Lithium-containing cement admixtures including a calcium aluminate phosphate cement; a lithium-ion-containing compound; and an aqueous base fluid and methods of introducing the lithium-containing cement admixtures into a subterranean formation. The lithium-containing cement admixtures may further comprise an aluminosilicate or an additive including a set retarder, a set accelerator, a suspension aid, a density reducing agent, a fluid loss control agent, a defoamer, and any combination thereof.

The embodiments herein relate generally to subterranean formation operations and, more particularly, to lithium-containing calcium aluminate phosphate admixtures.
Subterranean formation operations (e.g., stimulation operations, sand control operations, completion operations, etc.) often involve placing a cement column around a casing (or liner string) in a wellbore. In some instances, the cement column is formed by pumping a cement slurry through the bottom of the casing and out through an annulus between the outer casing wall and the formation face of the wellbore. The cement slurry then cures in the annular space, thereby forming a sheath of hardened cement that, inter alia, supports and positions the casing in the wellbore and bonds the exterior surface of the casing to the subterranean formation. This process is referred to as "primary cementing." Among other things, the cement column may keep fresh water zones from becoming contaminated with produced fluids from within the wellbore. As used herein, the term "fluid" refers to liquid phase fluids and gas phase fluids. The cement column may also prevent unstable formations from caving in, thereby reducing the chance of a casing collapse and/or stuck drill pipe. Finally, the cement column may also form a solid barrier to prevent fluid loss from the wellbore into the formation and the contamination of production zones with wellbore fluids. Remediation for these issues of a cement column after primary cementing operations is referred to as "secondary cementing," and may be costly in terms of equipment, materials, and operator time.
The degree of success of a subterranean formation operation involving placement of a cement column therefore depends, at least in part, upon the successful cementing of the wellbore casing. Cement slurries are typically designed to have a hydrostatic pressure between the formation pore pressure and the fracture gradient of the formation to prevent fluid migration within the cement slurry and prevent fracturing of the subterranean formation. As used herein, the term "formation pore pressure" refers to the pressure of the subsurface formation fluids within the subterranean formation itself. As used herein, the term "fracture gradient" refers to the pressure required to induce or enhance fractures in a subterranean formation at a given depth. During cement hydration, the hydrostatic pressure of the cement slurry decreases and it may drop below the formation pore pressure, allowing fluid invasion and migration within the cement slurry, a common obstacle of primary cementing. As used herein, the term "cement hydration" (or "cement setting") refers to the process of transforming a cement slurry into a solid, hardened mass, and the term "hydrating cement slurry" refers to the cement slurry itself which has not fully hydrated and become a solid, hardened mass.
The duration of cement hydration is critical to a cementing operation. For example, cement slurries must remain in liquid form for a period of time sufficient to pump the slurry through the casing and into the annular space, including calculated unavoidable delay time. Premature setting of the slurry results in hardened cement masses in unwanted areas in equipment, the wellbore, or the annular space, which may require costly remedial operations and production delay. Conversely, a cement slurry that takes a prolonged period of time to set after being placed in the annular space can result in significant wait on cement ("WOC") time and delay drill out, both of which increase rig time and operator time. This pump time for a particular cement slurry depends on, at least in part, the composition of the slurry, the conditions of the subterranean formation (e.g., temperature), the pump rate, and the like. The term "pump time," as used herein, refers to the time required to reach a consistency of the cement such that it is no longer deemed pumpable, defined herein as a consistency of greater than about 50 Bearden units of consistency ("Bc"), or greater than about 70 Bc, or greater than about 95 Bc. As used herein, the term "consistency" refers to a rheological property of a cement related to the cohesion of individual components of the cement, its ability to deform, and its ability to resist flow.
One type of cement is a calcium aluminate phosphate ("CAP") cement. CAP cements have been used in primary cementing operations due to their ability to set in desired timeframes and provide desired compressive strengths in geothermal wells with relatively high temperatures, or at least upwards of 60° C. (140° F.). However, some subterranean formations having hydrocarbon reservoirs exhibit much lower temperature ranges (e.g., below about 60° C. (140° F.), or below about 54° C. (130° F.), or below about 50° C. (120° F.)), where the heat of the subterranean formation is not able to aid in setting the CAP cement. Moreover, regardless of the formation temperature, lower density CAP cements may fail to achieve desired pump times and compressive strengths.

Lithium-containing calcium aluminate phosphate cement admixtures


A method of manufacturing an integrated circuit device is provided. A first feature, which has a first susceptibility to damage by chemical mechanical processing (CMP), is formed at a first height as measured from an upper surface of the substrate. A second feature, which has a second susceptibility to damage by the CMP, is formed at a second height as measured from the upper surface of the substrate and is laterally spaced from the first feature by a recess. The second height is greater than the first height, and the second susceptibility is less than the first susceptibility. A sacrificial coating is formed in the recess over an uppermost surface of the first feature. CMP is performed to remove a first portion of the sacrificial coating and expose an upper surface of the second feature while leaving a second portion of the sacrificial coating in place over the first feature.

The present disclosure relates to integrated circuit (IC) device manufacturing processes especially replacement gate processes.
In an effort to increase device densities, many years of research have been devoted to reducing critical dimensions (CDs) in semiconductor devices. This research has led to a long felt need to replace traditional gate materials with high-k dielectrics and metal gates. High-k dielectrics can provide enhanced capacitance in comparison to an equivalent thickness of silicon dioxide. Metal electrodes with suitable work functions can avoid charge carrier depletion proximate the electrode interface with the high-k dielectric. The electrodes for P-channel and N-channel transistors generally require different metals.
Suitable metals for gate electrodes can be adversely affected by processing used to form source and drain regions. In particular, annealing can cause an undesirable shift in the work function of electrode metals. This has led to the development of various new processes, including replacement gate (gate-last) processes. In a replacement gate process, a dummy gate stack is formed, which is a gate stack formed using polysilicon or other material in place of the gate metals. After source and drain regions are formed, the polysilicon is removed to form trenches which are then filled with the desired metals.

CMP-friendly coatings for planar recessing or removing of variable-height layers

Taiwan Semiconductor Manufacturing Co., Ltd.


Described herein are compositions comprising polymers prepared by melt polycondensation of 2-hydroxyalkyl acids. Methods of making and using the compositions are also disclosed.

The properties of polylactide, such as the glass-transition temperature Tg, crystallinity, lipophilicity, and degradation time can be changed by modifying the stereochemistry of the polymer, the molecular weight, or by copolymerization with a suitable copolymer. Although polylactide can be modified for use in various applications, polylactide often forms solid aggregates that make it difficult to formulate bioactive agents with polylactide. Additionally, polylactide is not suitable for use as an injectable without formulating the polylactide as a nano- or microparticle, or without adding further excipients.
As such, a need exists for compositions that overcome the foregoing deficiencies in polymers commonly used in the art, including polylactide. These needs and other needs are satisfied by the present invention.

Compositions comprising polymers prepared from 2-hydroxyalkyl acids


A hand-holdable steering mechanism is used as part of a medical device such as a catheter or an endoscope to allow movement of a steerable distal portion of the catheter or endoscope. The mechanism can include a housing and an actuation system. The actuation system is adapted for one-handed operation by a user, and it allows the user to achieve 360 degree articulation of the steerable distal portion. The actuation system can include a first actuator and a second actuator where the first and second actuators are movable with respect to each other. The first actuator can be at least partially disposed within the second actuator.

Steering mechanisms are used to steer or direct a medical instrument, for example a catheter or endoscope, to a desired position or location in a body of a patient. One known steering mechanism resembles a joystick. The configuration of the joystick usually includes a plate attached to control wires. The plate, however, must be large to accommodate the desired articulations of the steerable medical device. Additionally, the single control element encompassed in the joystick control mechanism makes the introduction of force leverage very difficult, especially in a procedure during which an increased leverage is needed for different articulation planes. Further, all control wires are manipulated by the joystick, therefore, movement of the joystick may cause additional, albeit unintended, articulation of the catheter or endoscope.
Another known steering mechanism includes multiple slidable buttons. Each button is connected to a puller wire so that when the button is moved, the puller wire moves the catheter in a single direction associated with the puller wire. Thus, at least four slidable buttons are required to achieve 360 degree articulation of the catheter or endoscope. The sliding motion of the buttons on this steering mechanism makes introduction of force leverage very difficult. Furthermore, the catheter can only be articulated along one plane at a time unless the user moves more than one button at the same time, which requires that the user either use multiple fingers or continuously move his or her hand to manipulate the buttons and operate the device.


A method and apparatus used to step and correct the position of raster lines in a sinusoidal or zig-zag deflection system. By combining the magnetic flux generated with a rotation “twister” coil and a vertical deflection coil, scan lines can be uniformly spaced and separated nearly to their ends. Accordingly, the magnetic flux generated with the twister coil is adjusted going in the left to right direction then reversed in polarity and readjusted while returning from right to left. It is this controlled twister flux that combines with the linear vertical deflection flux to straighten and then step each scan line to produce an aligned raster.

1. Field of the Invention
The invention relates to cathode ray tube displays. More specifically, the invention describes a method and apparatus for generating a dynamic rotation field to precisely align raster scan lines displayed on a cathode ray tube. The invention is of significant interest in low and very low power sinusoidal, wide and very wide angle deflection systems, as well as DTV, HDTV and VHDTV, and other high and very high resolution video displays.
2. Definitions
To align is to cause a video image to be adjusted so that distortion characteristics are minimized and the video image that is displayed on the cathode ray tube forms an image that is pleasing to the eye.
A cathode ray tube refers to the tube structure, the phosphor screen, the neck of the tube, the deflection and control windings, including the yoke, rotation and other coils, and the electron guns.
Coordinate locations are discrete physical locations on the face of the cathode ray tube, or a physical area on the CRT screen.
Correction and driver circuitry are one or more of the following: digital to analog converters, interpolation engine, pulse width modulators and pulse density modulators, as well as summing amplifiers, oscillators, op-amps, inverters comparators or any other components necessary to produce and condition correction signals to synchronously apply to control circuitry to generate an aligned video image.
Correction control signals are correction factor signals that have been combined in a manner to be applied to either horizontal control circuitry, vertical control circuitry, coils, or electron gun circuitry.
Correction factor data includes the encoded digital bytes or any other form of data, such as term multipliers that adjust standardized transformation equations, that are representative of the amount of correction required to align a video signal at a particular physical location on a cathode ray tube to counteract distortion characteristics at that location. Correction factor data may include data from the gain matrix table, data relating to electron gun characteristics and/or data relating to geometry characteristics of the cathode ray tube.
Correction factor parameters include various geometry characteristics of the cathode ray tube including horizontal size, raster rotation, vertical size, horizontal center, vertical center, pin cushioning, vertical linearity, keystoning, convergence, etc., and various electron gun characteristics of the cathode ray tube including contrast, brightness, luminosity, focus, color balance, color temperature, electron gun cutoff, etc.
Correction factor signals are digital correction signals that have been integrated or filtered.
Correction signals are digital correction signals and correction factor signals.
A decoder is a device for generating an electronic signal in response to one or more data bytes that may include PWMs, PDMs, DACs, interpolation engines, on screen display chips, etc.
A deflection yoke consists primarily of two coils: a horizontal and a vertical coil—designating horizontal or vertical deflection of the electron beam through the CRT. Of these coils the major power consumer is the horizontal coil because it is driven at a high horizontal scan frequency, whereas the vertical coil is driven at the lower vertical scan frequency. Other coils may also deflect, rotate or reshape the electron beam or beams and be incorporated within the Deflection Yoke assembly.
A device is any apparatus which incorporates a cathode ray tube as part of its implementation.
Digital correction signals are signals that are generated by decoders, such as pulse width modulators, pulse density modulators, digital to analog converters, etc. in response to correction factor data.
A digital monitor board is a circuit board that includes one or more of the following: vertical control circuitry, horizontal control circuitry, electron gun control circuitry, correction and driver circuitry, a logic device, digital to analog converters, and a memory. A digital monitor board may comprise an actual chassis monitor board used with a particular monitor, an ideal chassis board, a chassis board that can be adjusted to match the characteristics or specifications of a particular monitor board, etc.
A digitized signal is any electrical signal that has a digital nature.
A direction can be up, down, left, right, clockwise, anti-clockwise, brighter, dimmer, higher, lower, etc.
Discrete locations may be individual pixels on a cathode ray tube screen or may comprise a plurality of pixels on a cathode ray tube screen.
Distortion characteristics are the amount of any particular type of distortion as indicated by the distortion data measured at a number of different points on the cathode ray tube.
Distortion data is a measure of the amount of distortion that exists on a cathode ray tube with regard to the geometry characteristics of the tube, and/or electron gun characteristics of the tube. For example, distortion data can be measured as a result of misalignment of a video image or improper amplitude or gain of a video signal. Distortion data can be a quantitative measure of the deviation of correction factor parameters from a desired quantities value. Distortion data can be measured at coordinate locations on the cathode ray tube.
Driver signals are the electrical signals that are used to drive the deflection and control windings, and electron guns of the cathode ray tube.
Internal to raster is any part or section of a CRT raster as defined by its location on the raster.
Memory can be any desired storage medium including, but not limited to, EEPROMs, RAM, EPROMs, PROMs, ROMs, magnetic storage, magnetic floppies, bar codes, serial EEPROMs, flash memory, etc.
A non-volatile electronic storage device is an electrical memory device that is capable of storing data that does not require a constant supply of power.
A pattern generator is any type of video generator that is capable of generating a video signal that allows measurement of distortion data.
A processor is a logic device including, but not limited to state machines, micro-processors, etc.
A raster is all or part of the horizontal traces produced on the face of a CRT.
A rotation coil is a coil or winding used to rotate the raster in a CRT.
Rotational distortion characteristics are the amount of rotational distortion as indicated by the rotational distortion data measured at a number of different points on a cathode ray tube.
Rotational distortion data is a measure of the amount of rotational distortion that exists on a specific cathode ray tube with regard to the geometry characteristics of the tube. For example, rotational distortion data can be a result of misalignment of a video image on the face of the CRT. Rotational distortion data can be a quantitative measure of the deviation of rotational correction factor data from a desired quantitative value. Rotational distortion data can be measured at coordinate locations on the cathode ray tube.
Rotation driver signals are time dependent analog signals generated, by various methods, and applied synchronously to the CRT rotation coil to dynamically align traces of the CRT raster display.
A storage disk may include any type of storage device for storing data including magnetic storage devices such as floppy disks, optical storage devices, magnetic tape storage devices, magneto-optical storage devices, compact disks, etc.
A variable resistor is an apparatus capable of producing a changeable value of electrical resistance.
A video image is the displayed image that appears on the cathode ray tube screen that is produced in response to a video signal.
A video pattern is the video image of a pattern that appears on the cathode ray tube raster as a result of the video signal generated by the pattern generator.
A video signal is the electronic signal that is input to the electron guns of the cathode ray tube.

This patent is subject to a terminal disclaimer.

Method and apparatus for providing a dynamic rotational alignment of a cathode ray tube raster


A method for forming an interactive image of a property comprising determining at least a first measurement of a space within the property forming at least one measurement line, inputting the at least first measurement to a processor, and inputting textual information and at least one graphic image concerning the space to the processor. A property overview image is then formed using computer instructions, the at least first measurement, the at least one measurement line, the textual information, and the at least one graphic image. The property overview image is then output for viewing by a user.

A need exists for a method for forming an interactive image of a space, which can be a property including one or more structures or outside spaces, that compiles an interactive property overview image for land and structures within a property, a listing of features for the property, and one or more digital images of selected interior and exterior views of structures and outside spaces, into a single file, allowing a user to individually or simultaneously access floor plans of structures, birds-eye views and/or satellite images of land, the text information, and the one or more digital images. A property overview image can include one or more floor plan images of one or more structures, combined with depictions of outdoor land, spaces, features, and structures. Acreage plans can include multiple nested or embedded floor plans.
A further need exists for method for forming an interactive image of a property that incorporates accurate on-site measurements for one or more rooms of a structure or one or more dimensions of an outside space or geographical feature, records such measurements within a file relating to the property, and produces a property overview image that is drawn to scale, using one or more measurement lines representative of actual on-site measurements.
A need exists for method that produces graphical images that correspond to interior details of a property, such as the inside of closets, cabinetry, appliances, ceiling lines and features, roof lines and features, windows, flooring, and attics, and graphical images that correspond to outdoor details of a property, such as the locations and dimensions of trees, outdoor structures, lakes, farmland, fences, and other similar manmade and geographical outdoor features.
A further need exists for a method that produces rooms and outside spaces drawn to scale, graphic images representing indoor and outdoor features, annotated text information labeling and describing features, and optionally, icons for linking to digital images, in a single property overview image, providing a seamless, integrated product for use by property buyers, sellers, and real estate agents.
The present embodiments meet these needs.
The present embodiments are detailed below with reference to the listed Figures.

Method for forming an interactive image of indoor and outdoor spaces


An apparatus for generating a time-delayed product of two independent signals includes a fixed-wavelength laser. A first optical modulator is optically coupled to the fixed-wavelength laser and configured to modulate a fixed wavelength optical carrier with a first input signal of a set of input signals. The apparatus also includes a tunable laser. A second optical modulator is optically coupled to the tunable laser and configured to modulate a tunable optical carrier with a second input signal of the set of input signals. The apparatus also includes a dispersive element coupled to the second optical modulator, a first optical detector coupled to the dispersive element, a third optical modulator optically coupled to the first optical detector and the first optical modulator, an optical 90-degree hybrid element optically coupled to the third optical modulator, and a plurality of optical detectors optically coupled to the optical 90-degree hybrid element.

Real-time signal analysis is strictly dictated by the waveform bandwidth. Current electronic processors allow for complex analysis for signals with bandwidth smaller than 1 GHz. Examples of currently viable real-time electronic processing include Fourier and Hilbert transforms, correlation, convolution, pattern matching, and cyclostationary analysis. To perform any of these, a physical signal must first be digitized, mandating the use of an analog-to-digital (ADC) convertor processor in the front-end. While a number of applications can be served by sub-GHz signal analysis, a number of important applications require real-time analysis of signals with bandwidth exceeding 1 GHz.
With the emergence of high-capacity wireless communications, spectral analysis of wideband radio-frequency signals, associated with military applications in the past, has emerged as one of the most important applications. Current 5G wireless infrastructure incorporates signaling in excess of 1 GHz, requiring real-time spectral analysis for the purposes of provisioning, network surveillance, security and traffic conflict resolution. In electronic warfare, higher-order spectral analysis of the contiguous radio-frequency (RF) band (e.g., 1 kHz-110 GHz) is dictated by a need to identify, intercept and geolocate any emitter and classify its operation. In light wave (e.g., fiber optic) communication, it is necessary to analyze channels with aggregate capacity exceeding 400 Gbit/sec in order to provide real-time security and reverse transmission penalties. Current electronic processors possess neither the precision nor speed to satisfy these applications, causing a need for improved methods and systems that can address analysis of wideband signals.

Method and system for performing signal analysis using a hybrid photonic-electronic processor


A process for the preparation of chemical toner by mixing a colorant, a latex, optionally a wax, and a first coagulant of, for example, a polyaluminum sulfosilicate and a second cationic coagulant of, for example, a benzylalkonium chloride.

In U.S. Pat. No. 6,132,924, the disclosure of which is totally incorporated herein by reference, there is illustrated a process for the preparation of toner comprising mixing a colorant, a latex, and two coagulants, followed by aggregation and coalescence, and wherein one of the coagulants may be polyaluminum chloride.
In U.S. Pat. No. 6,268,102, the disclosure of which is totally incorporated herein by reference, there is illustrated a process for the preparation of toner comprising mixing a colorant, a latex, and two coagulants, followed by aggregation and coalescence, and wherein one of the coagulants is a polyaluminum sulfosilicate.
Illustrated in U.S. Pat. No. 5,994,020, the disclosure of which is totally incorporated herein by reference, are toner processes, and more specifically, a process for the preparation of toner comprising:
(i) preparing, or providing a colorant dispersion;
(ii) preparing, or providing a functionalized wax dispersion comprised of a functionalized wax contained in a dispersant mixture comprised of a nonionic surfactant, an ionic surfactant, or mixtures thereof;
(iii) shearing the resulting mixture of the functionalized wax dispersion (ii) and the colorant dispersion (i) with a latex or emulsion blend comprised of resin contained in a mixture of an anionic surfactant and a nonionic surfactant;
(iv) heating the resulting sheared blend of (iii) below about the glass transition temperature (Tg) of the resin particles;
(v) optionally adding additional anionic surfactant to the resulting aggregated suspension of (iv) to prevent, or minimize additional particle growth of the resulting electrostatically bound toner size aggregates during coalescence (iv);
(vi) heating the resulting mixture of (v) above about the Tg of the resin; and optionally,
(vii) separating the toner particles.
The appropriate components and processes of the above recited copending applications and patents may be selected for the processes of the present invention in embodiments thereof.
The present invention is generally directed to toner processes, and more specifically, to chemical processes which involve the aggregation and fusion of a resin containing latex, colorant like pigment, or dye, and additive particles into toner particles, and wherein aggregation can be primarily controlled by utilizing a coagulant of polyaluminum sulfosilicate (PASS), which silicate is commercially available, and is believed to be disclosed in U.S. Pat. Nos. 4,981,675; 5,069,893; 5,149,400; 5,296,213, the disclosures of which are totally incorporated herein by reference; and subsequently adding a cationic ionic surfactant as a second co-coagulant, such as SANIZOL B(trademark), that is a benzylalkonium chloride, and wherein there is preferably selected a latex comprised of, for example, submicron resin particles in the size range of, for example, about 0.1 to about 0.5 micron in volume average diameter, suspended in an aqueous phase of water, nonionic and anionic surfactants and optionally suspended in an anionic surfactant to which is added a colorant dispersion comprising, for example, submicron colorant particles in the size range of, for example, about 0.08 to about 0.5 micron in volume average diameter, anionic surfactant, or optionally a nonionic surfactant, or mixtures thereof, and optionally adding thereto a wax dispersion comprising, for example, submicron wax particles in the size range of about 0.1 to about 0.5 micron in volume average diameter suspended in an aqueous phase of water and an anionic surfactant, and wherein the resultant blend is preferably stirred and heated to a temperature below the resin Tg, resulting in aggregates to which is optionally added thereto a second latex, followed by adjusting the pH of the mixture with a base, and heating the mixture to a temperature above the resin Tg, followed by lowering the pH of the mixture with, for example, a metal salt to fuse the aggregates.
More specifically, the present invention is generally directed to the aggregation of latex, colorant and optionally a wax in the presence of polyaluminum sulfosilicate and optionally a coagulant, such as SANIZOL B(trademark), that is benzylalkonium chloride, and wherein the coalescence or fusion of the aggregates is accomplished by a reduction of the pH with an aqueous solution of, for example, aluminum sulfate, and wherein there are generated toner compositions with, for example, a volume average diameter of from about 1 micron to about 25 microns, and preferably from about 2 microns to about 12 microns, and a narrow particle size distribution of, for example, from about 1.10 to about 1.33, and preferably a size distribution in the range of 1.11 to 1.25, the size and size distribution being measured by a Coulter Counter, without the need to resort to conventional pulverization and classification methods. Furthermore, the present invention in embodiments enables minimum washing, for example about 2 to about 4 washings, to provide a suitable toner triboelectrical charge, such as greater than about 20 xcexcC/g at 20 percent RH. The toners generated can be selected for known electrophotographic imaging and printing processes, including digital color processes.
In the embodiments of the present invention when a co-coagulant, such as SANIZOL B(trademark), is used in conjunction with the polyaluminum sulfosilicate (PASS), the process time may be further reduced by about 30 to about 50 percent as compared, for example, to similar toner processes wherein there is selected polyaluminum sulfosilicate alone. Furthermore, the advantage of using a second coagulant, such as SANIZOL B(trademark), in combination with PASS over polyaluminum chloride (PAC) alone resides in better retention of colorant wherein the colorant is, for example, about 95 to 100 percent retained in the toner particles. Additionally, with the invention processes in embodiments, toner washing can be reduced by about 60 to about 75 percent and the triboelectric charging values of the toner obtained are substantially constant irrespective of the colorant selected. Furthermore, when the toners generated are roll milled and aged over a period of, for example, about 2 to about 3 hours, there results stable and negative toner charging with, for example, no or minimal wrong sign positively charged toner.
The toners generated with the processes of the present invention are especially useful for imaging processes, especially xerographic processes, which usually prefer a toner transfer efficiency in excess of greater than about 90 percent, such as those with a compact machine design without a cleaner or those that are designed to provide high quality colored images with excellent image resolution, acceptable signal-to-noise ratio, and image uniformity. Also, the toners obtained with the processes illustrated herein can be selected for digital imaging systems and processes.
With respect to the prior art, only a small part thereof has been selected and this part may or may not be fully representative of the prior art teachings or disclosures.
In xerographic systems, especially color systems, small sized toners of from about 2 to about 8 microns can be of value with regard to the achievement of high image quality for process color applications. Also, of value is the achievement of a low image pile height to eliminate, or minimize image feel and avoid paper curling after fusing. Paper curling can be particularly pronounced in xerographic color processes primarily because of the presence of relatively high toner coverage as a result of the application of three to four colored toners. During fusing, moisture escapes from the paper due to high fusing temperatures of from about 120xc2x0 C. to about 200xc2x0 C., and wherein with only one layer of toner selected, such as in one-color black or highlight color xerographic applications, the amount of moisture driven off during fusing can be reabsorbed by the paper and the resulting print remains relatively flat with minimal paper curl. In process color where toner coverage is high, the relatively thick toner plastic covering on the paper can inhibit the paper from reabsorbing the moisture, and cause substantial paper curling. These and other imaging shortfalls and problems are avoided or minimized with the toners and processes of the present invention.
Also, it can be preferable to select certain toner particle sizes, such as from about 2 to about 10 microns, and with a high colorant, especially pigment loading, such as from about 4 to about 15 percent by weight of toner, so that the mass of toner necessary for attaining the required optical density and color gamut can be significantly reduced to eliminate or minimize paper curl. Lower toner mass also ensures the achievement of image uniformity. However, higher pigment loadings often adversely affect the charging behavior of toners. For example, the charge levels may be too low for proper toner development or the charge distributions may be too wide and toners of wrong charge polarity may be present. Furthermore, higher pigment loadings may also result in the sensitivity of charging behavior to charges in environmental conditions such as temperature and humidity. Toners prepared in accordance with the processes of the present invention minimize, or avoid these disadvantages.
There is illustrated in U.S. Pat. No. 4,996,127 a toner of associated particles of secondary particles comprising primary particles of a polymer having acidic or basic polar groups and a coloring agent. The polymers selected for the toners of the ""127 patent can be prepared by an emulsion polymerization method, see for example columns 4 and 5 of this patent. In column 7 of this ""127 patent, it is indicated that the toner can be prepared by mixing the required amount of coloring agent and optional charge additive with an emulsion of the polymer having an acidic or basic polar group obtained by emulsion polymerization. In U.S. Pat. No. 4,983,488, there is disclosed a process for the preparation of toners by the polymerization of a polymerizable monomer dispersed by emulsification in the presence of a colorant and/or a magnetic powder to prepare a principal resin component and then effecting coagulation of the resulting polymerization liquid in such a manner that the particles in the liquid after coagulation have diameters suitable for a toner. It is indicated in column 9 of this patent that coagulated particles of 1 to 100, and particularly 3 to 70 microns, are obtained. This process results, it is believed, in the formation of particles with a wide particle size distribution. Similarly, the aforementioned disadvantages, for example poor particle size distributions are obtained hence classification is required resulting in low toner yields, are illustrated in other prior art, such as U.S. Pat. No. 4,797,339, wherein there is disclosed a process for the preparation of toners by resin emulsion polymerization, wherein similar to the ""127 patent certain polar resins are selected; and U.S. Pat. No. 4,558,108, wherein there is disclosed a process for the preparation of a copolymer of styrene and butadiene by specific suspension polymerization. Other prior art includes U.S. Pat. Nos. 3,674,736; 4,137,188 and 5,066,560.
Emulsion/aggregation/coalescence processes for the preparation of toners are illustrated in a number of Xerox patents, the disclosures of each of which are totally incorporated herein by reference, such as U.S. Pat. No. 5,290,654, U.S. Pat. No. 5,278,020, U.S. Pat. No. 5,308,734, U.S. Pat. No. 5,370,963, U.S. Pat. No. 5,344,738, U.S. Pat. No. 5,403,693, U.S. Pat. No. 5,418,108, U.S. Pat. No. 5,364,729, and U.S. Pat. No. 5,346,797; and also of interest may be U.S. Pat. Nos. 5,348,832; 5,405,728; 5,366,841; 5,496,676; 5,527,658; 5,585,215; 5,650,255; 5,650,256 and 5,501,935, 5,723,253, 5,744,520, 5,763,133, 5,766,818, 5,747,215, 5,827,633, 5,853,944, 5,804,349, 5,840,462, 5,869,215. The appropriate components and processes of the above Xerox Corporation patents can be selected for the processes of the present invention in embodiments thereof.
It is a feature of the present invention to provide toner processes with many of the advantages illustrated herein.
In another feature of the present invention there are provided simple and economical processes for the preparation of black and colored toner compositions with excellent colorant dispersions, thus enabling the achievement of excellent color print quality.
In another feature of the present invention there is provided a process for preparing toner particles which evidence similar charging behavior despite differential colorant chemistry.
Another feature of the present invention resides in a process for preparing pigmented toner particles with certain coagulants, and wherein the toner is spherical in shape allowing, for example, excellent toner transfer as compared to rough or nonspherical toner.
Yet another feature of the present invention resides in a process of preparing different toner size particles with two coagulants, and wherein minimum amounts of ionic surfactant may be selected.
Additionally, another feature of the present invention resides in a process capable of delivering differing toner morphology particles such as spherical.
A further feature of the present invention resides in the use of a metal salt for the reduction of the pH during coalescence, rather than an acid for the fusion of the aggregates, wherein the use of the metal salts during the pH reduction stage enables rapid spheroidization of the particles when compared to the use of an acid, such as nitric acid, as a pH reducer.
Aspects of the present invention relate to a process comprising
(i) blending a colorant dispersion of a colorant, water, and an anionic surfactant, or a nonionic surfactant with
(ii) a latex emulsion comprised of resin, water, and an ionic surfactant;
(iii) adding to the resulting blend a first coagulant of polyaluminum sulfosilicate (PASS) and a second cationic co-coagulant having an opposite charge polarity to that of the latex surfactant;
(iv) heating the resulting mixture below about the glass transition temperature (Tg) of the latex resin;
(v) adjusting with a base the pH of the resulting toner aggregate mixture from a pH which is in the range of about 1.8 to about 3 to a pH range of about 5 to about 9;
(vi) heating above about the Tg of the latex resin;
(vii) changing the pH of the mixture by the addition of a metal salt to arrive at a pH of from about 2.8 to about 5; and
(viii) optionally isolating the product; a process comprising
(i) blending a colorant dispersion of a colorant, water, and an anionic surfactant, a latex emulsion comprised of resin, water, and an ionic surfactant; and optionally adding a crosslinked gel in the form of a latex, which latex is comprised of a crosslinked resin, water, and an ionic surfactant;
(ii) optionally adding a wax dispersion comprised of submicron wax particles in the size diameter of about 0.1 to about 0.4 micron, and which particles are dispersed in an anionic surfactant of the same charge polarity of the anionic surfactant in the latex emulsion;
(iii) adding to the resulting blend mixture polyaluminum sulfosilicate (PASS) and a cationic co-coagulant with an opposite charge polarity to that of the latex surfactant to thereby initiate flocculation of the latex resin, colorant and, when present, wax;
(iv) heating the resulting mixture below or equal to about the glass transition temperature (Tg) of the latex resin to form toner sized aggregates;
(v) optionally adding a second latex comprised of submicron resin particles suspended in an aqueous phase resulting in an aggregate shell;
(vi) adjusting the pH with a base of from a pH which is in the range of about 1.9 to about 3 to a pH range of about 5 to about 9 to primarily stabilize the aggregates;
(vii) heating the resulting aggregate suspension of (vi) above about the Tg of the latex resin;
(viii) retaining the mixture (vii) at an optional temperature in the range of from about 70xc2x0 C. to about 95xc2x0 C. to initiate the fusion or coalescence of the toner aggregates;
(ix) changing the pH of the above (viii) mixture by the addition of a metal salt to arrive at a pH in the range of about 2.8 to about 5 to thereby accelerate the fusion or the coalescence resulting in toner comprised of resin and colorant, wherein the toner particle size is from about 2 to about 25 microns in volume average diameter;
(x) optionally washing the resulting toner slurry; and optionally isolating the toner; a process for the preparation of toner comprising
(i) mixing a colorant dispersion of colorant, and an anionic surfactant with a latex emulsion comprised of resin, and an anionic surfactant;
(ii) adding to the resulting blend a first coagulant of polyaluminum sulfosilicate and a second cationic co-coagulant with an opposite charge polarity to that of the latex surfactant;
(iii) heating the resulting mixture below about the glass transition temperature (Tg) of the latex resin;
(iv) optionally adding a second latex comprised of submicron resin particles suspended in an aqueous phase resulting in a coating wherein the coating is optionally of from about 0.1 to about 1 micron in thickness;
(v) adjusting with a base the pH of the resulting mixture from a pH which is in the range of about 1.8 to about 3 to a pH range of about 5 to about 9;
(vi) heating the resulting aggregate suspension of (v) above about the Tg of the latex resin (i);
(vii) changing the pH of the (vi) mixture by the addition of a metal salt to arrive at a pH of from about 2.5 to about 5; optionally heating above the Tg of the resin latex; and isolating the toner; a toner process utilizing an aqueous metal salt solution as a pH reducer to enable spheroidization of toner aggregates that otherwise may not be spheroidizable with the use of normal known pH reducers, such as acids; and wherein the metal salt can also be selected as a pH reducer during coalescence, and wherein the latex resin selected possesses a high molecular weight, for example from about 60,000 to about 1,000,000, and more specifically, from about 70,000 to about 700,000 and an onset glass transition temperature of about 58xc2x0 C. to about 85xc2x0 C., and more specifically, about 60xc2x0 C. to about 75xc2x0 C.; a process for the preparation of toner compositions, with a volume average diameter of from about 1 to about 25 microns, and more specifically, from about 2 to about 12 microns, and a particle size distribution of about 1.10 to about 1.28, and more specifically, from about 1.15 to about 1.25, each as measured by a Coulter Counter without the need to resort to conventional classifications to narrow the toner particle size distribution; a process for the preparation of pigmented toner particles wherein the latex selected can be prepared by batch polymerization or a semi-batch polymerization process containing submicron resin particles suspended in an aqueous phase of surfactants followed by aggregation in the presence of a dual coagulant comprised of polyaluminum sulfosilicate and a cationic surfactant, such as SANIZOL B(trademark), that is a benzylalkonium chloride; a toner process wherein there are provided toner compositions with low fusing temperatures of from about 140xc2x0 C. to about 185xc2x0 C., and which toner compositions exhibit excellent blocking characteristics at and above about, or equal to about 45xc2x0 C., and which toners generate excellent developed print quality and high resolution color prints; and an emulsion/aggregation toner process providing toner compositions which enable high image projection efficiency, such as for example over 75 percent as measured by the Match Scan II spectrophotometer available from Million-Roy; a process for the preparation of toner comprising mixing a colorant, a latex, a wax and a polyaluminum sulfosilicate or a polyaluminum chloride and a second co-coagulant of, for example, benzylalkonium chloride, alkylbenzyl methyl ammonium chloride, or dialkylbenzenealkyl ammonium chloride; a process for the preparation of toner comprising mixing a colorant, a latex, a wax, and a polyaluminum sulfosilicate and a benzylalkonium chloride as coagulants, and which coagulants assist in permitting aggregation and coalescence of colorant, resin latex, and when present wax; a process for preparing a chemical toner comprising
(i) generating a colorant dispersion of a colorant, water, an ionic surfactant, or a nonionic surfactant; a latex emulsion comprised of resin, water, nonionic and ionic surfactant; and wherein the
(ii) colorant dispersion is blended with the latex emulsion followed by optionally adding a wax dispersion comprised of submicron particles in the diameter size range of about 0.1 to about 0.5 micron dispersed in an anionic surfactant of the same charge polarity as that of the ionic surfactant in the latex emulsion;
(iii) adding to the resulting blend containing the latex and colorant a coagulant of polyaluminum sulfosilicate (PASS) and a second cationic co-coagulant with an opposite charge polarity to that of the latex surfactant to thereby initiate flocculation of the resin latex and colorant particles;
(iv) heating the resulting mixture below about the glass transition temperature (Tg) of the latex resin to form toner sized aggregates of resin and colorant;
(v) optionally adding a second latex comprised of submicron resin particles suspended in an aqueous phase to the formed toner aggregates of (iv) resulting in a shell wherein the shell is, for example, of from about 0.1 to about 1 micron in thickness;
(vi) adjusting with a base the pH of the resulting toner aggregate mixture from a pH of about 1.9 to about 3 to a pH of about 5 to about 8 to primarily stabilize the aggregate particles;
(vii) heating the resulting aggregate suspension of (vi) above the Tg of the latex resin;
(viii) retaining the mixture (vii) at a temperature in the range of from about 70xc2x0 C. to about 95xc2x0 C. for a period of, for example, about 3 to about 10 hours to initiate the fusion or coalescence of the toner aggregates;
(ix) changing the pH of the above (viii) mixture with a metal salt to arrive at a pH in the range of about 2.8 to about 5, and more specifically, about 3 to about 4.5 to accelerate the fusion or the coalescence resulting in toner particles comprised of resin, colorant, and optionally wax, wherein the toner particle size is about 2 about 25 microns;
(x) washing the resulting toner slurry; and
(xi) isolating the toner; followed by drying the toner particles; a process comprising
(i) mixing a colorant dispersion of a colorant, water, an anionic surfactant with a latex comprised of resin, water, and an ionic surfactant followed by adding a crosslinked gel in the form of a latex and comprised of resin, water, and an ionic surfactant, and wherein the
(ii) colorant dispersion is thoroughly blended with the latex emulsion followed by adding a wax dispersion comprised of submicron particles in the size range of about 0.1 to about 0.5 micron dispersed in an anionic surfactant of the same charge polarity as that of the ionic surfactant in the latex emulsion;
(iii) adding to the resulting blend containing the latex and colorant a coagulant of polyaluminum sulfosilicate (PASS) and a second cationic co-coagulant of benzylalkonium chloride having an opposite charge polarity to that of the surfactant latex to thereby initiate flocculation of the resin latex and colorant particles;
(iv) heating the resulting mixture about below or about equal to the glass transition temperature (Tg) of the latex resin to form toner sized aggregates;
(v) optionally adding a second latex comprised of submicron resin particles suspended in an aqueous phase resulting in a shell wherein the shell is, for example, of from about 0.1 to about 1 micron in thickness;
(vi) adjusting with a base the pH of the resulting toner aggregate mixture to about 5 to about 9 to primarily stabilize the aggregate particles;
(vii) heating the resulting aggregate suspension of (vi) above the Tg of the latex resin;
(viii) retaining the mixture (vii) temperature of, for example, from about 70xc2x0 C. to about 95xc2x0 C. to initiate the fusion or coalescence of the toner aggregates;
(ix) changing the pH of the above (viii) mixture to arrive at a pH of about 2.8 to about 5, and more specifically, from about 3 to about 4.5 to accelerate the fusion or coalescence resulting in toner particles comprised of resin, colorant, and wax, wherein the toner particle size is about 2 to about 25 microns;
(x) washing the resulting toner slurry; and
(xi) isolating the toner; followed by drying the toner particles;
a process wherein a crosslinked gel is added to the latex, and which gel is comprised of styrene-beta carboxyl ethyl acrylate (xcex2CEA), divinyl benzene; a process wherein the amount of divinyl benzene crosslinking agent is from about 0.05 to about 5 percent by weight of resin; a process where the amount of the crosslinked gel latex is from about 5 to about 30 percent by weight of toner; a process wherein the crosslinked gel latex to the linear latex of (i) ratio is about 5:95 to about 30:70 percent by weight of the final toner formulation; a process wherein the final toner formulation is comprised of a linear resin and optionally a crosslinked gel resin and a colorant; a process wherein the polyaluminum sulfosilicate is selected in an amount of from about 0.05 to about 7 percent by weight of toner solids of latex resin, colorant, optional wax and sulfosilicate, and wherein the latex resin, colorant, and wax amount totals about 100 percent; a toner process wherein there is selected a second coagulant of a cationic surfactant; a process wherein the second coagulant selected is, for example, an alkonium benzalkonium chloride, dialkylbenzenealkyl ammonium chloride, alkylbenzyl methyl ammonium chloride or alkylbenzyl dimethyl ammonium bromide and the like in an amount of from about 0.05 to about 5 weight percent by weight; a process wherein the metal salt to reduce the pH of the mixture during the coalescence (vii) is selected, for example, from sulfates, chloride, nitrates, and acetates of aluminum, magnesium, zinc, and potassium; a process wherein the metal salt is aluminum sulfate, aluminum chloride, zinc sulfate, magnesium sulfate, magnesium chloride, potassium-aluminum sulfate, and the preferred metal salt is aluminum sulfate; a process wherein the concentration of the metal salt used to reduce the pH is from about 0.01 to about 10 percent, and more specifically, from about 0.05 to about 7 weight percent by weight of toner; a process wherein the base is a hydroxide selected from the group consisting of sodium hydroxide, potassium hydroxide, and ammonium hydroxide, and wherein a specific base is sodium hydroxide; a process wherein there is added to the formed toner aggregates a second latex comprised of resin particles suspended in an aqueous phase containing an ionic surfactant, and wherein the second latex is selected in an amount of about 10 to about 40 percent by weight of the initial latex and forms a shell or coating on the toner aggregates; a process wherein the added latex contains the same resin as the initial latex, or wherein the added latex contains a dissimilar resin than that of the initial latex; a process wherein the temperature at which the aggregation is accomplished controls the size of the aggregates, and wherein the final toner size is from about 2 to about 15 microns in volume average diameter; a process wherein the aggregation temperature is from about 45xc2x0 C. to about 60xc2x0 C., and wherein the coalescence or fusion temperature is from about 85xc2x0 C. to about 95xc2x0 C.; a process wherein the colorant is a pigment, and wherein the pigment is in the form of dispersion, and which dispersion contains an ionic surfactant, and wherein the polyaluminum sulfosilicate and the benzylalkonium chloride function as coagulants and enable aggregation of the latex wax and the colorant; a process wherein the coagulant is added during or prior to aggregation of the latex resin and colorant, and which coagulant enables or initiates the aggregation; a process wherein the colorant is carbon black, cyan, yellow, red, green, blue, magenta, or mixtures thereof; a process wherein the toner isolated is from about 2 to about 25 microns in volume average diameter, and the particle size distribution (GSD) thereof is from about 1.15 to about 1.30; and wherein there is added to the surface of the formed toner additives, such as metal salts, metal salts of fatty acids, silicas, metal oxides, or mixtures thereof, each in an amount of from about 0.1 to about 10 weight percent of the obtained toner; a process which comprises mixing a latex, surfactant and colorant; heating in the presence of a polyaluminum sulfosilicate and benzyl alkonium chloride (SANIZOL B(trademark)) the resulting mixture below about, or equal to about the glass transition temperature of the latex resin; followed by the addition of a base to stabilize the toner aggregates; thereafter heating the resulting aggregates above about, or about equal to the glass transition temperature of the resin; and isolating, washing and drying the toner; a process wherein prior to isolating the heating is retained at a temperature of from about 70xc2x0 C. to about 95xc2x0 C. until fusion or coalescence of the aggregates is accomplished; a process wherein the polyaluminum sulfosilicate possesses a weight average molecular weight of from about 5,000 to about 100,000; a process wherein the sulfosilicate functions as a coagulant and enables or assists in enablement of the aggregation; a process wherein the polyaluminum sulfosilicate is of the formula
ALA(OH)B(SO4)C(SIOX)D(H2O)E
where A, B, C, D and E represent the number of segments of each species, and X represents the number of oxygens; a process wherein A is 1, B is from about 0.75 to about 2, C is from about 0.30 to about 1.12, D is from about 0.005 to about 0.1, X is from about 2 to about 4, and E is from about 4 to about 10; a process wherein the aggregation temperature is from about 40xc2x0 C. to about 62xc2x0 C., and more specifically, is from about 45xc2x0 C. to about 58xc2x0 C.; a process wherein the coalescence temperature is from about 75xc2x0 C. to about 95xc2x0 C., and more specifically, about 85xc2x0 C. to about 90xc2x0 C.; a process wherein there is added to the aggregate mixture prior to coalescence a base component; a process wherein the base is an alkali metal hydroxide; a process wherein the hydroxide is sodium hydroxide; a process wherein the pH of the mixture resulting after aggregation is increased from about 2 to about 2.6 to about 7 to about 8 during the coalescence, and wherein the base functions primarily as a stabilizer for the toner aggregates during the coalescence; a process wherein the amount of base selected is from about 8 to about 25 weight percent, and more specifically, is from about 10 to about 20 weight percent; a process wherein the amount of metal hydroxide selected is from about 11 to about 14 weight percent; a process wherein the metal salt to reduce the pH is a sulfate, a chloride, a nitrate, or an acetate of aluminum, magnesium, zinc, and potassium; a process wherein the salt is aluminum sulfate, aluminum chloride, zinc sulfate, magnesium sulfate, magnesium chloride, potassium-aluminum sulfate, or zinc acetate, and which salt is selected in an amount of from about 0.05 to about 10 percent, and more specifically, in the amount of about 0.1 about 7 weight percent by weight of toner; a process wherein the latex contains submicron polymer or resin particles containing a polymer selected from the group consisting of poly(styrene-alkyl acrylate), poly(styrene-1,3-diene), poly(styrene-alkyl methacrylate), poly(styrene-alkyl acrylate-acrylic acid), poly(styrene-1,3-diene-acrylic acid), poly(styrene-alkyl methacrylate-acrylic acid), poly(alkyl methacrylate-alkyl acrylate), poly(alkyl methacrylate-aryl acrylate), poly(aryl methacrylate-alkyl acrylate), poly(alkyl methacrylate-acrylic acid), poly(styrene-alkyl acrylate-acrylonitrile-acrylic acid), poly(styrene-1,3-dieneacrylonitrile-acrylic acid), and poly(alkyl acrylate-acrylonitrile-acrylic acid); a process wherein the latex contains a resin selected from the group consisting of poly(styrene-butadiene), poly(methylstyrene-butadiene), poly(methyl methacrylate-butadiene), poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene), poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene), poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene), poly(butyl acrylate-butadiene), poly(styrene-isoprene), poly(methylstyrene-isoprene), poly(methyl methacrylate-isoprene), poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene), poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene), poly(ethyl acrylate-isoprene), poly(propyl acrylate-isoprene), and poly(butyl acrylate-isoprene); poly(styrene-propyl acrylate), poly(styrene-butyl acrylate), poly(styrene-butadiene-acrylic acid), poly(styrene-butadiene-methacrylic acid), poly(styrene-butadiene-acrylonitrile-acrylic acid), poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butyl acrylate-methacrylic acid), poly(styrene-butyl acrylate-acrylononitrile), and poly(styrene-butyl acrylate-acrylononitrile-acrylic acid); and wherein the colorant is a pigment; a process for the preparation of toner particles resulting in images with excellent print quality, and wherein there is selected a latex comprised of submicron resin particles which are in the size range of about 0.05 to about 0.5 micron, and more specifically, in the size range of about 0.07 to about 0.35 micron, suspended in an aqueous water phase containing an ionic surfactant, which is selected in an amount of about 0.5 to about 5 percent, and more specifically, about 0.7 to about 2 percent by weight of solids, to which is added a colorant dispersion comprising submicron, for example less than, or equal to about 0.5 micron, colorant particles, anionic or a nonionic surfactant which is selected in the amount of about 0.5 to about 10 percent, and more specifically, about 0.6 to about 5 percent by weight of solids, which when blended together result in a mixture with a pH of about 2 to about 2.6 to which a polyaluminum sulfosilicate (PASS) solution containing an acid like nitric acid is added slowly over, for example, a period of about 2 to about 5 minutes, followed by the addition of a cationic coagulant surfactant solution of SANIZOL B(trademark) in water wherein the amount of PASS is from about 0.05 to about 0.8 percent by weight of the latex solids and colorant components, and specifically, from about 0.06 to about 0.5 percent by weight; and the second optional coagulant, such as SANIZOL B(trademark), is selected in the amount of about 0.05 to about 0.8 percent by weight of solids, and more specifically, from about 0.06 to about 0.5 percent by weight; further aggregating by stirring and heating from about 5 to about 10 degrees below the resin Tg, resulting in toner aggregates of a size of about 3 to about 15 microns, and more specifically, about 4 to about 8 microns with a narrow GSD of, for example, about 1.14 to about 1.28, and more specifically, about 1.17 to about 1.25, and which improved GSD enables the clean transfer of the toner particles in xerographic systems thereby providing enhanced resolution of the fused images; followed by adjusting the pH of the mixture from about 2 to about 2.6 to a pH of about 6 to about 9, and more specifically, to about 7 to about 8.5, or to a pH of about 8 with the addition of a dilute base solution of 4 weight percent of sodium hydroxide to primarily stabilize the aggregates, further stirring and increasing the mixture temperature above the resin Tg, in the range of about 70xc2x0 C. to about 95xc2x0 C., and more specifically, from about 85xc2x0 C. to about 93xc2x0 C. for a period of about 0.5 to about 1.5 hours, followed by changing the pH from about 8 to about 4.5 by the use of an aqueous metal salt solution, such as a dilute solution of aluminum sulfate in water wherein the concentration of aluminum sulfate is from about 0.5 to about 5 weight percent, and more specifically, about 0.75 to about 3.5 weight percent, and heating the mixture for an additional about 0.5 to about 4 hours, and more specifically, from about 0.6 to about 3 hours, to fuse or coalesce the aggregates, and then washing and drying the toner; a toner process wherein a wax dispersion is added to the latex and colorant mixture; a process wherein the use of an aqueous solution of a metal salt to reduce the pH of step (ix) enables rapid spheroidization of the toner particles; and the rapid spheroidization with the use of a metal salt as a pH reducer enhances by about 2 to about 4 times faster than that when an acid is selected; and a process for the preparation of toner compositions which comprises blending an aqueous colorant dispersion containing a pigment, such as carbon black, phthalocyanine, quinacridone or RHODAMINE B(trademark) type, red, green, orange, brown, violet, yellow, fluorescent colorants and the like, with a latex emulsion derived from the emulsion polymerization of monomers selected, for example, from the group consisting of styrene, butadiene, acrylates, methacrylates, acrylonitrile, acrylic acid, methacrylic acid, itaconic or Beta Carboxy Ethyl Acrylate (xcex2CEA) and the like, and which latex contains an ionic surfactant, such as sodium dodecylbenzene sulfonate, and optionally a nonionic surfactant, and which process is accomplished in the presence of a metal salt, or PASS and a second coagulant cationic surfactant, heating the resulting flocculent mixture at a temperature below the resin Tg for an effective length of time of, for example, about 0.5 hour to about 3 hours to form toner sized aggregates; and optionally adding a known amount of delayed latex wherein the latex can be the same as the above initial latex or dissimilar, followed by adjusting the pH of the mixture with a dilute base solution of sodium hydroxide, and subsequently heating the aggregate suspension at a temperature at or below 95xc2x0 C. for a period of 0.5 to 1 hour, adjusting the pH of the mixture from about 8 to about 4.5 with an aqueous dilute metal salt of aluminum sulfate to provide spherical toner particles, isolating the toner product by, for example, filtration, washing and drying in an oven, fluid bed dryer, freeze dryer, or spray dryer.
The particle size of the toner provided by the processes of the present invention in embodiments can be controlled, for example, by the temperature at which the aggregation of latex, colorant, such as pigment, and optional additives is conducted. In general, the lower the aggregation temperature, the smaller the aggregate size, and thus the final toner size. For a latex polymer with a glass transition temperature (Tg) of about 55xc2x0 C. and a reaction mixture with a solids content of about 14 percent by weight, an aggregate size of about 7 microns in volume average diameter is obtained at an aggregation temperature of about 53xc2x0 C.; the same latex will provide an aggregate size of about 5 microns at a temperature of about 48xc2x0 C. under similar conditions.
Illustrative examples of specific latex resin, polymer or polymers selected for the process of the present invention include known polymers such as poly(styrene-butadiene), poly(methyl methacrylate-butadiene), poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene), poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene), poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene), poly(butyl acrylate-butadiene), poly(styrene-isoprene), poly(methylstyrene-isoprene), poly(methyl methacrylate-isoprene), poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene), poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene), poly(ethyl acrylate-isoprene), poly(propyl acrylate-isoprene), poly(butyl acrylate-isoprene), poly(styrene-butylacrylate), poly(styrene-butadiene), poly(styrene-isoprene), poly(styrene-butyl methacrylate), poly(styrene-butyl acrylate-acrylic acid), poly(styrene-butadiene-acrylic acid), poly(styrene-isoprene-acrylic acid), poly(styrene-butyl methacrylate-acrylic acid), poly(butyl methacrylate-butyl acrylate), poly(butyl methacrylate-acrylic acid), poly(styrene-butyl acrylate-acrylonitrile-acrylic acid), poly(acrylonitrile-butyl acrylate-acrylic acid), and the like. The crosslinked gel latex when selected can contain divinyl benzene as an additional monomer during the latex formation. The latex polymer, or resin is generally present in the toner compositions of the present invention in various suitable amounts, such as from about 75 weight percent to about 98, or from about 80 to about 95 weight percent of the toner or of the solids, and the latex size suitable for the processes of the present invention can be, for example, more specifically, from about 0.05 micron to about 0.7 micron in volume average diameter as measured by the Brookhaven nanosize particle analyzer. Other sizes and effective amounts of latex polymer may be selected in embodiments. The total of all toner components, such as resin and colorant, is about 100 percent, or about 100 parts.
The polymer selected for the process of the present invention can be prepared by emulsion polymerization methods, and the monomers utilized in such processes include, for example, styrene, acrylates, methacrylates, butadiene, isoprene, acrylic acid, methacrylic acid, itaconic acid, beta carboxy ethyl acrylate, acrylonitrile, and the like. Known chain transfer agents, for example dodecanethiol, from, for example, about 0.1 to about 10 percent, or carbon tetrabromide in effective amounts, such as for example from about 0.1 to about 10 percent, can also be utilized to control the molecular weight properties of the polymer when emulsion polymerization is selected. Other processes of obtaining polymer particles of from, for example, about 0.01 micron to about 2 microns can be selected from polymer microsuspension process, such as disclosed in U.S. Pat. No. 3,674,736, the disclosure of which is totally incorporated herein by reference; polymer solution microsuspension process, such as disclosed in U.S. Pat. No. 5,290,654, the disclosure of which is totally incorporated herein by reference, mechanical grinding processes, or other known processes. Also, the reactant initiators, chain transfer agents, and the like as disclosed in U.S. Ser. No. 922,437, the disclosure of which is totally incorporated herein by reference, can be selected for the processes of the present invention.
Examples of waxes include those as illustrated herein, such as those disclosed in the aforementioned copending applications, polypropylenes and polyethylenes commercially available from Allied Chemical and Petrolite Corporation, wax emulsions available from Michaelman Inc. and the Daniels Products Company, EPOLENE N-15 commercially available from Eastman Chemical Products, Inc., VISCOL 550-P, a low weight average molecular weight polypropylene available from Sanyo Kasei K.K., and similar materials. The commercially available polyethylenes selected have, it is believed, a molecular weight Mw of from about 1,000 to about 1,500, while the commercially available polypropylenes are believed to have a molecular weight of from about 4,000 to about 5,000. Examples of functionalized waxes include, amines, amides, for example aqua SUPERSLIP 6550, SUPERSLIP 6530 available from Micro Powder Inc., fluorinated waxes, for example POLYFLUO 190, POLYFLUO 200, POLYFLUO 523XF, AQUA POLYFLUO 411, AQUA POLYSILK 19, POLYSILK 14 available from Micro Powder Inc., mixed fluorinated, amide waxes, for example MICROSPERSION 19 also available from Micro Powder Inc., imides, esters, quaternary amines, carboxylic acids or acrylic polymer emulsion, for example JONCRYL 74, 89, 130, 537, and 538, all available from SC Johnson Wax, chlorinated polypropylenes and polyethylenes commercially available from Allied Chemical and Petrolite Corporation and SC Johnson wax.
Various known colorants, such as pigments, selected for the processes of the present invention and present in the toner in an effective amount of, for example, from about 1 to about 25 percent by weight of toner, and preferably in an amount of from about 3 to about 10 percent by weight, that can be selected include, for example, carbon black like REGAL 330(copyright); magnetites, such as Mobay magnetites MO8029(trademark), MO8060(trademark); Columbian magnetites; MAPICO BLACKS(trademark) and surface treated magnetites; Pfizer magnetites CB4799(trademark), CB5300(trademark), CB5600(trademark), MCX6369(trademark); Bayer magnetites, BAYFERROX 8600(trademark), 8610(trademark); Northern Pigments magnetites, NP-604(trademark), NP-608(trademark); Magnox magnetites TMB-100(trademark), or TMB-104(trademark); and the like. As colored pigments, there can be selected cyan, magenta, yellow, red, green, brown, blue or mixtures thereof. Specific examples of pigments include phthalocyanine HELIOGEN BLUE L6900(trademark), D6840(trademark), D7080(trademark), D7020(trademark), PYLAM OIL BLUE(trademark), PYLAM OIL YELLOW(trademark), PIGMENT BLUE 1(trademark) available from Paul Uhlich and Company, Inc., PIGMENT VIOLET 1(trademark), PIGMENT RED 48(trademark), LEMON CHROME YELLOW DCC 1026(trademark), E.D. TOLUIDINE RED(trademark) and BON RED C(trademark) available from Dominion Color Corporation, Ltd., Toronto, Ontario, NOVAPERM YELLOW FGL(trademark), HOSTAPERM PINK E(trademark) from Hoechst, and CINQUASIA MAGENTA(trademark) available from E.l. DuPont de Nemours and Company, and the like. Generally, colored pigments that can be selected are cyan, magenta, or yellow pigments, and mixtures thereof. Examples of magentas that may be selected include, for example, 2,9-dimethyl-substituted quinacridone and anthraquinone dye identified in the Color Index as CI 60710, CI Dispersed Red 15, diazo dye identified in the Color Index as CI 26050, CI Solvent Red 19, and the like. Illustrative examples of cyans that may be selected include copper tetra(octadecyl sulfonamido) phthalocyanine, x-copper phthalocyanine pigment listed in the Color Index as CI 74160, CI Pigment Blue, and Anthrathrene Blue, identified in the Color Index as CI 69810, Special Blue X-2137, and the like; while illustrative examples of yellows that may be selected are diarylide yellow 3,3-dichlorobenzidene acetoacetanilides, a monoazo pigment identified in the Color Index as CI 12700, CI Solvent Yellow 16, a nitrophenyl amine sulfonamide identified in the Color Index as Foron Yellow SE/GLN, CI Dispersed Yellow 33 2,5-dimethoxy-4-sulfonanilide phenylazo-4xe2x80x2-chloro-2,5-dimethoxy acetoacetanilide, Yellow 180 and Permanent Yellow FGL. Colored magnetites, such as mixtures of MAPICO BLACK(trademark), and cyan components may also be selected as pigments for the processes of the present invention, wherein the pigment amount is in the range of 3 to 15 weight percent of the toner. Dye examples include known suitable dyes, reference the Color Index, and a number of U.S. patents, such as food dyes, and the like.
Colorants include pigment, dye, mixtures of pigment and dyes, mixtures of pigments, mixtures of dyes, and the like.
Examples of initiators for the latex preparation include water soluble initiators, such as ammonium and potassium persulfates, in suitable amounts, such as from about 0.1 to about 8 percent, and more specifically, from about 0.2 to about 5 percent (weight percent). Examples of organic soluble initiators include VAZO peroxides, such as VAZO 64, 2-methyl 2-2xe2x80x2-azobis propanenitrile, VAZO 88, 2-2xe2x80x2-azobis isobutyramide dehydrate in a suitable amount, such as from about 0.1 to about 8 percent. Examples of chain transfer agents include dodecane thiol, octane thiol, carbon tetrabromide and the like in various suitable amounts, such as from about 0.1 to about 10 percent, and more specifically, from about 0.2 to about 5 percent by weight of monomer.
Surfactants for the preparation of the latexes and the colorant dispersions can be ionic or nonionic surfactants, in effective amounts of, for example, from about 0.01 to about 15, or from about 0.01 to about 5 weight percent of the reaction mixture. Anionic surfactants include sodium dodecylsulfate (SDS), sodium dodecylbenzene sulfonate, sodium dodecyinaphthalene sulfate, dialkyl benzenealkyl, sulfates and sulfonates, abitic acid, available from Aldrich, NEOGEN R(trademark), NEOGEN SC(trademark) obtained from Kao, and the like. Examples of cationic surfactants are dialkyl benzenealkyl ammonium chloride, lauryl trimethyl ammonium chloride, alkylbenzyl methyl ammonium chloride, alkyl benzyl dimethyl ammonium bromide, benzalkonium chloride, cetyl pyridinium bromide, C12, C15, C17 trimethyl ammonium bromides, halide salts of quaternized polyoxyethylalkylamines, dodecylbenzyl triethyl ammonium chloride, MIRAPOL(trademark) and ALKAQUAT(trademark) available from Alkaril Chemical Company, SANIZOL(trademark) (benzalkonium chloride) available from Kao Chemicals, and the like, selected in effective amounts of, for example, from about 0.01 percent to about 10 percent by weight. The molar ratio of the cationic surfactant used for flocculation to the anionic surfactant used in the latex preparation is, for example, from about 0.5 to about 4.
Examples of nonionic surfactants selected in various suitable amounts, such as about 0.1 to about 5 weight percent, are polyvinyl alcohol, polyacrylic acid, methalose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxy poly(ethyleneoxy) thanol, available from Rhone-Poulenac as IGEPAL CA-210(trademark), IGEPAL CA-520(trademark), IGEPAL CA-720(trademark), IGEPAL CO-890(trademark), IGEPAL CO-720(trademark), IGEPAL CO-290(trademark), IGEPAL CA-210(trademark), ANTAROX 890(trademark) and ANTAROX 897(trademark), can be selected.
Examples of the first coagulant are polyaluminum sulfosilicates, which, for example, can be represented by the formula
ALA(OH)B(SO4)C(SIOX)D(H2O)E
wherein
A is the number of Al segments and can be a number of about 1 to about 2;
B is a number of from about 0.75 to about 2;
C is from about 0.30 to about 1.12;
D is from about 0.005 to about 0.1;
X is a number equal to or greater than 2 but less than or equal to about 4 wherein 3=B+2C+2D (X-2); and
E is a number of larger than about 4, such as from about 5 to about 10, or more generally, wherein A, B, C, D, X and E represent the number of segments or atoms with respect to X, which represents the number of oxygen atoms.
Examples of the second surfactant coagulant are dialkyl benzenealkyl ammonium chloride, lauryl trimethyl ammonium chloride, alkylbenzyl methyl ammonium chloride, alkyl benzyl dimethyl ammonium bromide, and the like, and wherein alkyl contains, for example, from about 5 to about 20 carbon atoms, with the amounts of each of the first and second coagulant being from about 0.03 percent to about 1 percent by weight of toner aggregates, and more specifically, from about 0.05 to about 0.5 percent by weight of toner aggregates.
Examples of metal salts used as a pH reducer for (ix) can be selected from, for example, halides like chlorides, sulfates, nitrates, and acetates of aluminum, magnesium, zinc, and potassium, and more specifically, wherein the salt is aluminum sulfate, aluminum chloride, zinc sulfate, magnesium sulfate, magnesium chloride, or potassium-aluminum sulfate, or water soluble metal salts, that is metal salts that are readily soluble in water.
The toner may also include known charge additives in effective suitable amounts of, for example, from 0.1 to 5 weight percent, such as alkyl pyridinium halides, bisulfates, the charge control additives of U.S. Pat. Nos. 3,944,493; 4,007,293; 4,079,014; 4,394,430 and 4,560,635, the disclosures of which are totally incorporated herein by reference, negative charge enhancing additives like aluminum complexes, other known charge additives, and the like.
Surface additives that can be added to the toner compositions after washing or drying include, for example, metal salts, metal salts of fatty acids, colloidal silicas, metal oxides, strontium titanates, mixtures thereof, and the like, which additives are each usually present in an amount of from about 0.1 to about 2 weight percent, reference for example U.S. Pat. Nos. 3,590,000; 3,720,617; 3,655,374 and 3,983,045, the disclosures of which are totally incorporated herein by reference. Specific additives include zinc stearate and AEROSIL R972(copyright) available from Degussa. The coated silicas of U.S. Pat. No. 6,190,815 and U.S. Pat. No. 6,004,714, the disclosures of which are totally incorporated herein by reference, can also be selected in amounts, for example, of from about 0.1 to about 2 percent, which additives can be added during the aggregation or blended into the formed toner product.
Developer compositions can be prepared by mixing the toners obtained with the processes of the present invention, from about 2 percent toner concentration to about 8 percent toner concentration, with known carrier particles, including coated carriers, such as steel, ferrites, and the like, reference U.S. Pat. Nos. 4,937,166 and 4,935,326, the disclosures of which are totally incorporated herein by reference. The carrier particles can also be comprised of a core with a polymer coating thereover, such as polymethylmethacrylate (PMMA) having dispersed therein a conductive component like conductive carbon black. Carrier coatings include silicone resins, fluoropolymers, mixtures of resins not in close proximity in the triboelectric series, thermosetting resins, and other known components.
Imaging methods are also envisioned with the toners of the present invention, reference for example a number of the patents mentioned herein, and U.S. Pat. Nos. 4,265,990; 4,858,884; 4,584,253 and 4,563,408, the disclosures of which are totally incorporated herein by reference.


A method and software interface enables serial data streams to be trapped, parsed, tested for suitability for automated handling by a medication preparation system. Only those portions of the serial data stream that are not suitable for such handling are released for printing and manual handling. A serial data interface includes a listener software module (“LSM”) that receives serial data streams and a parser software module (“PSM”) communicatively connectable to the LSM that processes the serial data streams received from the LSM. A set of configuration rules accessible by the PSM defines the manner of processing by the PSM on the serial data streams. A data structure results that enables data handling by an automated medication preparation system.

The task of integrating multiple systems into a computer network is often associated with custom programming and delays. This is particularly true when dealing with proprietary network components such as may often be found in hospital environments. For example, hospital information systems are conventionally employed to manage patient data and input medications that are to be administered to a patent. An electronic hospital information system typically must interact with an electronic pharmacy system within an automated facility, the interface between these two systems requires that the software communicate and process the data appropriately. When integrating a new network component into an existing system, the software providers of each system must meet and agree upon specifications prior to even establishing a project timetable, in order to ensure that the necessary communications and processing needs are met. This is attendant with great expense and difficulty.
On the other hand, most hospital information systems and pharmacy systems send data to label printers that identify a patient, a medication to be administered, the time of administration, contra-indications, and other data. It makes no difference whether the label printer is a local or network device. Thus, one way of obtaining a reliable data stream from one system for importing into another is to capture the data that is intended to be printed to a label. However, in order to operate on this data, subsequent processing is required. The present invention provides improvements in device interaction by initiating tasks in response to the receipt of data at a serial port that parse and manage the information in that data stream for handling by other network devices. In further aspects, the present invention identifies label data in a serial data stream and divides the label data into a first stream that launches automated medication preparation processes and a second stream that is redirected to a conventional printer.


An apparatus for determining a disintegration time of compressed pharmaceutical mold bodies includes a vessel filled with a liquid, a frame lowerable into the vessel filled with the liquid, a center column attached to the frame, a floor attached to the center column, wherein the floor contains a plurality of holes, a grid covering the holes from below, a test tube disposed upright and positioned in one of the holes, a disk having passing through holes and movably insertable into the test tube as a weight onto an individual pharmaceutical form body, wherein the passing through holes are running parallel to the direction of the center axis of the disk. A permanent magnet is disposed centered within the disk and has a magnetic field directed axially, wherein the center hole of the disk exhibits a bore hole starting from a lower cover face of the disk, wherein the permanent magnet is seated in the bore hole, wherein the permanent magnet exhibits a permanent magnet hole centeredly in the direction of a center axis, which permanent magnet hole is aligned with the center hole within the disk.

1. Field of the Invention
The present invention relates to a device for determining the disintegration time of compressed pharmaceutical mold bodies, such as tablets and capsules, comprising a frame which can be lowered into a vessel filled with a liquid, having a center column and a floor including a plurality of bore holes, wherein the bore holes are covered from below with a sieve and wherein test tubes in upright position are disposed within the frame, wherein in each case a disk with holes passing through the disk in the direction of the center axis can be movably brought in into the test tube as a weight onto individual pharmaceutical mold bodies, wherein a permanent magnet is disposed at the lower side of the disk directed toward the floor, wherein in each case a magnetic field sensor element is disposed below the grid of the floor, as well as a method for this purpose.
2. Brief Description of the Background of the Invention Including Prior Art
The disintegration time measurement of compressed pharmaceutical mold bodies, such as tablets and capsules, is performed according to a standardized test arrangement in order to assure the reproducibility of the measurement results, in particular according to Deutsches Arzneibuch, DAB 10, 3. Supplement 1994 or Europaeisches Arzneibuch or USP (USA). It is determined by the disintegration test, if the tablets or capsules disintegrate in a liquid medium within the pre-scribed time under precisely performed conditions. The main part of the apparatus comprises a rigid frame, which contains six cylindrical test tubes made of glass. Each test tube is furnished with a cylindrical disk made of a transparent plastic material of a precisely pre-scribed relative density and size, which exhibits 5 bore holes passing through, wherein one of the bore holes is led through the center axis of the disk. The test tubes are supported in a vertical position by an upper transparent plate made of plastic material and by a lower transparent plate made of plastic material, wherein the transparent plates in each case have six bore holes. All bore holes have the same distance from the center point and the same distance from each other. A sieve made of stainless steel wire is disposed at the bottom side of the lower plate. A metal column is disposed in the middle of the plates such that the apparatus can be hanged at the metal column in a hanging device and can be moved upward and downward by way of a motor uniformly 28 to 32 times each minute over 50 to 60 mm. For this purpose the apparatus is hanged in a suitable vessel, wherein the vessel contains the pre-scribed liquid. After the filling in of a tablet or capsule into each tube and placing the disk as a weight, then the determination of the dissolution time of the tablets or capsules is performed by observation of the measurement device and taking of the time of the disintegration time by an operating person.
A disintegration apparatus for test bodies, in particular tablets has become known from the German patent DE 3520034 C1, wherein the test bodies are disposed in containers of the disintegration basket between a Hall generator and a disk furnished with a magnet. The containers of the disintegration basket are heated to a constant temperature with a heating means. When the test body disintegrates, then the disk moves together with the magnet toward the Hall generator, such that the Hall generator delivers a signal, which is led to a registration apparatus after the surpassing of a switching threshold and can be displayed. The transfer of the energy for electrical switching circuits in a disintegration basket is performed through contacts or through a high frequency emitter and high frequency receiver. The transfer of the signals to the registration apparatus is performed by optoelectrical components.
An automatic disintegration time measurement apparatus for the pharmaceutical quality control and production control of tablets and sugar-coated pills within a conducting test liquid is known from the German printed patent document DE 9419245 U1, which disintegration time measurement apparatus comprises a basket like frame disposed in a beaker glass with a plurality of glass tubes disposed in the basket like frame, wherein the floors of the glass tubes are formed by circular sieve plates as stand faces for the glass tubes, wherein each sieve plate comprises two wire grid halves being flown through by current and forming electrodes, wherein the wire grid halves are disposed at a distance and are thereby forming a slot. A test sample is disposed in each glass tube, wherein the test sample is covered by a float, and wherein the float rests on the test sample. The float exhibits on the bottom side an embedded contact frame made of a metallic material. Upon motion of the beaker glass and the disintegration of the tablets, the conductivity of the test fluid changes, wherein the conductivity can be measured between the wire grid halves and the contact frame of the float.
A tablet disintegration time measurement apparatus with moving small tubes in a bath liquid is known from U.S. Pat. No. 3,618,295 having a multitude of electrodes disposed opposite to each other at a distance on the floor of the small tubes containing the tablets. The presence of a tablet interferes with an electromagnetic field applied at the electrodes, wherein the interference influences a time clock, wherein the signals of the time clock can be evaluated.
A device for determining the disintegration time of compressed pharmaceutical mold bodies has become known from the World Intellectual Property Organization publication WO 97/14035, wherein an electric coil is disposed at the floor of the frame around each hole, wherein the electrical coil is part of an electrical oscillating circuit, wherein a conductor loop is disposed on the disk for a path depending damping of the electrical oscillating circuit, wherein the electrical oscillating circuit and the conductor loop are jointly connected to an electrical evaluation device for oscillation generation and evaluation of the measurement results. The coil can be formed as an insertion coil, a single layer coil, or as a multiple layer coil.
Conventional steps for fully automatic measurement started on the one hand always with impermissible changes of the test apparatus, wherein such changes however are permissible only in a very small range according to Deutsches Arzneibuch DAB 10. On the other hand the device according to the last recited document WO 97/14035 delivers relatively precise measurement results, however requires an extensive electronic expenditure in the signal generation and signal evaluation.
It is an object of the present invention to furnish a device of the kind initially recited, which captures contactless the motion of the disks within the device and without larger changes of the pre-scribed parameters for the apparatus according to Deutsches Arzneibuch DAB 10 and which is to determine continuously the decreasing thickness of compressed pharmaceutical mold bodies during the dissolution process.
It is another object of the present invention to furnish a device which reliably and precisely measures a disintegration behavior of a tablet or capsule.
The present invention provides that the central hole of the disk exhibits centeredly a bore starting at the lower cover face of the disk, where a permanent magnet is seated in the bore, wherein the permanent magnet exhibits centeredly a bore hole in the direction of the center axis, wherein the bore hole is aligned with the central bore within the disk, wherein the magnetic field sensor element is disposed in the region of the peripheral edge of the cover face of the permanent magnet in the region of the largest gradient of the magnetic field of the permanent magnet as seen in a top planar view.
Usually the residual thickness of a pharmaceutical mold body is a pre-given set point value. If the actual value of the pharmaceutical mold body is the residual thickness, then the pharmaceutical mold body is deemed to be dissolved.
Advantageously the apparatus is constructed such that the geometry and the thickness of the disks employed as well as the geometry of the test tubes and the construction of the sieve floor of the frame remains unchanged. Similarly the disks and the frames are exchangeable amongst each other, without that a re-calibration of the apparatus has to be performed. In particular such disks can be employed, which exhibit according to the prescription also five holes, wherein one of the five holes is a centered middle hole. The disks are only constructed such that a permanent magnet with a hole is disposed within this disk around the centered middle bore, such that the central bore of the disk is continued by the hole of the permanent magnet. The sleight addition in weight by the permanent magnet can be balanced in a simple way by insertion of small hollow spaces into the disk, such that the pre-scribed weight of the disk is maintained.
Advantageously, the permanent magnet is formed cylindrical and of tubular or sleeve shape, wherein the longitudinal extension of the permanent magnet is larger than the diameter of the permanent magnet. This way the magnetic stray of the permanent magnet can be maintained small. The permanent magnet is completely surrounded of plastic material within the disk, for example a plastic sleeve is inserted into the hole of the permanent magnet.
The magnetic field sensor element can be a Hall generator or a magneto-resistive sensor or a saturable core probe, wherein a Hall generator is preferred, where the Hall generator is capable of measuring even smallest changes in field strength.
The magnetic field sensor element or, respectively, the Hall generator is disposed in the region of the largest gradient of the magnetic field, as soon as the permanent magnet stands directly opposed to the magnetic field sensor element in the final position of the disk. For this reason it is advantageous that the main part of the sensor with small dimensions is disposed so far spaced apart that the main part of the sensor with small dimensions is disposed immediately below the annular front face of the magnet, that is in a top planar view sideways to the hole of the permanent magnet.
Furthermore each channel is measured several times during a disintegration process with the apparatus and an average value formed from the measurements. It is also possible to scan each of the six magnetic field sensor elements by way of a fast multiplexer.
The novel features which are considered as characteristic for the invention are set forth in the appended claims. The invention itself, however, both as to its construction and its method of operation, together with additional objects and advantages thereof, will be best understood from the following description of specific embodiments when read in connection with the accompanying drawing.

Device for determining the disintegration time of compressed pharmaceutical mold bodies, such as tablets and capsules, as well as a method for this purpose