDC electrical power transmission, it is typically necessary to convert alternating current (AC) electrical power to direct current (DC) and back again. Recent developments in the power electronics field have led to an increased use of voltage-source converters (VSCs) for AC to DC and DC to AC conversion. VSCs make use of semiconductor switching elements that can be controllably turned on and off. Insulated gate bipolar transistors (IGBTs) connected with respective anti-parallel diodes have commonly been used as the semiconductor switching elements.
Typically a VSC will comprise a phase limb for each electrical phase of the AC network. Each phase limb may be coupled to the DC network at respective positive and negative DC terminals, e.g. between positive and negative DC busbars, and will also be connected to the AC network via at least one AC node. A phase limb will comprise a plurality of converter arms, with each converter arm extending between an AC node and one of the DC terminals or some other defined DC voltage such as ground. In a symmetric monopole arrangement a phase limb may have two converter arms, a positive converter arm extending between the AC node and the positive DC terminal and a negative converter arm extending between the AC node and the negative DC terminal. In other arrangements, for instance a bipole scheme, there may be more converter arms, for instance there may be two converter arms in series between the positive DC terminal and a ground terminal to form a positive pole, with an AC node at the midpoint of the series connection. Likewise a negative pole is formed by a similar arrangement connected between the ground terminal and the negative DC terminal.
In each case, each converter arm includes a switching apparatus, referred to as a valve.
Various designs of VSC are known. One such variant is the modular multilevel converter (MMC). The valves of an MMC may be formed, at least partly, from a series connection of a plurality of modular units or cells, each cell having an energy storage element, such as a capacitor, and switching elements, such as IGBTs, arranged such that the energy storage element can be selectively connected in series between terminals of the cell or bypassed. The series connection of such cells is sometimes referred to as a chain-link circuit or chain-link converter or simply a chain circuit and the individual cells or links are often referred to as sub-modules, with a plurality of cells together forming a module. Such chain-link circuits can be used for voltage wave-shaping and can allow conversion between AC and DC with relatively low distortion. Such chain-link circuits may also be used in other VSC variants.
The cells of the chain-link circuit may, depending on the type of VSC, be implemented with the switching elements arranged with the energy storage element in a half-bridge type configuration, so the energy storage element may be connected in series between the cell terminals in one orientation or may be bypassed. However, for some VSC designs at least some of the cells of the chain-link circuit may be implemented with the switching elements arranged with the energy storage element in a full-bridge type configuration, so the energy storage element may be bypassed or may be connected in series between the cell terminals in either of two reverse orientations so as to present voltages of opposite polarity at the cell terminals.


In a generation system, while a mark image including a prescribed mark is displayed on the display screen of a display panel, a capturing device captures a plurality of partial images in which a portion of the display screen is seen and generates capture data of each of the plurality of partial images. A correction data generation device specifies, for each of the plurality of partial images captured by the capturing device, an object area in the partial image on the basis of the mark included in the partial image. The correction data generation device extracts, for each of the plurality of partial images, an object portion that corresponds to the object area from the capture data of the partial images, and synthesizes a plurality of extracted object portions, thereby generating screen image data that corresponds to the capture data of the entire display screen.

An unevenness correction system for correcting brightness unevenness occurring in a display screen of a display panel is conventionally known. For example, Patent Literature 1 discloses an unevenness correction system in Which a screen image of a whole display screen of a display panel is captured with a test image displayed on the display screen, and correction data to be used for correcting brightness unevenness is generated based on the thus captured image data of the whole display screen.

Generation system, generation method, and storage medium


The invention concerns an optical system adapted to split an optical path from a taking optical system into a finder optical system, which has a camera-shake correction function best suited for the finder optical system, and so on. This optical system comprises a taking optical system and a finder optical system. The taking optical system comprises an optical path splitter means operable to split an optical path into the finder optical system, and the finder optical system includes a relay optical system RLS for re-forming a subject image once. Anti-shake is implemented by shifting an optical subsystem RL that forms a part of the finder optical system in a plane vertical to an optical axis.

The present invention relates generally to an optical system, a finder optical system, a relay type finder optical system, an eyepiece optical system and a single-lens reflex camera, and more specifically to an optical system having a camera-shake correction function capable of preventing image-shakes by camera-shake (e.g., upon hand-hold photographing), a relay optical system designed especially for taking systems such as digital cameras, film cameras and video cameras, an eyepiece optical system having a wide field of view, a long eye relief and a compact total length, a compact relay type finder optical system using the same, and a single-lens reflex camera using the same.
Prior art finder optical systems having a camera-shake correction function include the following.
The finder optical system set forth in patent publication 1 is configured as shown in FIG. 45. In this optical system, the camera-shake correction lens L is located in a non-TTL finder optical system wherein the taking optical system is separate from the finder optical system. Then, the camera-shake correction lens L is decentered parallel with the optical axis of the finder optical system by means of a driving system A, thereby implementing correction of shakes of light incident from a subject on the optical system.
The optical system set forth in patent publication 2 is configured as depicted in FIGS. 46, 47 and 48. In FIGS. 46 and 47, the lens L that forms a part of the objective lens is moved vertically to the optical axis, and in FIG. 48, the eyepiece lens E is moved vertically to the optical axis. In this way, correction of camera-shake is implemented.
With the above prior arts, a lens group having a camera-shake preventive function, i.e., an anti-shake group is used. As this anti-shake group is decentered, it produces aberrations that lead to image-formation capability deteriorations. It also produces decentration distortion that may otherwise cause an image shape to turn asymmetric with respect to the optical axis. There is thus the need of preventing such image-formation capability deteriorations and asymmetric image shape due to anti-shake
Further, as the anti-shake group is heavy, it gives an increasing load to an actuator for the movement of the anti-shake group; that is, it is necessary to lighten the anti-shake group.
Furthermore, a low sensitivity to anti-shake causes an increase in the amount of movement of the anti-shake group. A high sensitivity to anti-shake, in contrast, renders control of movement of the anti-shake group difficult. To eliminate this problem, the sensitivity to anti-shake must be set at a proper value.
With anti-shake optical systems, much care must thus be taken of anti-shake functions.
The optical systems disclosed in patent publications 1 and 2 teach nothing about how the problems to be solved with anti-shake optical systems are addressed. In other words, these prior arts are still less than satisfactory in terms of practically optimum anti-shake methods, and how they are feasible. In particular, some patent publications do not present any optical path diagrams.
The optical systems disclosed in patent publications 1 and 2 are all directed to a non-TTL finder optical system with a taking optical system separate from a finder optical system.
By the way, single-lens reflex cameras comprising an image pickup plane smaller than conventional Leica-format size have been proposed and commercialized. Especially the market for single-lens reflex cameras using CCDs, C-MOSs or other electronic image pickup devices are now expanding. Decreased image pickup planes need a finder system of higher magnification. Although it is necessary to shorten the focal length of the whole finder optical system so as to make finder magnification high, this renders it difficult to set up a finder system in a widely available penta prism mode. Another technique known in the art is to use a relay type finder optical system, as typically taught in patent publications 3 and 4. Never until now, however, is there proposed any relay optical system, and any eyepiece optical system that is of good performance, is suitable for use with a small image pickup lane, and can be compactly laid out.
Further, there is still desired an eyepiece optical system or lens that ensures a relatively wide field of view, a long distance (eye relief) from the eyepiece lens the viewer's pupil (eye point), and a compact whole length inclusive of the position of an image being viewed as set by an image-formation lens, and a display position. Such eyepiece optical systems as set forth in patent publications 5 and 6 have so far been available. However, although they have a sufficiently wide angle of view, yet they are of inadequate eye relief.
Still, an eyepiece optical system having a long eye relief is desired in view of camera body construction as well.
Patent Publication 1
JP (A)) 9-329820
Patent Publication 2
JP (A) 2003-91027
Patent Publication 3
JP (A) 4-337705
Patent Publication 4
JP (A) 1-101530
Patent Publication 5
JP (A) 8-43749
Patent Publication 6
JP (A) 9-54258

Optical system, finder optical system, relay type finder optical system, eyepiece optical system, and single-lens reflex camera


A hydrokinetic turbine system, including a plurality of hydrokinetic turbines is installed on a bed of a body of water. Each turbine has a shroud with a forward entrance portion and rear exit portion. The shroud includes a propeller disposed in a middle portion thereof. An inner surface of the shroud includes a plurality of rifling vanes formed therein to induce water entering the forward entrance portion to rotate in a vortex-like fashion. A plurality of pre-spin guard blades disposed adjacent the forward entrance portion also induce rotation of water and serve to provide a barrier preventing objects from passing into the forward entrance portion. A plurality of stabilizers extending from an exterior surface of the shroud that position the forward entrance portion in the direction of current flow.

A global problem that is receiving a lot of attention is how to supply energy to the population of the world. As a proposed solution, many believe that it would be highly beneficial if the use of fossil fuels was decreased and replaced with renewable sources of energy. Accordingly, efforts have been made to harness natural kinetic resources to meet ever increasing electrical power generation needs. However, about 90% of U.S. electric production sill comes from nonrenewable sources.
A significant percentage of the efforts to use renewable sources of energy has been concentrated on wind powered systems. In the U.S., wind powered systems currently only account for about 10% of renewable electricity sources despite wind systems having increased in their prevalence by 35% from the period of April 2008 to April 2009, according to Energy Information Association ("EIA") Reports. Conversely, while conventional hydroelectric systems account for about 77% of the U.S. renewable energy supply, they have fallen out of favor in the U.S. as more evidence is uncovered on the potential enormous environmental and geological impact created by such systems.
One of the principal reasons for the small percentage of wind powered generating systems is that they suffer from the obvious problem that wind energy is inherently intermittent. Wind power generating systems are also somewhat limited in terms of where they can be located and typically, need to be located in areas that are known to experience a significant amount of wind. This presumes that these high wind areas would be susceptible to construction of such wind power generating systems, which they frequently are not.
Common hydroelectric systems include submersible plants for producing electricity from ocean currents. Those plants are typically fastened to the sea bottom by wires and comprise turbines arranged to be driven by tidal water. However, the power generated from submersible plants needs to be increased without substantially increasing the energy gathering costs in order for this energy source to be commercially attractive.
Consequently, vast scientific and financial resources have been expended in pursuit of hydrokinetic turbines which can convert kinetic energy within a normal flow of a body of water into a useful amount of electrical energy at a reasonable cost. Despite these efforts, hydrokinetic turbines deployed in the normal flow of a body of water have nevertheless not been successfully developed to the point where they can deliver adequate amounts of electric power at a reasonable "per kilowatt hour" cost, with an acceptable level of reliability. This is complicated by the fact that hydrokinetic power systems are limited by the number of available locations for their installation and typically can only provide the desired results in rivers that are fast flowing and deep.
In addition to the limitations with hydrokinetic systems, the successful deployment of the individual hydrokinetic turbines is also inherently problematic. First, the rotation of a turbine about an axis in one direction generates an equal yet opposing counter-torque in the opposite direction. To counteract this counter-torque and maintain stability of the hydrokinetic turbine, a mounting apparatus such as a series of anchored support posts or columns are attached to the hydrokinetic turbine and then anchored to a stationary structure, such as the floor of a river, a bridge or some other immovable object. While this serves to stabilize the hydrokinetic turbine, it prevents ease of adjustment of the turbine location to a different point within the moving body of water where current flow is optimum. As the characteristics of the flowing body of water change due to an increased volume of water, freezing, etc., the point of optimum flow also changes. The lack of mobility of a deployed hydrokinetic turbine limits the adaptability of the turbine to such differing conditions and creates a corresponding decrease in the efficiency of the system.
Further, existing hydrokinetic turbines are relatively expensive. Conventional turbines, and specifically hydrokinetic turbines, have typically been constructed of steel or lightweight metal such as marine aluminum for a variety of reasons. First, constructing these of metal provides increased durability, particularly in harsh surroundings. Second, a fairly heavily weighted turbine housing, in conjunction with conventional anchoring mechanisms described above, provides the configuration best able to withstand and minimize the effects of counter-torque generated by rotation of the turbine blades and shaft. On the downside, the cost of manufacturing a hydrokinetic turbine from a metal material is extremely expensive.
Accordingly, there exists a need for a hydrokinetic turbine which overcomes the existing problems with hydrokinetic technology. More specifically, there exists a need for a hydrokinetic turbine which can be stabilized in a path of water flow without complex anchoring mechanisms. There is a further need for a hydrokinetic turbine which can be placed in a particular optimal position in a path of water flow, then easily maneuvered to a different position within the body of water in the event of a change of location of the optimal path of water flow. Finally, there is a need for a hydrokinetic turbine unit complying with the above-stated needs which is also economical to build and operate.

Hydrokinetic turbine structure and system


The invention relates to colorant preparations containing the following main constituents: A) at least one dispersed (A1) or dissolved (A2) colorant; B) if a colorant corresponding to (A1) is used, a dispersing agent; C) a low-molecular polytetrahydurofurane (C1), optionally mixed with one or more difficult-to-evaporate, water-soluble or water-miscible organic solvents (C2); and D) water.

The present invention relates to novel colorant preparations comprising
A) at least one dispersed (A1) or dissolved (A2) colorant,
B) a dispersant in the case of a colorant (A1),
C) a low molecular weight polytetrahydrofuran (C1), if desired in mixture with one or more high-boiling water-soluble or -miscible organic solvents (C2), and
D) water
as essential constituents.
This invention further relates to the use of these colorant preparations as inks in the ink-jet process and to a process for printing sheetlike or three-dimensionally configured substrates by the ink-jet process using these colorant preparations.
Inks for use in the ink-jet process (such as Thermal Ink Jet, Piezo Ink Jet, Continuous Ink Jet, Valve Jet) have to meet a whole series of requirements. They have to have a viscosity and surface tension suitable for printing, they have to be stable in storage, i.e., they should not coagulate or flocculate, and they must not lead to cloggage of the printer nozzle, which can be problematical especially in the case of inks containing dispersed, i.e., undissolved, colorant particles. Stability in storage further requires of these inks that the dispersed colorant particles do not sediment. Finally, in the case of Continuous Ink Jet, the inks shall be stable to the addition of conducting salts and be free from any tendency to flock out with an increase in the ion content. In addition, the prints obtained have to meet colorists"" requirements, i.e., show brilliance and depth of shade, and have good fastness properties, e.g., for example rubfastness, lightfastness, waterfastness and wetrubfastness, and good drying behavior.
WO-A-99/01516 discloses pigmented ink-jet inks which differ from the present colorant preparations because of component (C).
It is an object of the present invention to provide novel colorant preparations having advantageous application properties in the ink-jet process, including in particular good start-of-print and sustained use behavior with good drying behavior.
We have found that this object is achieved by the colorant preparations defined at the beginning.
Colorant preparations according to the invention may include essentially insoluble dispersed colorant (A1) (finely divided organic or inorganic pigments or dyes which are insoluble in the water/solvent mixture) or dissolved colorant (A2) (dyes which are soluble in the water/solvent mixture). Colorant preparations according to the invention may also include colorant mixtures, but preferably only one colorant is present. Pigment-based colorant preparations according to the invention are preferred. By way of brightening agents, these pigment preparations may include dyes, especially direct, acid or reactive dyes, that are similar in hue to the pigment.
There now follow examples of useful pigments (A1), vat dyes being included among the organic pigments on account of the overlap with organic pigments.
Organic Pigments:
monoazo pigments: C.I. Pigment Brown 25;
C.I. Pigment Orange 5, 13, 36 and 67;
C.I. Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 52:1, 52:2, 53, 53:1, 53:3, 57:1, 63, 112, 146, 170, 184, 210, 245 and 251;
C.I. Pigment Yellow 1, 3, 73, 74, 65, 97, 151 and 183;
disazo pigments: C.I. Pigment Orange 16, 34 and 44;
C.I. Pigment Red 144, 166, 214 and 242;
C.I. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188;
anthanthrone pigments: C.I. Pigment Red 168 (C.I. Vat Orange 3);
anthraquinone pigments: C.I. Pigment Yellow 147 and 177;
C.I. Pigment Violet 31;
anthrapyrimidine pigments: C.I. Pigment Yellow 108 (C.I. Vat Yellow 20);
quinacridone pigments: C.I. Pigment Red 122, 202 and 206;
C.I. Pigment Violet 19;
quinophthalone pigments: C.I. Pigment Yellow 138;
dioxazine pigments: C.I. Pigment Violet 23 and 37;
flavanthrone pigments: C.I. Pigment Yellow 24 (C.I. Vat Yellow 1);
indanthrone pigments: C.I. Pigment Blue 60 (C.I. Vat Blue 4) and 64 (C.I. Vat Blue 6);
isoindoline pigments: C.I. Pigment Orange 69;
C.I. Pigment Red 260;
C.I. Pigment Yellow 139 and 185;
isoindolinone pigments: C.I. Pigment Orange 61;
C.I. Pigment Red 257 and 260;
C.I. Pigment Yellow 109, 110, 173 and 185;
isoviolanthrone pigments: C.I. Pigment Violet 31 (C.I. Vat Violet 1);
metal complex pigments: C.I. Pigment Yellow 117, 150 and 153;
C.I. Pigment Green 8;
perinone pigments: C.I. Pigment Orange 43 (C.I. Vat Orange 7);
C.I. Pigment Red 194 (C.I. Vat Red 15);
perylene pigments: C.I. Pigment Black 31 and 32;
C.I. Pigment Red 123, 149, 178, 179 (C.I. Vat Red 23), 190 (C.I. Vat Red 29) and 224;
C.I. Pigment Violet 29;
phthalocyanine pigments: C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 and 16;
C.I. Pigment Green 7 and 36;
pyranthrone pigments: C.I. Pigment Orange 51;
C.I. Pigment Red 216 (C.I. Vat Orange 4);
thioindigo pigments: C.I. Pigment Red 88 and 181 (C.I. Vat Red 1);
C.I. Pigment Violet 38 (C.I. Vat Violet 3);
triarylcarbonium pigments: C.I. Pigment Blue 1, 61 and 62;
C.I. Pigment Green 1;
C.I. Pigment Red 81, 81:1 and 169;
C.I. Pigment Violet 1, 2, 3 and 27;
C.I. Pigment Black 1 (aniline black);
C.I. Pigment Yellow 101 (aldazine yellow);
C.I. Pigment Brown 22;
vat dyes (in addition to those already mentioned above):
C.I. Vat Yellow 2, 3, 4, 5, 9, 10, 12, 22, 26, 33, 37, 46, 48, 49 and 50;
C.I. Vat Orange 1, 2, 5, 9, 11, 13, 15, 19, 26, 29, 30 and 31;
C.I. Vat Red 2, 10, 12, 13, 14, 16, 19, 21, 31, 32, 37, 41, 51, 52 and 61;
C.I. Vat Violet 2, 9, 13, 14, 15, 17 and 21;
C.I. Vat Blue 1 (C.I. Pigment Blue 66), 3, 5, 10, 12, 13, 14, 16, 17, 18, 19, 20, 22, 25, 26, 29, 30, 31, 35, 41, 42, 43, 64, 65, 66, 72 and 74;
C.I. Vat Green 1, 2, 3, 5, 7, 8, 9, 13, 14, 17, 26, 29, 30, 31, 32, 33, 40, 42, 43, 44 and 49;
C.I. Vat Brown 1, 3, 4, 5, 6, 9, 11, 17, 25, 32, 33, 35, 38, 39, 41, 42, 44, 45, 49, 50, 55, 57, 68, 72, 73, 30, 81, 82, 83 and 84;
C.I. Vat Black 1, 2, 7, 8, 9, 13, 14, 16, 19, 20, 22, 25, 27, 28, 29, 30, 31, 32, 34, 36, 56, 57, 58, 63, 64 and 65;
Inorganic Pigments:
white pigments: titanium dioxide (C.I. Pigment White 6), zinc white, pigment grade zinc oxide; zinc sulfide, lithopone; lead white;
black pigments: iron oxide black (C.I. Pigment Black 11), iron manganese black, spinel black (C.I. Pigment Black 27); carbon black (C.I. Pigment Black 7);
color pigments: chromium oxide, chromium oxide hydrate green; chrome green (C.I. Pigment Green 48); cobalt green (C.I. Pigment Green 50); ultramarine green;
cobalt blue (C.I. Pigment Blue 28 and 36); ultramarine blue; iron blue (C.I. Pigment Blue 27); manganese blue;
ultramarine violet; cobalt violet, manganese violet;
iron oxide red (C.I. Pigment Red 101); cadmium sulfoselenide (C.I. Pigment Red 108); molybdate red (C.I. Pigment Red 104); ultramarine red;
iron oxide brown, mixed brown, spinel and corundum phases (C.I. Pigment Brown 24, 29 and 31), chrome orange;
iron oxide yellow (C.I. Pigment-Yellow 42); nickel titanium yellow (C.I. Pigment Yellow 53; C.I. Pigment Yellow 157 and 164); chrome titanium yellow; cadmium sulfide and cadmium zinc sulfide (C.I. Pigment Yellow 37 and 35); chrome yellow (C.I. Pigment Yellow 34), zinc yellow, alkaline earth metal chromates; Naples yellow; bismuth vanadate (C.I. Pigment Yellow 184);
interference pigments: metallic effect pigments based on coated metal platelets; pearl luster pigments based on mica platelets coated with metal oxide; liquid crystal pigments.
Preferred pigments in this context are monoazo pigments (especially laked BONS pigments, naphthol AS pigments), disazo pigments (especially diaryl yellow pigments, bisacetoacetanilide pigments, disazopyrazolone pigments), quinacridone pigments, quinophthalone pigments, perinone pigments, phthalocyanine pigments, triarylcarbonium pigments (alkali blue pigments, laked rhodamines, dye salts with complex anions), isoindoline pigments and carbon blacks.
Examples of particularly preferred pigments are specifically: C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Violet 19, C.I. Pigment Blue 15:3 and 15:4, C.I. Pigment Black 7, C.I. Pigment Orange 5, 38 and 43 and C.I. Pigment Green 7.
These pigments are very useful for preparing ink-jet ink sets based on colorant preparations according to the invention. The level of each pigment in the individual inks is conformed to the respective requirements (e.g., trichromism).
The following pigment combinations are particularly recommended:
C.I. Pigment Yellow 138, C.I. Pigment Violet 19, C.I. Pigment Blue 15:3 and C.I. Pigment Black 7;
C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Blue 15:3 or 15:4 and C.I. Pigment Black 7;
C.I. Pigment Yellow 138, C.I. Pigment Violet 19, C.I. Pigment Blue 15:3, C.I. Pigment Black 7, C.I. Pigment Orange 43 and C.I. Pigment Green 7;
C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Blue 15:3 or 15:4, C.I. Pigment Black 7, C.I. Pigment Orange 5 and C.I. Pigment Green 7;
C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Blue 15:3 or 15:4, C.I. Pigment Black 7, C.I. Pigment Orange 38 and C.I. Pigment Green 7;
C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Blue 15:3 or 15:4, C.I. Pigment Black 7, C.I. Pigment Orange 43 and C.I. Pigment Green 7.
Useful dyes (A1), which are essentially insoluble in the water/solvent mixture, in addition to the vat dyes already mentioned include in particular azo, anthraquinone, quinophthalone, benzodifuran, methine and azamethine dyes which are free of acidic or ionic groups.
Examples of useful dyes (A1) are specifically:
C.I. Disperse Yellow 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 11:1, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 179, 180, 181, 182, 183, 184, 184:1, 200, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 219, 220, 221, 222, 223, 224, 225, 226, 227 and 228;
C.I. Disperse Orange 1, 2, 3, 3:3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 25:1, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 41:1, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 126, 127, 128, 129, 130, 131, 136, 137, 138, 139, 140, 141, 142, 143, 145, 146, 147 and 148;
C.I. Disperse Red 1, 2, 3, 4, 5, 5:1, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 30:1, 31, 32, 33, 34, 35, 36, 38, 39, 40, 41, 43, 43:1, 46, 48, 50, 51, 52, 53, 54, 55, 55:1, 56, 58, 59, 60, 61, 63, 65, 66, 69, 70, 72, 73, 74, 75, 76, 77, 79, 80, 81, 82, 84, 85, 86, 86:1, 87, 88, 89, 90, 91, 92, 93, 94, 96, 97, 98, 100, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 115, 116, 117, 118, 120, 121, 122, 123, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 151:1, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 167:1, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 190:1, 191, 191:1, 192, 193, 194, 195, 211, 223, 273, 274, 275, 276, 277, 278, 279, 280, 281, 302:1, 305, 306, 307, 308, 309, 310, 311, 312, 313, 314, 315, 316, 317, 318, 319, 320, 321, 322, 323, 324, 325, 326, 327, 328, 329, 330, 331, 332, 333, 334, 335, 336, 338, 339, 340, 341, 342, 343, 344, 346, 347, 348, 349, 356 and 367;
C.I. Disperse Violet 1, 2, 3, 4, 4:1, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 31, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 70, 81, 86, 87, 88, 89, 91, 92, 93, 94, 96 and 97;
C.I. Disperse Blue 1, 1:1, 2, 3, 3:1, 4, 5, 6, 7, 7:1, 8, 9, 10, 11, 12, 13, 13:1, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 23:1, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 38, 39, 40, 42, 43, 44, 45, 47, 48, 49, 51, 52, 53, 54, 55, 56, 58, 60, 60:1, 61, 62, 63, 64, 64:1, 65, 66, 68, 70, 72, 73, 75, 76, 77, 79, 80, 81, 81:1, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 111, 112, 113, 114, 115, 116, 117, 118, 119, 121, 122, 123, 124, 125, 126, 127, 128, 130, 131, 132, 133, 134, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 165:2, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 195, 281, 282, 283, 283:1, 284, 285, 286, 287, 288, 289, 290, 291, 292, 293, 294, 316, 317, 318, 319, 320, 321, 322, 323, 324, 325, 326, 327, 328, 329, 330, 331, 332, 333, 334, 335, 336, 337, 338, 339, 340, 341, 342, 343, 344, 345, 346, 347 and 349;
C.I. Disperse Green 1, 2, 5, 6 and 9;
C.I. Disperse Brown 1, 2, 3, 4, 4:1, 5, 7, 8, 9, 10, 11, 18, 19, 20 and 21;
C.I. Disperse Black 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 22, 24, 25, 26, 27, 28, 29, 29:1, 30, 31, 32, 33, 34 and 36;
C.I. Solvent Yellow 2, 3, 7, 12, 13, 14, 16, 18, 19, 21, 25, 25:1, 27, 28, 29, 30, 33, 34, 36, 42, 43, 44, 47, 56, 62, 72, 73, 77, 79, 81, 82, 83, 83:1, 88, 89, 90, 93, 94, 96, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 141, 143, 144, 145, 146, 157, 160:1, 161, 162, 163, 167, 169, 172, 173, 176, 179, 180, 181, 182, 183, 184, 185, 186, 187, 189, 190 and 191;
C.I. Solvent Orange 1, 2, 3, 4, 5, 7, 11, 14, 20, 23, 25, 31A, 40:1, 41, 45, 54, 56, 58, 60, 62, 63, 70, 75, 77, 80, 81, 86, 99, 102, 103, 105, 106, 107, 108, 109, 110, 111, 112 and 113;
C.I. Solvent Red 1, 2, 3, 4, 8, 16, 17, 18, 19, 23, 24, 25, 26, 27, 30, 33, 35, 41, 42, 45, 48, 49, 52, 68, 69, 72, 73, 83:1, 84:1, 89, 90, 90:1, 91, 92, 106, 109, 111, 118, 119, 122, 124, 125, 127, 130, 132, 135, 141, 143, 145, 146, 149, 150, 151, 155, 160, 161, 164, 164:1, 165, 166, 168, 169, 172, 175, 179, 180, 181, 182, 195, 196, 197, 198, 207, 208, 210, 212, 214, 215, 218, 222, 223, 225, 227, 229, 230, 233, 234, 235, 236, 238, 239, 240, 241, 242, 243, 244, 245, 247 and 248,
C.I. Solvent Violet 2, 8, 9, 11, 13, 14, 21, 21:1, 26, 31, 36, 37, 38, 45, 46, 47, 48, 49, 50, 51, 55, 56, 57, 58, 59, 60 and 61;
C.I. Solvent Blue 2, 3, 4, 5, 7, 18, 25, 26, 35, 36, 37, 38, 43, 44, 45, 48, 51, 58, 59, 59:1, 63, 64, 67, 68, 69, 70, 78, 79, 83, 94, 97, 98, 99, 100, 101, 102, 104, 105, 111, 112, 122, 124, 128, 129, 132, 136, 137, 138, 139 and 143,
C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35;
C.I. Solvent Brown 1, 3, 4, 5, 12, 20, 22, 28, 38, 41, 42, 43, 44, 52, 53, 59, 60, 61, 62 and 63;
C.I. Solvent Black 3, 5, 5:2, 7, 13, 22, 22:1, 26, 27, 28, 29, 34, 35, 43, 45, 46, 48, 49 and 50;
Also useful are substituted benzodifuranone dyes whose basic structure conforms to the formula
Such dyes may be substituted on either or both phenyl rings. Useful substituents include halogen, alkyl (which may be interrupted by nonadjacent oxygen atoms), alkoxy (whose alkyl radical may be interrupted by oxygen atoms and may in addition be substituted), hydroxyl, substituted or unsubstituted amino, cyano, nitro and alkoxycarbonyl.
It is further possible to use dyes of the following formulae:
Further examples of insoluble dyes (A1) are recited in WO-A-97/46623, 98/24850 and 99/29783.
The undissolved, dispersed colorant (A1) should be very finely divided. It is preferred for 95%, particularly preferably 99%, of the particles of colorant (A1) to have a particle size xe2x89xa61 xcexcm, preferably xe2x89xa60.5 xcexcm.
Useful dyes (A2), which are soluble in the water/solvent mixture, are in particular arylmethane, azo, methine, rhodamine and metal complex dyes containing acidic or ionic groups.
Examples of useful dyes (A2) are specifically:
C.I. Basic Yellow 2, 37, 78, 94, 96, 97, 98, 102 and 111;
C.I. Basic Orange 2, 60, 62 and 63;
C.I. Basic Red 1, 14, 49, 108 and 111;
C.I. Basic Violet 1, 3, 4, 10, 11, 49 and 50;
C.I. Basic Blue 26, 152, 157, 158 and 161;
C.I. Basic Green 1 and 4;
C.I. Basic Brown 1;
C.I. Acid Orange 7 and 8;
C.I. Acid Blue 9;
C.I. Direct Yellow 4, 5, 11, 15, 127, 131 and 147;
C.I. Direct Red 239 and 254;
C.I. Direct Blue 161, 199, 279 and 281;
C.I. Reactive Red 120.
Colorant preparations according to the invention generally include from 0.01 to 20% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 1 to 6% by weight, of colorant (A), particularly useful amounts for colorant (A1) being within the range from 1 to 6% by weight and for colorant (A2) within the range from 1 to 10% by weight.
When colorant preparations according to the invention are based on undissolved colorants (A1), they will include a dispersant (B). In the case of dissolved colorants (A2), it will be appreciated that component (B) is not necessary.
Component (B) may in principle be any dispersant known for aqueous systems.
Particularly useful components (B) include water-soluble dispersants based on one or more water-soluble alkoxylated phenols (B1), one or more arylsulfonic acid-formaldehyde condensation products (B2), one or more condensation products of an at least difunctional isocyanate with compounds (B3) each bearing one isocyanate-reactive group, one or more alkoxylated hydroxynaphthalenes (B4) or one or more alkoxylation products of at least difunctional aliphatic or aromatic amines having up to 8 carbon atoms.
Preferred dispersants (B1) are alkoxylated phenols of the formula I or II
where
a is from 0 to on average 125,
b is on average from 37 to 250, the ratio b:a being at least 1:1 when b greater than 37, and
d is 0 or 1,
or mixtures thereof.
The products of the formulae I and II can be obtained by reacting the phenol derivatives of the formula III or IV
with propylene oxide and subsequent reaction of the adduct with ethylene oxide or by reacting III and/or IV with ethylene oxide. If desired, the adducts are reacted with chlorosulfonic acid or sulfur trioxide to convert them completely or partially into acid sulfuric esters and the resulting acid esters are neutralized with alkalis.
The phenols of the formulae III and IV can be obtained by reacting phenol or 2,2-(p,pxe2x80x2-bishydroxydiphenyl)propane with 3 or 4 mol of styrene in the presence of an acid as catalyst. The phenols III and IV are reacted according to known processes first with ethylene oxide or only with ethylene oxide in the presence of acidic or alkaline catalysts to form the corresponding alkoxylation products I and II where d=0. The alkoxylation can be carried out, for example, according to the process described in U.S. Pat. No. 2,979,528. When b greater than 37, it is mandatory that the ratio       b    a     greater than   1.
The acid sulfuric esters are prepared by reaction of the alkoxylation products with chlorosulfonic acid or sulfur trioxide, the amount being selected so that all the free hydroxyl groups are sulfated or only a portion thereof. The latter case produces mixtures of compounds of the formulae I and II which contain free and sulfated hydroxyl groups. For use as dispersant, the as-synthesized acid esters of sulfuric acid are converted into water-soluble salts. Advantageous water-soluble salts are the alkali metal salts, for example the sodium or potassium salts. For this two equivalents of the basic compounds are required in the case of chlorosulfonic acid, one equivalent in the case of sulfur trioxide. The basic compound used is advantageously an aqueous alkali metal hydroxide. The neutralization temperature should not exceed 70xc2x0 C. The salts obtained can be used in the form of aqueous solutions or else isolated as such and used in solid form.
Preference is given to dispersants (B1) where a is from 0 to on average 2.5, b is on average from 37 to 250 and d is from 0 to on average 0.5. Particular preference is given to dispersants (B1) where a is 0 to on average 2.5, b is on average from 50 to 100 and d is on average 0.5.
The dispersants (B1) are known; cf. U.S. Pat. No. 4,218,218, for example.
The condensation products (B2) are obtainable by sulfonation of aromatic compounds such as naphthalene itself or naphthalene-comprising mixtures and subsequent condensation of the resulting arylsulfonic acids with formaldehyde.
A suitable starting material for preparing arylsulfonic acids is, for example, a mixture of aromatic compounds which are obtainable by thermal cracking of a naphthenic residue oil and fractionation of the cracking products. Naphthenic residue oils are obtained for example in the cracking of light gasoline and are also referred to as high boiling aromatic hydrocarbon oils. The naphthenic residue oil is preferably thermally cracked at 1400-1700xc2x0 C. The cracking products are then subjected to a fractional distillation. The fraction which passes over at atmospheric pressure (1013 mbar) and 100-120xc2x0 C. is collected and used as the aromatic compound in the sulfonation. Such a fraction is customarily obtained as a by-product in the known acetylene oil quench process (Ullmann""s Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 1985, Volume A1, pages 107 to 112).
This aromatics fraction is a mixture of a multiplicity of aromatic substances whose structures and amount can in practice not be determined in detail. The following aryl compounds are the main representatives of this aromatics fraction:
The aromatics fraction further comprises in terms of identified constituents in amounts from 0.1 to about 2% by weight of the following aryl compounds: fluorene, indan, methylstyrene, phenanthrene, methylindan, dimethylnaphthalene, ethylnaphthalene, xylenes, tetralin, styrene, methylethylbenzene, anthracene, fluoranthrene, pyrene, acenaphthylene and toluene.
Particularly suitable arylsulfonic acids generally comprise xcex1- and xcex2-naphthalenesulfonic acids, the ratio of the xcex1- to the xcex2-isomers being customarily within the range from 20:1 to 1:8, especially within the range from 10:1 to 1:5.
The condensation products based on the abovementioned aromatics fraction preferably have a sulfonic acid group content of not more than 40% by weight.
The preparation of dispersant (B2) can be effected in the presence of aromatic or long-chain aliphatic carboxylic acids, their salts, anhydrides or mixtures thereof.
Examples of suitable aromatic carboxylic acids and derivatives thereof are naphthalenecarboxylic acid, naphthalic acid, terephthalic acid, isophthalic acid, benzoic acid, trimellitic acid, phenylacetic acid, phenoxyacetic acid, salicylic acid, p-hydroxybenzoic acid, diphenylacetic acid, m-hydroxybenzoic acid, benzenetetracarboxylic acid or acid anhydrides such as phthalic anhydride, trimellitic anhydride, benzene-1,2,4,5-tetracarboxylic dianhydride or naphthalic anhydride.
Suitable long-chain aliphatic carboxylic acids include in particular saturated or olefinically unsaturated, linear or branched aliphatic monocarboxylic acids having from 8 to 22, preferably from 8 to 18, carbon atoms of a natural or synthetic origin, for example higher fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid or linolenic acid or synthetically produced carboxylic acids such as 2-ethylhexanoic acid, isononanoic acid or isotridecanoic acid.
Suitable salts of the carboxylic acids mentioned are the alkali metal, ammonium or alkaline earth metal salts, said alkali metal, ammonium or alkaline earth metal salts being obtainable, for example, by neutralization of the corresponding carboxylic acids with sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, magnesium carbonate, calcium oxide, calcium hydroxide, ammonia or alkanolamines such as ethanolamine, diethanolamine or triethanolamine.
Particular preference is given to sodium benzoate, sodium phenylacetate, sodium salicylate, sodium 4-hydroxybenzoate, sodium terephthalate, sodium 2-hydroxy-3-naphthalenecarboxylate, naphthalene-1-carboxylic acid, phthalic anhydride or benzoic acid.
Dispersants (B2) which are particularly suitable in this case comprise from 50 to 97% by weight, especially from 70 to 95% by weight, of arylsulfonic acid/formaldehyde condensation products and from 3 to 50% by weight, especially from 5 to 30% by weight, of aromatic or long-chain aliphatic carboxylic acids, their salts or their anhydrides or mixtures thereof.
To prepare the arylsulfonic acid/formaldehyde condensation products (B2) it is advantageous to start from pure naphthalene (purity generally  greater than 95%).
In the condensation, it is customary to use from 0.5 to 1.5 mol, preferably from 0.7 to 1 mol, of formaldehyde per mole of naphthalene.
The sulfonic acid group content of these condensation products is advantageously within the range from about 40 to 50% by weight.
The dispersants (B2) are known; cf. for example U.S. Pat. No. 5,186,846, DE-A-11 37 005 or EP-A-380 778.
The dispersants (B3) are condensation products of at least difunctional isocyanates, which serve as point of attachment, with a polymeric compound (hereinafter referred to as stabilizer block) which is terminated at one end by an isocyanate-reactive group and which makes solid particles to be dispersed compatible with the dispersion medium, and an anchor group block, which can be either a homo- or copolymer of a nitrogenous monomer or an organic phosphonic ester, which each possess an isocyanate-reactive group and which each sorb onto the solid particles to be dispersed.
The isocyanate connecting the stabilizer block and the anchor group block is a diisocyanate or a more highly functional polyisocyanate having an average NCO functionality of from 2.0 to 4.5.
The diisocyanates can be aromatic or aliphatic, preference being given to aliphatic diisocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4xe2x80x2-di(isocyanatocyclohexyl)methane, 1-isocyanato-3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexane (isophorone diisocyanate) or 2,4- or 2,6-diisocyanato-1-methylcyclohexane, particular preference being given to hexamethylene diisocyanate and isophorone diisocyanate.
The higher polyisocyanates may likewise be aromatic or aliphatic. Here too preference is given to aliphatic polyisocyanates, especially those having an average NCO functionality of from 1.7 to 5, especially about 3. The following groups are mentioned by way of example:
(a) Isocyanurate group containing polyisocyanates of aliphatic and/or cycloaliphatic diisocyanates. Particular preference is given here to the corresponding isocyanato-isocyanurates based on hexamethylene diisocyanate and isophorone diisocyanate. These isocyanurates are in particular simple trisisocyanatoalkyl or trisisocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologs containing more than one isocyanurate ring. The isocyanato-isocyanurates generally have an NCO content of from 10 to 30% by weight, in particular from 15 to 25% by weight, and an average NCO functionality of from 2.6 to 4.5.
(b) Uretdione diisocyanates having aliphatically and/or cycloaliphatically attached isocyanate groups, which are preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
(c) Biuret group containing polyisocyanates having aliphatically attached isocyanate groups, especially tris(6-isocyanatohexyl)biuret or its mixtures with its higher homologs. These biuret group containing polyisocyanates generally have an NCO content of from 18 to 25% by weight and an average NCO functionality of from 3 to 4.5.
(d) Urethane and/or allophanate group containing polyisocyanates having aliphatically or cycloaliphatically attached isocyanate groups, as are obtainable for example by reaction of excess amounts of hexamethylene diisocyanate or of isophorone diisocyanate with simple polyhydric alcohols, such as trimethylolpropane, glycerol, 1,2-dihydroxypropane or mixtures thereof. These urethane and/or allophanate group containing polyisocyanates generally have an NCO content of from 12 to 20% by weight and an average NCO functionality of from 2.5 to 3.
(e) Oxadiazinetrione group containing polyisocyanates, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such oxadiazinetrione group containing polyisocyanates are preparable from diisocyanate and carbon dioxide.
(f) Uretoneimine-modified polyisocyanates.
The polymeric compound forming the stabilizer block is preferably a polymeric compound of the general formula V
R1xe2x80x94Mnxe2x80x94XHxe2x80x83xe2x80x83(V)
where
R1 is hydrogen, linear or branched C1-C28-alkyl, linear or branched, singly or multiply unsaturated C2-C28-alkenyl, linear or branched, singly or multiply unsaturated C2-C28-alkynyl or the residue of polymerization initiator or of a chain regulator,
M represents identical or different polymerized units of monomers selected from the group consisting of xcex1,xcex2-ethylenically unsaturated mono- or dicarboxylic acids;
unsubstituted or hydroxyl-, C1-C6-alkoxy-, polyalkyleneoxy- or halogen-mono- or -polysubstituted C1-C20-(cyclo)alkyl or C7-C20-aralkyl esters, amides, nitriles or anhydrides of xcex1,xcex2-ethylenically unsaturated mono- or dicarboxylic acids; vinyl or allyl esters of aliphatic or aromatic carboxylic acids; vinyl or allyl ethers; ethylenically unsaturated sulfonic acids or sulfonic acid derivatives; halogenated or unhalogenated ethylenically unsaturated aliphatic C2-C20 hydrocarbons; aromatic ethylenically unsaturated compounds and compounds polymerizable to form polyphosphacenes; or is
xe2x80x94Oxe2x80x94COxe2x80x94R6xe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94R6xe2x80x94
or xe2x80x94COxe2x80x94Oxe2x80x94R7xe2x80x94Oxe2x80x94COxe2x80x94R8xe2x80x94
where R2, R3, R4 and R5 are independently H, C1-C6-alkyl, C6-C20-aryl, xe2x80x94CH2xe2x80x94Cl or xe2x80x94CH2xe2x80x94OH, and R6, R7 and R8 are independently a C2-C20-alkylene, arylene or aralkylene group, and
n is an integer between 0 and 10,000, preferably xe2x89xa72, especially xe2x89xa73, particularly preferably within the range from 30 to 1000, and
X is COO, O, S or NR9, where R9 is H or a C1-C6-alkyl group.
The polymeric compound V is preferably constructed using C1-C8-alkyl (meth)acrylates. Particular preference is given to polymerizing one or more C1-C4-alkyl methacrylates, especially methyl methacrylate and/or butyl methacrylate. The isocyanate-reactive group XH is preferably a hydroxyl group which may be introduced into the terminal position of the polyacrylate with the aid of initiators which provide a hydroxyl free radical on decomposition and/or with the aid of chain regulators which contain a hydroxyl group.
The polymeric compound V is most preferably a mono(generally C1-C18, preferably C1-C4)alkyl ether of a poly (especially C2-C4)alkylene glycol, which may be obtained for example by reacting an alkanol with an alkene oxide, such as ethylene oxide, propylene oxide and butylene oxide, or epichlorohydrin. Of particular suitability are C1-C18 (especially C1-C4) alkanols alkoxylated with from 5 to 10,000, preferably from 5 to 80, mol of ethylene oxide and/or propylene oxide, and polyethylene glycol monomethyl ethers are very particularly useful.
The weight average molecular weight of the stabilizer block is preferably within the range from about 250 to 100,000, especially within the range from about 500 to 7000.
An anchor group block embodiment useful for constructing the dispersant (B3) is based on homo- or copolymers of one or more monomers selected from the group consisting of N-vinylamides, N-vinyllactams and vinyl- or allyl-substituted nitrogenous heterocycles. Examples of particularly useful monomers are N-vinylpyrrolidone, N-vinylpyridine, N-vinylcaprolactam, N-vinylimidazole and N-vinylformamide, of which N-vinylpyrrolidone is preferred. The homo- or copolymer preferably has a K value of from 10 to 100, especially from 10 to 30. Termination in the form of a hydroxyl group as isocyanate-reactive group may be accomplished by conducting the polymerization in water or a lower alcohol such as isopropanol or by polymerization in the presence of an appropriate chain regulator and/or initiator.
A further anchor group block embodiment useful for constructing the dispersant (B3) is formed of phosphonic esters of the formula VI
where
R10 and R11 are independently C1-C4-alkyl, especially
R10=R11=methyl or ethyl;
Q is NR(2-p) or CR(3-p) (R=H or C1-C8-alkyl);
R12 and R13 are independently a chemical bond or unsubstituted or C1-C8-alkyl- or aryl-substituted C1-C10-alkylene with or without interruption by O, NR, CO, COO, OCO, CONR or NRCO;
p is 1 or 2; and
Y is COO, O, S or NR14, where R14 is H or a C1-C6 alkyl group.
Preferred examples of these phosphonic esters are diethyl N,N-bis(hydroxyethyl)aminomethylphosphonate, the dimethyl or diethyl esters of 3-hydroxymethylamino-3-oxopropylphosphonic acid, 3-aminopropylphosphonic acid, 1-aminopropylphosphonic acid, 2-aminooctylphosphonic acid, 1-aminooctylphosphonic acid, 1-aminobutylphosphonic acid, hydroxymethylphosphonic acid and 1-hydroxyethylphosphonic acid.
The reaction of the di- or polyisocyanate with the stabilizer block and the anchor group block can take place in two steps or in a one-pot reaction. Preferably, however, the reaction takes place in two steps where the di- or polyisocyanate is reacted with the stabilizer block in the first step. The reaction can take place in the absence or presence of a solvent, preference being given to the reaction in the presence of a solvent, such as acetone, THF, toluene, dioxane. When the stabilizer block has been prepared by polymerization of an ethylenically unsaturated compound, the reaction of the stabilizer block with the di- or polyisocyanate can advantageously be carried out in the same solvent as the free-radical polymerization. The reaction can be carried out without catalyst or preferably in the presence of a catalyst, such as a tertiary amine, especially triethylamine, or a metal salt, especially tin octoate or lead octoate, or an organometallic compound, such as dibutyltin dilaurate or titanium tetramethoxide. The reaction is generally carried out at a temperature from room temperature to 125xc2x0 C., especially within the range from 40 to 90xc2x0 C.
Further details concerning the dispersants (B3) are described in DE-A-198 42 952.
The dispersants (B4) are alkoxylated hydroxynaphthalenes, and ethoxylated xcex2-hydroxynaphthalenes are preferred. The dispersants (B4) generally have a molecular weight MW in the range from 2000 to 40,600 g/mol, especially in the range 20,000 to 35,000 g/mol and particularly in the range from 25,000 to 30,000 g/mol.
The dispersants (B4) are generally known and available in a conventional manner by alkoxylation of hydroxynaphthalene.
Dispersants (B5) are usefully alkoxylation products of at least bifunctional aliphatic or aromatic amines having up to 8 carbon atoms, especially initially propoxylated and then ethoxylated amines. Useful amino components include polyfunctional aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and hexamethylenediamine and aromatic amines such as phenylenediamine and also alcoholamines such as monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, tri(2-propanol)amine, 2-amino-1-butanol, N-butyl-di(2-propanol)amine and aminophenols, preference being given to polyfunctional alkyleneamines, especially ethylenediamine.
The average molecular weight of the condensation products (B5) is preferably in the range from 3000 to 20,000 g/mol and particularly in the range from 4000 to 15,000 g/mol.
The ethylene oxide content of these block copolymers is customarily in the range from 20 to 45% by weight.
The dispersants (B5) are known and described for example in U.S. Pat. No. 2,979,528 and DE-A 31 51 753.
Colorant preparations according to the invention include generally from 0.1 to 25% by weight, preferably from 0.5 to 10% by weight, of dispersant (B) in the case of an undissolved colorant (A1).
Component (C) of colorant preparations according to the invention is an organic solvent. Low molecular weight polytetrahydrofuran (C1) is an essential constituent of component (C); it can be used alone or preferably in mixture with one or more high-boiling water-soluble or -miscible organic solvents (C2).
The polytetrahydrofuran (C1) used according to the invention customarily has an average molecular weight MW of from 150 to 500 g/mol, preferably from 200 to 300 g/mol, particularly preferably about 250 g/mol (corresponding to a molecular weight distribution of from 225 to 275 g/mol; Poly-THF 250, BASF).
The polytetrahydrofuran (C1) may be prepared in known manner by cationic polymerization of tetrahydrofuran. The products are linear polytetramethylene glycols.
When the polytetrahydrofuran (C1) is present in a mixture with further organic solvents (C2), the invention provides that the solvents used be high-boiling (i.e., boiling point generally  greater than 100xc2x0 C.) and hence water-retaining organic solvents that are soluble in or miscible with water.
Useful solvents (C2) include polyhydric alcohols, preferably branched or unbranched polyhydric alcohols containing from 2 to 8, especially from 3 to 6, carbon atoms, such as ethylene glycol, 1,2- and 1,3-propylene glycol, glycerol, erythritol, pentaerythritol, pentitols such as arabitol, adonitol and xylitol and hexitols such as sorbitol, mannitol and dulcitol.
Useful solvents (C2) further include polyethylene glycols and polypropylene glycols (which is also to be understood as meaning the lower polymers (di-, tri- and tetramers)) and their mono (especially C1-C6, in particular C1-C4) alkyl ethers. Preference is given to polyethylene and polypropylene glycols having average molecular weights of from 100 to 1500 g/mol, in particular from 200 to 800 g/mol, mainly from 300 to 500 g/mol. Examples are diethylene glycol, triethylene glycol, tetraethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, di-, tri- and tetra-1,2- and -1,3-propylene glycol and di-, tri- and tetra-1,2- and -1,3-propylene glycol monomethyl, monoethyl, monopropyl and monobutyl ether.
Useful solvents (C2) further include pyrrolidone and N-alkylpyrrolidones whose alkyl chain preferably contains from 1 to 4, especially 1 or 2, carbon atoms. Examples of useful alkylpyrrolidones are N-methylpyrrolidone, N-ethylpyrrolidone and N-(2-hydroxyethyll)pyrrolidone.
Examples of particularly preferred solvents (C2) are 1,2-propylene glycol, 1,3-propylene glycol, glycerol, sorbitol, diethylene glycol, polyethylene glycol (MW from 300 to 500 g/mol), diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, pyrrolidone, N-methylpyrrolidone and N-(2-hydroxyethyl)pyrrolidone.
The polytetrahydrofuran (C1) may be mixed with one or more (e.g., two, three or four) solvents (C2).
Colorant preparations according to the invention generally include from 0.1 to 40% by weight, preferably from 5 to 30% by weight, particularly preferably from 10 to 25% by weight and very particularly preferably from 10 to 20% by weight, of solvent component (C).
The weight ratio of (C2) to (C1) is preferably within the range from 20:1 to 1:1. Colorant preparations according to the invention accordingly preferably include from 0.5 to 20% by weight, especially from 1 to 10% by weight, of polytetrahydrofuran (C1) and from 1 to 30% by weight, especially from 1 to 20% by weight, of solvent (C2).
An example of a particularly preferred solvent component (C) is the combination of from 1 to 10% by weight of polytetrahydrofuran (MW from 150 to 500 g/mol), from 1 to 10% by weight of glycerol, sorbitol and/or propylene glycol, from 1 to 10% by weight of polyethylene glycol (MW from 300 to 500 g/mol) and from 1 to 10% by weight of di- and/or triethylene glycol monobutyl ether (amounts each based on the weight of the colorant preparation).
The solvent component (C), including especially the aforementioned particularly preferred solvent combination, may advantageously be supplemented by urea (generally from 0.5 to 3% by weight, based on the weight of the colorant preparation), which further enhances the water-retaining effect of solvent mixture (C).
Water is the main constituent (D) of colorant preparations according to the invention. The water content is customarily within the range from 50 to 95% by weight. The preferred water content is from 60 to 80% by weight in the case of binder-free preparations and from 50 to 75% by weight in the case of binder-containing preparations.
Colorant preparations according to the invention may self-evidently include further assistants of the type which are customary especially for (aqueous) ink-jet inks and in the printing and coatings industry. Examples of such assistants include preservatives (such as 1,2-benzisothiazolin-3-one and its alkali metal salts, glutaraldehyde and/or tetramethylolacetylenediurea), antioxidants, degassers/defoamers (such as acetylenediols and ethoxylated acetylenediols, which customarily contain from 20 to 40 mol of ethylene oxide per mole of acetylenediol and also have a dispersing effect), viscosity regulators, flow agents, wetters (e.g., wetting surfactants based on ethoxylated or propoxylated fatty or oxo alcohols, propylene oxide/ethylene oxide block copolymers, ethoxylates of oleic acid or alkylphenols, alkylphenol ether sulfates, alkylpolyglycosides, alkyl phosphonates, alkylphenyl phosphonates, alkyl phosphates, alkylphenyl phosphates or preferably polyether siloxane copolymers, especially alkoxylated 2-(3-hydroxypropyl)heptamethyl trisiloxanes, which generally have a block of from 7 to 20 and preferably of from 7 to 12 ethylene oxide units and a block of from 2 to 20 and preferably of from 2 to 10 propylene oxide units and may be present in the colorant preparations in amounts of from 0.05 to 1% by weight), anti-settlers, luster improvers, lubricants, adhesion improvers, anti-skinning agents, delusterants, emulsifiers, stabilizers, water repellents, light control additives, hand improvers, antistats and bases such as triethanolamine for regulating the pH. If such assistants are part of the pigment preparations of the invention, their total amount is generally xe2x89xa62% by weight, especially xe2x89xa61% by weight, based on the weight of the colorant preparation.
Binder-free colorant preparations according to the invention customarily have a dynamic viscosity of from 1 to 7 mm2/sec, preferably from 1 to 5 mm2/sec, especially from 1 to 3 mm2/sec. Binder-containing colorant preparations according to the invention have a dynamic viscosity of generally from 1 to 25 mm2/sec, preferably from 1 to 15 mm2/sec, mainly from 1 to 10 mm2/sec.
The surface tension of colorant preparations according to the invention (binder-free or -containing) is generally within the range from 24 to 70 mN/m, especially from 30 to 60 mN/m.
The pH of colorant preparations according to the invention is generally from 5 to 10, preferably from 7 to 9.
Colorant preparations according to the invention which are based on undissolved colorant (A1) are advantageously prepared as follows:
The colorant (A1), for example in the form of an aqueous presscake, is mixed together with the dispersant (B) in the presence of water and dispersed in a suitable apparatus. The resulting mixture is then ground in a mill to the desired particle size distribution (generally xe2x89xa61 xcexcm, preferably xe2x89xa60.5 xcexcm). After the desired colorant concentration has been set by addition of solvent (C), water and optionally further assistants, the preparation is filtered using a filtering means with fines removal within the range from 1 to 0.5 xcexcm.
Particularly useful starting materials for preparations of dissolved dye (A2) are more highly concentrated dye solutions, for example paper dye liquid formulations from 10 to 30% strength by weight. These are, if appropriate, desalted and filtered (e.g., nanofiltration) before the desired dye concentration is set.
The colorant preparations of the invention can be used with advantage in the process of the invention for printing sheetlike or three-dimensionally configured substrates by the ink-jet process, which comprises printing the colorant preparations onto the substrate and if desired subsequently fixing the print obtained.
In the ink-jet process, the typically aqueous inks are sprayed as small droplets directly onto the substrate. There is a continuous form of the process, in which the ink is pressed at a uniform rate through a nozzle and the jet is directed onto the substrate by an electric field depending on the pattern to be printed, and there is an interrupted or drop-on-demand process, in which the ink is expelled only where a colored dot is to appear, the latter form of the process employing either a piezoelectric crystal or a heated hollow needle (bubble or thermal jet process) to exert pressure on the ink system and so eject an ink droplet. These techniques are described in Text. Chem. Color 19 (1987), No. 8, 23-29, and 21 (1989), No. 6, 27-32.
The colorant preparations of the invention are particularly useful as inks for the bubble jet process or the process employing a piezoelectric crystal.
If the print is to be fixed, this may be done in a known manner and as described in WO-A-99/01516 by, for example, applying a binder, if desired in the form of a dispersion or emulsion, to the printed substrate and curing the binder or laminating on a film.
However, the colorant preparations of the invention may also already contain the thermally or radiation-chemically curable binder, generally in an amount of from 2 to 20% by weight (reckoned on 100% solids).
Useful thermally curable binders include for example binders that are based on acrylates containing methylol groups and that crosslink by polycondensation in particular.
Preferred systems are mixtures of
from 1 to 10% by weight of N-methylol(meth)acrylamide or its C1-C4-alkyl ethers and if desired monomers containing halohydrin groups such as 2-hydroxy-3-chloropropylene acrylate and
from 90 to 99% by weight of comonomers, for example selected from the group consisting of butadiene, styrene, (meth)acrylic acid, (meth)acrylonitrile, (meth)acrylic and vinyl esters having up to 12 carbon atoms, vinyl chloride and N-vinylpyrrolidone as described for example in DE-A-16 19 656.
Acrylic acid derivatives containing methylol groups effect additional crosslinking under the action of acids or of compounds that detach protons on heating such as ammonium phosphates.
Useful thermally curable binders further include for example binders which are based on polyurethane prepolymers and which likewise crosslink by polycondensation.
Radiation-curable binders for the purposes of the present invention are binders which are curable by irradiation with high energy radiation, i.e., electromagnetic radiation especially from 220 to 450 nm (UV radiation) or electron beams. Suitable are not only free-radically but also cationically polymerizable binder components and also mixtures thereof.
Examples are acrylate, vinyl or epoxy monomers, prepolymers, polymers and mixtures thereof.
Further details concerning these binders are disclosed in WO-A-99/01516.
The colorant preparations of the invention may be printed on all types of substrate materials. Examples of substrate materials include
coated or uncoated cellulosics such as paper, paperboard, cardboard, wood and woodbase,
coated or uncoated metallic materials such as foils, sheets or workpieces composed of aluminum, iron, copper, silver, gold, zinc or alloys thereof,
coated or uncoated silicatic materials such as glass, porcelain and ceramics,
polymeric materials of any kind such as polystyrene, polyamides, polyesters, polyethylene, polypropylene, melamine resins, polyacrylates, polyacrylonitrile, polyurethanes, polycarbonates, polyvinyl chloride, polyvinyl alcohols, polyvinyl acetates, polyvinylpyrrolidones and corresponding copolymers and block copolymers, biodegradable polymers and natural polymers such as gelatin,
textile materials such as fibers, yarns, threads, knits, wovens, nonwovens and garments composed of polyester, modified polyester, polyester blend fabrics, cellulosics such as cotton, cotton blend fabrics, jute, flax, hemp and ramie, viscose, wool, silk, polyamide, polyamide blend fabrics, polyacrylonitrile, triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride, polyester microfibers and glass fiber fabric,
leatherxe2x80x94both natural and artificialxe2x80x94in the form of smooth leather, nappa leather or suede leather,
comestibles and cosmetics.
The substrate material may be sheetlike or three-dimensional in configuration and may be printed with the colorant preparations of the invention both uniformly and imagewise.
Colorant preparations according to the invention are useful ink-jet inks having altogether advantageous application properties, especially good start-of-print behavior and good sustained use behavior (cogation), and, especially when using the particularly preferred solvent combination (C), good drying behavior, and producing prints of high quality, i.e., brilliance and depth of shade, and also high rubfastness, lightfastness, waterfastness and wetrubfastness. They are particularly useful for printing coated and uncoated paper.


The present invention is a shim or shim assembly that clips onto a brake caliper piston. It is generally a rimmed round (disc or annular) shape to cap the edges of the caliper piston and includes surface features for lubrication, and improved fitting. Reduced noise from frictional fretting is provided along with protection of piston's outer rim. Reduced thermal transfer into the piston is also provided.

1. Field of the Invention
The invention relates to noise-reducing shims for disc brake systems, and more particularly relates to shims for mounting on the brake piston.
2. Description of the Related Art
In a disc brake caliper, a hydraulically actuated piston forces, by action and reaction, a pair of opposing brake pads to pinch a rotor attached to a vehicle wheel. Brake pads have a stiff backing plate with friction pads affixed to one side. Shims of a thin material are often used on the side of the plate contacted by the piston. The shim's function is to reduce the frequency of occurrence of a loud and annoying squeal noise from what are otherwise mechanically perfect brakes. At least some of the noise comes from the fact that, to prevent jamming, the plate has some freedom of radial movement within the caliper so that the rotor can be freed, while the piston has little freedom of movement.
In braking, the rigid rotor is frictionally engaged by the hard brake pad (which is in turn supported by its hard backing plate). The brake pad can frictionally slide to some degree against the rigid piston and caliper.
High frictional forces are generated during this sliding movement which can cause squeal. Like a stick of chalk forced at an angle across a rigid board, friction can lead to very severe vibrational noise. As well, these recurring forces can lead to fretting and chipping of the piston rim. A great many designs of shims have been tried over the years to fit between the piston and the plate to reduce such friction and resulting squeal. None have been entirely satisfactory.
Brake squeal is a very expensive problem for car and brake manufacturers as customers invariably want the noise remedied under warranty even though the brakes are otherwise perfect.
Shims are typically designed to fit against the backing plate of the brake pad. Almost every separate vehicle model has a unique backing plate size and shape. This requires large and therefore expensive inventories.
Piston-side shims are less well-known, but have certain advantages. One advantage is that there are fewer variations in piston size and shape across vehicle models.
However, existing piston-side shims are bulky and have undesirably complex manufacturing requirements. Further, such piston-side shims are not designed to optimize smooth sliding potential against the brake backing plate, and accordingly may not be effective in reducing vibrational noise. It would desirable to allow the shim to slide smoothly against the backing plate to reduce the undesirable friction. At the same time, the shim must be maintained in a secured and well-located state on the piston edge to prevent the piston edge from becoming exposed on one edge when contacted with the backing plate (i.e. to prevent scraping and fretting of the piston edge which can lead to damage).