There are provided an apparatus for fine pattern formation, which can form a fine pattern with high accuracy by direct writing with ink, a production process of fine nozzles provided in the apparatus for fine pattern formation, and a method for fine pattern formation. Fine pattern formation with high accuracy could have been realized by the apparatus for fine pattern formation, comprising: a silicon substrate; a plurality of fine holes which extend through the silicon substrate from the surface of the silicon substrate to the back surface of the silicon substrate and have a silicon oxide layer on the wall surface thereof; fine nozzles which are protruded, integrally with the silicon oxide layer, on the back surface side of the silicon substrate from each opening of the fine holes; a silicon nitride layer provided on the surface and side of the silicon substrate; a support member provided on the surface side of the silicon substrate; an ink passage for supplying ink to the opening of each fine hole on the surface side of the silicon substrate; and an ink supplying device connected to the ink passage.

The present invention relates to an apparatus for fine pattern formation, a process for producing fine nozzles, and a method for fine pattern formation, and particularly to an apparatus for fine pattern formation, which can be applied, for example, to pattern formation for the production of liquid crystal displays, plasma displays, and flat displays of electroluminescence or the like, and conductor pattern formation and correction of conductor patterns of printed wiring boards, a process for producing fine nozzles used in the apparatus for fine pattern formation, and a method for the fine pattern formation.
Fine patterns, for example, for color filters for liquid crystal displays have been formed by photolithography, printing, electrodeposition, or the like. Among these pattern formation methods, photolithography is advantageous in accuracy and quality of appearance. The photolithography, which can realize wiring of a pattern with high accuracy, is also used in the formation of conductor patterns in printed wiring boards.
In an example of the production of a color filter by photolithography, a photosensitive resist is coated on a thin film of a metal, such as chromium, formed, for example, by sputtering or vapor deposition, exposure through a photomask and development are carried out to prepare a resist pattern, and the thin metal film is patterned by etching using the resist pattern as a mask to form a black matrix. Next, a color pigment-containing photosensitive resist is coated, followed by exposure through a photomask and development to form a colored layer for a color filter. On the other hand, in the case of a printed wiring board, a photosensitive resist pattern is formed on a copper plating, and the copper plating is etched using the photosensitive resist pattern as a mask to produce a conductor pattern.
The above-described conventional fine pattern formation by photolithography, such as pattern formation for a color filter and conductor pattern formation, however, disadvantageously suffers from a complicated process, which is an obstacle to a reduction in production cost.
Under the above circumstances, the present invention has been made, and it is an object of the present invention to provide an apparatus for fine pattern formation, which can form a fine pattern with high accuracy by direct writing of a pattern with ink, a production process of fine nozzles provided in the apparatus for fine pattern formation, and a method for fine pattern formation.
In order to attain the above object, according to one aspect of the present invention, there is provided an apparatus for fine pattern formation comprising: a silicon substrate; a plurality of fine holes which extend through the silicon substrate from the surface of the silicon substrate to the back surface of the silicon substrate and have a silicon oxide layer on the wall surface thereof; fine nozzles which are protruded, integrally with the silicon oxide layer, on the back surface side of the silicon substrate from each opening of the fine holes; a silicon nitride layer provided on the surface and side of the silicon substrate; a support member provided on the surface side of the silicon substrate; an ink passage for supplying ink to the opening of each fine hole on the surface side of the silicon substrate; and an ink supplying device connected to the ink passage.
In this apparatus, preferably, the diameter of the openings in the fine nozzles is in the range of 1 to 100 xcexcm in a variation within xc2x11 xcexcm and the fine nozzles are provided at a pitch in the range of 2 to 1000 xcexcm.
According to another aspect of the present invention, there is provided an apparatus for fine pattern formation, comprising: a silicon substrate; a plurality of fine nozzles protruded from the back surface of the silicon substrate; a plurality of fine holes which extend at fine nozzle formed sites through the silicon substrate from the surface of the silicon substrate to the back surface of the silicon substrate and have a silicon oxide layer on the wall surface thereof; a support member provided on the surface side of the silicon substrate; an ink passage for supplying ink to the opening of each fine hole on the surface side of the silicon substrate; and an ink supplying device connected to the ink passage, said fine nozzles each comprising a nozzle base provided integrally with the silicon substrate, an inner surface layer of silicon oxide provided on the inner wall surface of nozzle bases in communication with the fine holes, and an end face layer of silicon oxide provided integrally with the inner surface layer of silicon oxide so as to cover the front end face of the nozzle bases.
In this apparatus, preferably, the diameter of the openings in the fine nozzles is in the range of 1 to 100 xcexcm in a variation within xc2x11 xcexcm and the fine nozzles are provided at a pitch in the range of 4 to 1000 xcexcm.
In the above apparatuses for fine pattern formation, preferably, the protrusion length of the fine nozzles is in the range of 1 to 150 xcexcm.
In the above apparatuses for fine pattern formation, preferably, the fine holes in their openings on the surface side of the silicon substrate are in the form of tapered concaves which have been widened toward the surface side of the silicon substrate. Alternatively, in the above apparatuses for fine pattern formation, preferably, the fine holes in their openings on the surface side of the silicon substrate are in the form of multistaged concaves which have been widened toward the surface side of the silicon substrate.
In the above apparatuses for fine pattern formation, preferably, fine holes are divided into two or more groups and ink passages are provided separately from each other or one another for respective fine hole groups.
According to still another aspect of the present invention, there is provided a process for producing a plurality of fine nozzles, formed of silicon oxide, protruded from one surface of a silicon substrate and in communication with fine holes which extend through the silicon substrate and have a silicon oxide layer on the wall surface thereof, said process comprising: a first step of providing a silicon substrate having on its whole surface a silicon nitride layer and forming a mask pattern having a plurality of fine openings on the silicon nitride layer in its portion located on one surface of the silicon substrate; a second step of forming through fine holes in the silicon substrate by deep etching using the mask pattern as a mask; a third step of removing the mask pattern and oxidizing the inside of the through fine holes of the silicon substrate to form a silicon oxide layer; and a fourth step of removing a part of the silicon nitride layer and a part of the silicon substrate from one surface of the silicon substrate by dry etching to expose the silicon oxide layer by a predetermined length, thereby forming fine nozzles.
In the fourth step, preferably, etching is started with the surface from which the mask pattern has been removed.
According to a further aspect of the present invention, there is provided a process for producing a plurality of fine nozzles protruded from one surface of a silicon substrate, said fine nozzles comprising a nozzle base, provided integrally with the silicon substrate, and a silicon oxide end face layer covering the front end face of the nozzle base, said nozzle base being in communication with fine holes, which extend through the silicon substrate and have a silicon oxide layer on the wall surface thereof, and having a silicon oxide inner surface layer on its inner wall surface, said process comprising: a first step of providing a silicon substrate having on its whole surface a silicon nitride layer and patterning the silicon nitride layer in its portion located on one surface of the silicon substrate to form a pattern having a plurality of small openings; a second step of forming a mask thin film so as to cover the pattern of the silicon nitride layer and patterning the mask thin film to form a mask pattern having fine openings located within the small openings; a third step of forming through fine holes in the silicon substrate by deep etching using the mask pattern as a mask; a fourth step of removing the mask pattern and oxidizing sites within the through fine holes in the silicone substrate and sites exposed within the small openings to form a silicon oxide layer; a fifth step of removing the silicon nitride layer and removing a part of the silicon substrate by dry etching using the silicon oxide layer as a mask from the surface side, on which the silicon oxide layer has been formed, to form nozzle bases having a predetermined length, thereby forming fine nozzles.
According to a still further aspect of the present invention, there is provided a process for producing a plurality of fine nozzles, formed of silicon oxide, protruded from one surface of a silicon substrate and in communication with fine holes which extend through the silicon substrate and have a silicon oxide layer on the wall surface thereof, said process comprising: a first step of providing a silicon substrate of  less than 100 greater than  surface crystal orientation having on its whole surface a silicon nitride layer and patterning the silicon nitride layer in its portion located on one surface side of the silicon substrate to form a pattern having a plurality of openings for taper; a second step of etching the surface of the silicon substrate by crystallographically anisotropic etching using the silicon nitride layer as a mask to form tapered concaves; a third step of forming a mask thin film on both surfaces of the silicon substrate and patterning the mask thin film in its portion located on the surface of the silicon substrate remote from the tapered concaves to form a mask pattern having fine openings such that the center of each opening substantially conforms to the center of each tapered concave through the silicon substrate; a fourth step of forming through fine holes in the silicon substrate by deep etching using, as a mask, the mask pattern and the mask thin film; a fifth step of removing the mask pattern and the mask thin film and oxidizing sites within the through fine holes in the silicone substrate and sites exposed within the tapered concaves to form a silicon oxide layer; and a sixth step of removing a part of the silicon nitride layer and a part of the silicon substrate by dry etching from the surface side of the silicon substrate remote from the tapered concaves to expose the silicon oxide layer by a predetermined length, thereby forming fine nozzles.
According to another aspect of the present invention, there is provided a process for producing a plurality of fine nozzles protruded from one surface of a silicon substrate, said fine nozzles comprising a nozzle base, provided integrally with the silicon substrate, and a silicon oxide end face layer covering the front end face of the nozzle base, said nozzle base being in communication with fine holes, which extend through the silicon substrate and have a silicon oxide layer on the wall surface thereof, and having a silicon oxide inner surface layer on its inner wall surface, said process comprising: a first step of providing a silicon substrate of  less than 100 greater than  surface crystal orientation having on its whole surface a silicon nitride layer and patterning the silicon nitride layer in its portion located on one surface side of the silicon substrate to form a pattern having a plurality of openings for taper; a second step of etching the surface of the silicon substrate by crystallographically anisotropic etching using the silicon nitride layer as a mask to form tapered concaves; a third step of patterning the silicon nitride layer in its portion located on the surface side of the silicon substrate remote from the tapered concaves to form a pattern having small openings such that the center of each opening substantially conforms to the center of each tapered concave through the silicon substrate; a fourth step of forming a mask thin film on both surfaces of the silicon substrate and patterning the mask thin film in its portion located on the surface side of the silicon substrate remote from tapered concaves to form a mask pattern having fine openings located within the small openings; a fifth step of forming through fine holes in the silicon substrate by deep etching using, as a mask, the mask pattern and the mask thin film; a sixth step of removing the mask pattern and the mask thin film and oxidizing sites within the through fine holes in the silicone substrate, sites exposed within the small openings, and sites exposed within the tapered concaves to form a silicon oxide layer; and a seventh step of removing the silicon nitride layer and removing a part of the silicon substrate by dry etching using the silicon oxide layer as a mask from the surface side of the silicon substrate remote from the tapered concaves to form nozzle bases having a predetermined length, thereby forming fine nozzles.
According to still another aspect of the present invention, there is provided a process for producing a plurality of fine nozzles, formed of silicon oxide, protruded from one surface of a silicon substrate and in communication with fine holes which extend through the silicon substrate and have a silicon oxide layer on the wall surface thereof, said process comprising: a first step of providing a silicon substrate having on its whole surface a silicon nitride layer, forming a mask pattern having a plurality of fine openings on the silicon nitride layer in its portion located on one surface of the silicon substrate, and forming, on the silicon nitride layer on the other surface of the silicon substrate, a mask pattern having wide openings such that the center of each wide opening substantially conforms to the center of each fine opening through the silicon substrate; a second step of forming fine holes having predetermined depth in the silicon substrate by deep etching using the mask pattern having fine openings as a mask; a third step of forming wide concaves in the silicon substrate by deep etching using the mask pattern having wide openings as a mask in such a manner that the openings of the fine holes are exposed within the wide concaves, thereby forming multistaged concaves; a fourth step of removing the mask pattern and oxidizing sites within the fine holes of the silicon substrate and sites exposed within the wide concaves to form a silicon oxide layer; and a fifth step of removing a part of the silicon nitride layer and a part of the silicon substrate from the surface of the silicon substrate remote from the wide concaves by dry etching to expose the silicon oxide layer by a predetermined length, thereby forming fine nozzles.
According to a further aspect of the present invention, there is provided a process for producing a plurality of fine nozzles protruded from one surface of a silicon substrate, said fine nozzles comprising a nozzle base, provided integrally with the silicon substrate, and a silicon oxide end face layer covering the front end face of the nozzle base, said nozzle base being in communication with fine holes, which extend through the silicon substrate and have a silicon oxide layer on the wall surface thereof, and having a silicon oxide inner surface layer on its inner wall surface, said process comprising: a first step of providing a silicon substrate having on its whole surface a silicon nitride layer and patterning the silicon nitride layer in its portion located on one surface of the silicon substrate to form a pattern having a plurality of small openings; a second step of forming a mask thin film so as to cover the pattern of the silicon nitride layer and then patterning the mask thin film to form a mask pattern having fine openings located within the small openings, and, in addition, patterning the mask thin film on the other surface to form a mask pattern having wide openings such that the center of each wide opening substantially conforms to the center of each fine opening through the silicon substrate; a third step of forming fine holes having predetermined depth in the silicon substrate by deep etching using the mask pattern having fine openings as a mask; a fourth step of forming wide concaves in the silicon substrate by deep etching using the mask pattern having wide openings as a mask in such a manner that the openings of the fine holes are exposed within the wide concaves, thereby forming multistaged concaves; a fifth step of removing the mask pattern and oxidizing sites within the fine holes of the silicon substrate, sites exposed within the wide concaves, and sites exposed within the small openings to form a silicon oxide layer; and a sixth step of removing the silicon nitride layer and removing a part of the silicon substrate by dry etching using the silicon oxide layer as a mask from the surface of the silicon substrate remote from the wide concaves to form nozzle bases having a predetermined length, thereby forming fine nozzles.
According to the above invention, ink supplied to the fine holes in the silicon substrate can be ejected through the fine nozzles and deposited onto a pattern object to directly write a pattern on the pattern object, and the amount of ink deposited can be varied as desired by varying the amount of ink supplied.
Furthermore, in order to attain the above object, according to a further aspect of the present invention, there is provided an apparatus for fine pattern formation comprising: a silicon substrate; a plurality of fine holes which extend through the silicon substrate from the surface of the silicon substrate to the back surface of the silicon substrate and have a silicon oxide layer on the wall surface thereof; fine nozzles which are protruded, integrally with the silicon oxide layer, on the back surface side of the silicon substrate from each opening of the fine holes; a reinforcing layer provided at least on the front end face and outer face of the fine nozzles; a support member provided on the surface side of the silicon substrate; an ink passage for supplying ink to the opening of each fine hole on the surface side of the silicon substrate; and an ink supplying device connected to the ink passage.
In the above apparatus for fine pattern formation, preferably, the thickness of the reinforcing layer is at least twice the thickness of the fine nozzles.
In the above apparatus for fine pattern formation, preferably, the reinforcing layer is formed of any one of silicon oxide and phosphorus silicon glass.
In the above apparatus for fine pattern formation, preferably, the fine nozzles have an opening diameter in the range of 1 to 100 xcexcm and are provided at a pitch in the range of 4 to 1000 xcexcm. Alternatively, in the above apparatus for fine pattern formation, preferably, the fine nozzles have a projection length in the range of 1 to 400 xcexcm.
In the above apparatus for fine pattern formation, preferably, the fine holes in their openings on the surface side of the silicon substrate are in the form of tapered concaves which have been widened toward the surface side of the silicon substrate. Alternatively, in the above apparatus for fine pattern formation, preferably, the fine holes in their openings on the surface side of the silicon substrate are in the form of multistaged concaves which have been widened toward the surface side of the silicon substrate.
In the above apparatus for fine pattern formation, preferably, the fine holes are divided into two or more groups and ink passages are provided separately from each other or one another for respective fine hole groups.
In the above apparatus for fine pattern formation, preferably, a water-repellent layer is provided at least on the reinforcing layer, which is provided on the outer face of the fine nozzles, and on the back surface side of the silicon substrate.
In the above apparatus for fine pattern formation, preferably, the water-repellent layer is formed of fluorocarbon.
According to the present invention, the provision of the reinforcing layer in the fine nozzles can enhance the mechanical strength of the fine nozzles, ink supplied to the fine holes in the silicon substrate can be ejected through the fine nozzles and deposited on the pattern object to directly write a pattern, and the amount of ink deposited can be varied as desired by varying the amount of ink supplied.
Further, in order to attain the above object, according to another aspect of the present invention, there is provided an apparatus for fine pattern formation, comprising: a silicon substrate; a plurality of fine holes provided so as to extend through the silicon substrate from the surface of the silicon substrate to the back surface of the silicon substrate; a main electrode provided on the surface side of the silicon substrate; a counter electrode provided on the back surface side of the silicon substrate while leaving a predetermined space between the main electrode and the counter electrode; a support member provided on the surface side of the silicon substrate; an ink passage for supplying ink to openings in the fine holes on the surface side of the silicon substrate; and an ink supplying device connected to the ink passage.
In the above apparatus for fine pattern formation, preferably, nozzles are protruded from the openings of the fine holes on the back surface side of the silicon substrate.
In the above apparatus for fine pattern formation, preferably, the wall surface of the fine holes has a silicon oxide layer and the nozzles are formed of silicon oxide.
In the above apparatus for fine pattern formation, preferably, the counter electrode is in a drum or flat plate form.
In the above apparatus for fine pattern formation, preferably, the fine holes have an opening diameter in the range of 1 to 100 xcexcm and are provided at a pitch in the range of 2 to 1000 xcexcm.
In the above apparatus for fine pattern formation, preferably, the nozzles have a protrusion length in the range of 10 to 400 xcexcm.
In the above apparatus for fine pattern formation, preferably, the fine holes in their openings on the surface side of the silicon substrate are in the form of tapered concaves which have been widened toward the surface side of the silicon substrate. Alternatively, in the above apparatus for fine pattern formation, preferably, the fine holes in their openings on the surface side of the silicon substrate are in the form of multistaged concaves which have been widened toward the surface side of the silicon substrate.
In the above apparatus for fine pattern formation, preferably, the fine holes are divided into two or more groups and ink passages are provided separately from each other or one another for respective fine hole groups. Alternatively, in the above apparatus for fine pattern formation, preferably, main electrodes are separately provided for respective fine hole groups.
According to still another aspect of the present invention, there is provided a method for fine pattern formation, comprising the step of: while relatively scanning any one of the apparatuses for fine pattern formation and a pattern object in a predetermined direction, continuously or intermittently ejecting ink supplied at low pressure from the ink passage onto the pattern object through the fine holes in such a state that a voltage is applied to the main electrode in the apparatus for fine pattern formation, whereby a stripe pattern or a dot pattern is formed.
In the above method for fine pattern formation, preferably, stripes constituting the pattern are formed by supplying ink through a plurality of fine holes arranged on an identical line along the scanning direction.
According to a further aspect of the present invention, there is provided a method for fine pattern formation, comprising the steps of: disposing any one of the above apparatuses for fine pattern formation at a predetermined position of a pattern object; and ejecting a given amount of ink supplied at low pressure from the ink passage onto the pattern object through the fine holes in such a state that a voltage is applied to the main electrode of the apparatus for fine pattern formation, whereby a pattern is formed.
In the above method for fine pattern formation, preferably, the voltage applied to the main electrode is regulated to control ink ejection width and the amount of ink ejected.
According to the present invention, supplied ink can be ejected through the fine holes in the silicon substrate by an electric field formed between the main electrode and the counter electrode and a low pressure applied at the time of supply of the ink and can be deposited onto a pattern object to directly write a pattern, and the amount of ink deposited can be varied as desired by varying the field strength and the ink supply pressure to control ink ejection width and the amount of ink ejected. As used herein, the term xe2x80x9cinkxe2x80x9d generally refers to a liquid composition comprising a colorant, such as a dye or a pigment, and a binder or a vehicle. For example, in display members or circuit formation applications, however, the ink widely embraces pastes containing metallic or magnetic fine particles or ceramic or other fine particles, and liquid compositions containing a resin or a phosphor material or an organic EL material, and photoresists.


A coating composition having outstanding electrically conductive and electromagnetic radiation absorptive properties is disclosed with a water emulsion polymer binder. The binder is a blend of a first emulsion containing a conjugated diene as monomer or comonomer, and a second emulsion containing an acrylic, aliphatic or aromatic polyurethane, polyester urethane, polyester, epoxy, polyamide, polyimide, vinyl, fluoropolymer, or silicone polymer. An effective amount of electrically conductive and electromagnetic radiation absorptive particles is dispersed in the binder. The particles include a combination of graphite particles, carbon nanotubes and metal containing particles. An effective amount of water is also present.

1. Field of the Invention
The present invention is directed to electrically conductive and electromagnetic radiation absorptive coating compositions and the like.
2. Brief Description of the Prior Art
A variety of coating compositions are known which have electrically conductive or electromagnetic radiation absorptive properties or the like. The solvent for many of the coating compositions has been primarily a volatile organic compound (VOC). A VOC-based binder system has several drawbacks. It may be toxic, flammable, and possibly explosive. The VOC raw material is costly to purchase and the waste is expensive to discard. Generally, VOC solvent emitted from coating operations is an environmental air pollutant. Expensive equipment and procedures are required to capture and contain VOC solvent emissions in order to reduce air pollution and enable proper waste disposal.
Coating compositions are also known which use electrically conductive or electromagnetic radiation absorptive microspheres. However, these coating compositions have been limited by the binder systems employed.
Finally, coating compositions are known which use a plurality of electrically conductive particles. However, these coating compositions have also been limited by the binder systems employed.
Accordingly, it is an object of the present invention to provide an aqueous based coating composition having electrically conductive or electromagnetic radiation absorptive properties or the like.
It is a further object of the present invention to provide a coating composition which is electrically conductive or electromagnetic absorptive or the like having an improved binder system.
It is another object of the present invention to provide an aqueous based coating composition having electrically conductive and electromagnetic radiation absorptive properties particularly useful for coating plastic surfaces, fiber reinforced plastics, flexible plastic objects and other flexible materials as well as metal surfaces and the like.
These and other objects of the invention will become more apparent upon reading the following description of the invention.

This patent is subject to a terminal disclaimer.

Electrically conductive and electromagnetic radiation absorptive coating compositions and the like


Additive manufacturing apparatus including a build module is presented. The build module includes a support structure; a powder supply chamber formed in the support structure; and powder applicator disposed on the support structure and located proximate to the powder supply chamber. The build module further includes a powder recovery chamber and a plurality of build plates spatially disposed around the powder recovery chamber, the plurality of build plates configured to move around the powder recovery chamber. The build module is configured such that during an additive manufacturing process step, a build plate of the plurality of build plates is disposed between the powder supply chamber and the powder recovery chamber, and the powder applicator is configured to distribute a required amount of the powder material from the powder supply chamber on the build plate and deposit any excess powder material in the powder recovery chamber. Related processes are also presented.

Embodiments of the disclosure generally relate to an additive manufacturing apparatus. More particularly, embodiments of the disclosure relate to an additive manufacturing apparatus including a plurality of build plates configured to move around a powder recovery chamber.
Powder bed technologies are some examples of additive manufacturing processes. However, in powder bed technology, as the build takes place in the powder bed, conventional additive manufacturing systems may use a large amount of powder, which may increase the associated costs with the process. Further, the higher build times of typical powder-based technologies could result in lower efficiencies of the associated additive manufacturing processes. The dwell time of the re-coater blade, i.e., the time taken by the blade to drive across the build plate, may affect the build times in these systems
Accordingly, there remains a need for an additive manufacturing apparatus that allows for minimization of powder usage and wastage in the additive manufacturing apparatus, and accelerated build times.

Additive manufacturing apparatus and related process


The disclosure provides novobiocin analogues with noviose replacements which are useful as Hsp90 inhibitors in the treatment of cancer.

The Hsp90 molecular chaperone has emerged as a promising target for the treatment of cancer. While most current therapies are directed at disrupting a single molecular function, Hsp90 is distinctive in its regulation of multiple oncogenic pathways. There are more than 100 client proteins that depend upon Hsp90 for their folding and conformational maintenance, many of which contribute to cancer cell proliferation.
Novobiocin, a member of the coumermycin family of antibiotics, was isolated from streptomyces and shown to manifest potent activity against Gram-positive bacteria. Novobiocin elicits antimicrobial activity through binding the ATP-binding pocket of DNA gyrase and prohibiting ATP-hydrolysis.
The present disclosure is directed to novel novobiocin analogues having a modified sugar.

Novobiocin analogues having modified sugar moieties


A drain valve device based on capacitive sensing for a water tank of a toilet includes a drain valve disposed in the water tank of the toilet to control the water tank to drain water; a capacitive sensing control module that opens the drain valve; and an assembly fixture used to connect the capacitive sensing control module to the drain valve to make the capacitive control module and the drain valve form an integration. The assembly fixture connects the capacitive sensing control module and the drain vale to form the integration, so that during assembly of the drain valve, the capacitive sensing control module is affixed to the toilet water tank at the same time. Thus, assembly is simple and convenient, and there is no need to dispose an assembly hole in the water tank cover so the structure is simpler.

The drain valve used in the ceramic toilet water tank in the existing market is usually coupled a button or a sensing window of the water tank cover to form a mechanical type, hydraulic type, sensing type or air control drain valve, the drain valves are needed to connect to the button or the sensing component in other places, such as in the water tank cover, by pushing bars or electric wires or pipes, when assembling, it needs to assemble the button or the sensing component after the drain valve is assembled. Therefore, existing drain valves has some defects: firstly, the drain valve and the button or sensing component need to be assembled separately, the assembly is complicated and inconvenient; secondly, for a sensing type drain valve, the electric wires are exposed out of the structure and located in the water tank, it goes against the water proof performance.
There are proposal that the sensing control portion to open the drain valve is hanging to the ceramic wall of the water tank, a motor is used to drive the chain to lift the flapper up so as to achieve drainage. However, different ceramic water tank have different wall thickness, not all sensing control component can be hung to the wall, so that it is not suitable for all; besides, as different water tanks have different height, the chain needs to be height adjusted, the assembly is complicated; and as the flapper is located at the center of the water tank, the sensing control component needs to be hung at the center, but when the flapper is open, it blocks at the front of the water tank, thus influencing the sensing operation.

Toilet tank drive valve device based on capacitive sensing


An apparatus and method are disclosed for user and moving vehicle detection in which sensor data for a portable device is processed to determine whether the portable device is in a moving vehicle. Following a determination the portable device is in a moving vehicle, the sensor data is to characterize an association between the user and the portable device to determine whether the portable device is connected to the user. If the user is connected to the portable device, it is then determined if the portable device is being held in hand. If the portable device is held in hand, it is then determined if the user is operating the moving vehicle. Output from an image sensor of the portable device may be used in determining if the user is the operator.

Portable electronic devices, such as those configured to be handheld or otherwise associated with a user, are employed in a wide variety of applications and environments. The ubiquity of such devices as mobile phones, wearables, including smart watches and glasses, digital still cameras and video cameras, handheld music and media players, portable video game devices and controllers, tablets, mobile internet devices (MIDs), personal navigation devices (PNDs), other APPlication acCESSORIES (or Appcessories for short) and other similar devices speaks the popularity and desire fir these types of devices. Increasingly, such devices are equipped with one or more sensors or other systems for determining the position or motion of the portable device with increasing sophistication and accuracy. Likewise, additional sensing capabilities are commonly available in the form of proximity and ambient light sensors, image sensors, barometers, magnetometers and the like. Still further, such portable devices often feature navigation systems, such as a Global Navigation Satellite Systems (GNSS), that enable precise determinations regarding geophysical position and movement. Corresponding advances in computation power, size, power consumption and prices make such portable devices powerful computing tools with extensive capabilities to detect their environment.
Given the noted popularity in portable devices having some or all of these capabilities, the user of such a portable device is typically associated with it to varying degrees throughout the course of the day. The user may be holding the portable device in hand, and further may be employing it for one of its functions such as phoning, texting, viewing, photographing, playing games or any of a wide variety of other applications. Alternatively, the user may also be carrying the portable device in a pocket, a holster, a purse, a backpack, or in any other manner that creates some type of physical connection with the user. Yet another possibility is that the portable device is in the possession of the user, but not physically connected, such as when the device is resting on a nearby surface or deposited in a holder.
However, even though the portable device may be associated with the user, there are circumstances during which it would be undesirable for the user to have certain types of interactions with the portable device. For example, when the user is operating a moving vehicle, safety may be compromised if the user was interacting with the portable device in a manner that required manual input and/or unduly distracted from the moving vehicle operation. Indeed, a number of jurisdictions have enacted "hands-free" laws that prohibit holding portable devices while driving.
Correspondingly, there is a need for techniques to determine whether a portable device is in a moving vehicle. Further, there is a need for techniques to determine how the portable device is associated with the user, and in particular, to determine whether the portable device is being held in the hand. Still further, there is a need for techniques to determine whether the user is operating the moving vehicle once it is determined the portable device is hand held and in a moving vehicle. It would be desirable to leverage the noted capabilities of the portable device for performing these determinations. In turn, the information about the user's association with the portable device and whether the user is operating the moving vehicle may be used for a number of purposes. For example, the portable device may warn the user when an unsafe association is detected and/or the user's behavior may be analyzed for entities such as insurance companies or employers for users whom operating moving vehicles is part of the job. As will be described in the following materials, this disclosure satisfies these and other needs.

Method and apparatus for user and moving vehicle detection


A frequency selective hearing protection device and method utilizes adaptive filtering to hinder transmission of frequency components in ambient sound above a preselected threshold level. Sound frequency components which are not above the threshold level, such as normal speech, are allowed to pass. Electrical analog signals produced by a transducer are converted to a stream of digital input signals. The digital input signals are applied to a digital filter such as an FIR filter implementing a time domain difference equation. As a result, digital output signals are produced which are reconverted to analog output signals and applied to an actuator to produce audible sound. To adjust the frequency response of the invention to suppress gain at frequency components above the threshold, windows of input and output data signals are first assembled. Respective frequency domain transforms such as fast Fourier transforms provide spectrums representative of frequency component amplitudes. Any violator components exceeding the threshold level are distinguished and coefficient values of the difference equation are altered to suppress gain at those frequencies. Preferably, the coefficient values are readjusted to again allow the frequencies to pass if the threshold is not exceeded in preselected number of subsequent digital input signals.

1. Field of the Invention
The present invention relates to systems for preventing discomfort and hearing loss due to high amplitude sound. More particularly, the invention relates to such a system utilizing an adaptive digital filter to selectively hinder transmission of sound frequency components above a preselected threshold level while allowing transmission of other sound frequency components.
2. Description of the Prior Art
Exposure to environments of high amplitude sound has often been a source of discomfort and hearing loss. To alleviate such problems, workers at construction sites and in industrial facilities have frequently been provided with sound blocking earplugs. While these earplugs are generally effective at reducing high power noise, the sound blockage function is nonselective. Thus, all sound is suppressed, not merely high power noise. As a result, verbal communication is also restricted.

Frequency selective sound blocking system for hearing protection


A process for the preparation of a radiation-sensitive silver halide emulsion comprised of high bromide cubical silver halide grains is described, the process comprising: (a) providing in a stirred reaction vessel a dispersing medium and high bromide silver halide seed grains, the seed grains comprising at least 5 mole % of the final emulsion silver, and (b) precipitating a silver halide shell which comprises at least 5 mole % of the final emulsion silver onto the seed grains by introducing at least a silver salt solution into the dispersing medium at a rate such that the normalized shell molar addition rate, Rs, is above 1.0xc3x9710xe2x88x923 minxe2x88x922, Rs satisfying the formula:       R    s    =            M      s                      M        t                          t        s        2

This invention is directed to the preparation of radiation sensitive high bromide silver halide photographic emulsions, including emulsions useful in electronic printing methods wherein information is recorded in a pixel-by-pixel mode in a radiation sensitive silver halide emulsion layer. It particularly relates to the preparation of the exterior portions of silver halide emulsion grains after formation of a core.
In referring to grains and emulsions containing two or more halides, the halides are named in order of ascending concentrations.
The term xe2x80x9chigh bromidexe2x80x9d and xe2x80x9chigh chloridexe2x80x9d in referring to silver halide grains and emulsions indicate greater than 50 mole percent bromide or chloride, respectively, based on total silver.
The term xe2x80x9cequivalent circular diameterxe2x80x9d or xe2x80x9cECDxe2x80x9d indicates the diameter of a circle having an area equal to the projected area of a grain or particle.
The term xe2x80x9csizexe2x80x9d in referring to grains and particles, unless otherwise described, indicates ECD.
The term xe2x80x9cregular grainxe2x80x9d refers to a silver halide grain that is internally free of stacking faults, which include twin planes and screw dislocations.
The term xe2x80x9ccubic grainxe2x80x9d is employed to indicate a regular grain is that bounded by six {100} crystal faces. Typically the corners and edges of the grains show some rounding due to ripening, but no identifiable crystal faces other than the six {100} crystal faces. The six {100} crystal faces form three pairs of parallel {100} crystal faces that are equidistantly spaced.
The term xe2x80x9ccubical grainxe2x80x9d is employed to indicate grains that are at least in part bounded by {100} crystal faces satisfying the relative orientation and spacing of cubic grains. That is, three pairs of parallel {100} crystal faces are equidistantly spaced. Cubical grains include both cubic grains and grains that have one or more additional identifiable crystal faces. For example, tetradecahedral grains having six {100} and eight {111} crystal faces are a common form of cubical grains.
The term xe2x80x9croundness coefficientxe2x80x9d (hereinafter assigned the symbol xe2x80x9cnxe2x80x9d) and the term xe2x80x9croundness indexxe2x80x9d (hereinafter assigned the symbol xe2x80x9cQxe2x80x9d) are measures of the degree to which silver halide grain corners are rounded as defined by Mehta et al. in U.S. Pat. No. 6,048,683. xe2x80x9cnxe2x80x9d is chosen to satisfy the formula xn+yn=Rn, where R is any vector extending from the center of a {100} crystal face of a grain to the projected peripheral edge of the grain viewed normal to the {100} crystal face, x is an X axis coordinate of R, y is a Y axis coordinate of R, and X and Y are mutually perpendicular axes in the plane of the {100} crystal face. For a circle, the roundness coefficient is 2, while for a square the roundness coefficient is increased to infinity. For convenience, roundness index Q is defined as being equal to 2/n. Thus, the Q of a square is zero, while that for a circle is 1. The degree to which regular silver halide grains having {100} crystal faces exhibit corner rounding is determined by looking at the projected area of a grain in a photomicrograph viewed normal to a {100} crystal face. The value of n that most closely matches the peripheral boundery of the {100} grain face is the roundness coefficient of the grain. From measurement of a representative number of grains, an average roundness coefficient n and roundness index Q can be determined for an emulsion.
The term xe2x80x9ccentral portionxe2x80x9d or xe2x80x9ccorexe2x80x9d in referring to silver halide grains refers to an interior portion of the grain structure that is first precipitated relative to a later precipitated portion.
The term xe2x80x9cshellxe2x80x9d in referring to silver halide grains refers to an exterior portion of the silver halide grain which is precipitated on a central portion.
The term xe2x80x9cdopantxe2x80x9d is employed to indicate any material within the rock salt face centered cubic crystal lattice structure of a silver halide grain other than silver ion or halide ion.
The term xe2x80x9cdopant bandxe2x80x9d is employed to indicate the portion of the grain formed during the time that dopant was introduced to the grain during precipitation process.
The term xe2x80x9cnormalized shell molar addition ratexe2x80x9d, hereinafter assigned the symbol Rs, is a measure of the intensity of rate of addition of silver salt solution to a reaction vessel during formation of a shell. Rs is defined by the formula:       R    s    =            M      s                      M        t                          t        s        2
where Ms is the number of moles of silver halides added to the reaction vessel during the formation of the shell, ts is the run time, in minutes, of the silver salt solution for the formation of the shell, and Mt is total moles of silver halides in the reaction vessel at the end of the precipitation.
The term xe2x80x9clog Exe2x80x9d is the logarithm of exposure in lux-seconds.
Photographic speed is reported in relative log units and therefore referred to as relative log speed. 1.0 relative log speed unit is equal to 0.01 log E.
The term xe2x80x9ccontrastxe2x80x9d or xe2x80x9cxcex3xe2x80x9d is employed to indicate the slope of a line drawn from stated density points on the characteristic curve.
The term xe2x80x9crapid access processingxe2x80x9d and xe2x80x9crapid access processorxe2x80x9d are employed to indicate the capability of providing dry-to-dry processing in 90 seconds or less. The term xe2x80x9cdry-to-dryxe2x80x9d is used to indicate the processing cycle that occurs between the time a dry, imagewise exposed element enters a processor to the time it emerges, developed, fixed and dry
Research Disclosure is published by Kenneth Mason Publications, Ltd., Dudley House, 12 North St., Emsworth, Hampshire P010 7DQ, England.
Double-jet precipitation is a common practice in the making of silver halide emulsions. Silver salt solution and halide salt solution are introduced simultaneously, but separately, into a precipitation reactor under mixing. In order to achieve desired crystal characteristics, typically, the silver ion activity or the halide ion activity is controlled during the precipitation by adjusting the feed rates of the salt solutions using either a silver ion sensor or a halide ion sensor.
Formation of silver halide emulsions typically involves a crystal nuclei-forming step wherein addition of silver ion results primarily in the precipitation of new crystal nuclei, and a subsequent double-jet growth step wherein the rate at which silver and halide are introduced is controlled to primarily grow the crystals already previously formed while avoiding the formation of new seed grains, i.e., renucleation. Addition rate control to avoid renucleation, and thereby generally provide for a more monodisperse grain size final grain population, is generally well known in the art, as illustrated by Wilgus German OLS No. 2,107,118; Irie U.S. Pat. No. 3,650,757; Kurz U.S. Pat. No. 3,672,900; Saito U.S. Pat. No. 4,242,445; Teitschied et al European Patent Application 80102242; xe2x80x9cGrowth Mechanism of AgBr Crystals in Gelatin Solutionxe2x80x9d, Photographic Science and Engineering, Vol. 21, No. 1, January/February 1977, p. 14, et seq. The term xe2x80x9ccritical crystal growth ratexe2x80x9d is used in the art to describe the growth rate obtained at the maximum rate of silver ion and halide ion addition which does not produce renucleation. While maintaining silver and halide addition rates below that which form new grain populations is advantageous during grain growth in terms of controlling the emulsion grain population characteristics, it also can restrict obtainable emulsion concentrations (i.e., batch yields) and lengthen emulsion manufacturing times.
U.S. Pat. Nos. 5,549,879; 6,043,019; 6,048,683 and 6,265,145 disclose double jet techniques for preparing silver halide grains wherein silver and halide salt solutions are added at a xe2x80x9cpulsed flowxe2x80x9d rate designed to generate a second grain population (i.e., at a rate above that which would provide for the critical crystal growth rate), with multiple short xe2x80x9cpulsesxe2x80x9d being separated by hold periods designed to allow the new grain population to be ripened out. U.S. Pat. No. 5,549,879, e.g., discloses introducing an aqueous silver nitrate solution from a remote source by a conduit which terminates close to an adjacent inlet zone of a mixing device, which is disclosed in greater detail in Research Disclosure, Vol. 382, February 1996, Item 38213. Simultaneously with the introduction of the aqueous silver nitrate solution and in an opposing direction, aqueous halide solution is introduced from a remote source by a conduit which terminates close to an adjacent inlet zone of the mixing device. The mixing device is vertically disposed in a reaction vessel and attached to the end of a shaft, driven at high speed by any suitable means. The lower end of the rotating mixing device is spaced up from the bottom of the vessel, but beneath the surface of the aqueous silver halide emulsion contained within the vessel. Baffles, sufficient in number to inhibit horizontal rotation of the contents of the vessel are located around the mixing device. The described apparatus is operated in a xe2x80x9cpulse flowxe2x80x9d manner comprising the steps of: (a) providing an aqueous solution containing silver halide particles having a first grain size; (b) continuously mixing the aqueous solution containing silver halide particles; (c) simultaneously introducing a soluble silver salt solution and a soluble halide salt solution into a reaction vessel of high velocity turbulent flow confined within the aqueous solution for a time t, wherein high is at least 1000 rpm; (d) simultaneously halting the introduction of the soluble silver salt solution and the soluble halide salt solution into the reaction for a time T wherein T greater than t, thereby allowing the silver halide particles to grow; and (e) repeating steps (c) and (d) until the silver halide particles attain a second grain size greater than the first grain size. Advantages of the pulse flow technique described include permitting easier scalability of the precipitation method. There is no disclosure of use of such pulse flow technique to enable larger emulsion concentrations (i.e., batch yields) or shorten emulsion manufacturing times. To the contrary, the disclosed need for relatively long hold times between pulsed addition of silver and halide salts can result in longer manufacturing times.
Jagannathan et al. U.S. Pat. No. 6,043,019 teaches the use of pulsed flow growth for high bromide tabular grain emulsion after a speed-enhancing amount of iodide is added to the reaction vessel. Such emulsions are more robust for chemical sensitization, have an improved speed-granularity relationship and they exhibit reduced intrinsic fog. Thus, pulsed growth appears to affect iodide incorporation in tabular grains in a beneficial way. There is no disclosure of use of such pulse flow technique to enable preparation of high bromide emulsion grains having desired performance characteristics while increasing emulsion concentrations (i.e., batch yields) or shorten emulsion manufacturing times. To the contrary, the pulsed addition of silver halide salts is described specifically for only the outer 5 to 50 percent (and more preferably for only the outer 5 to 30 percent) of silver forming the final tabular grain emulsion, and the pulses are separated by hold times. Further, there is no disclosure of use of the described process to prepare high bromide cubical emulsion grains.
Mehta et al. U.S. Pat. No. 6,048,683 teaches a pulse flow process for the preparation of high chloride cubical silver halide grains grown in the presence of a thioether ripening agent wherein the resulting silver chloride grains exhibit an average grain roundness coefficient, n, in the range of from 2 to less than 15. Mehta et al. U.S. Pat. No. 6,265,145 teaches a process for the preparation of high chloride cubical silver halide grains containing from 0.05 to 3 mole percent iodide where iodide is incorporated in the grains by introducing at least a silver salt solution into the dispersing medium at a rate such that the normalizing molar addition rate Rn is above 5xc3x9710xe2x88x922 minxe2x88x921 where Rn satisfies the formula       R    n    =                    Q        f                          C        f              M
where Qf is the volumetric rate of addition, in liters/min, of silver salt solution to the reaction vessel, Cf is the concentration, in moles/liter, of the silver salt solution, and M is the total moles of silver halide in the host grains in the reaction vessel at the precise moment of addition of the silver salt solution. There is no disclosure, however, of use of the above processes to prepare high bromide silver halide cubical grain emulsions.
In one aspect, this invention is directed to a process for the preparation of a radiation-sensitive silver halide emulsion comprised of high bromide cubical silver halide grains, the process comprising: (a) providing in a stirred reaction vessel a dispersing medium and high bromide silver halide seed grains, the seed grains comprising at least 5 mole % of the final emulsion silver, and (b) precipitating a silver halide shell which comprises at least 5 mole % of the final emulsion silver onto the seed grains by introducing at least a silver salt solution into the dispersing medium at a rate such that the normalized shell molar addition rate, Rs, is above 1.0xc3x9710xe2x88x923 minxe2x88x922, Rs satisfying the formula:       R    s    =            M      s                      M        t                          t        s        2
where Ms is the number of moles of silver halides added to the reaction vessel during the formation of the shell, ts is the run time, in minutes, of the silver salt solution for the formation of the shell, and Mt is total moles of silver halide in the reaction vessel at the end of the precipitation of the shell; wherein the concentration of silver halide grains in the reaction vessel at the end of the precipitation of the shell is at least 0.5 mole/L.
In another aspect, this invention is directed towards a high bromide cubic silver halide grain emulsion prepared in accordance with the above process, wherein the silver halide grains of the emulsion have an average cubic edge length of less than 0.4 micrometers and an average roundness index Q of less than 0.35.
In further aspects, this invention is directed towards a photographic element, and especially a radiographic recording element, comprising a support and at least one light sensitive silver halide emulsion layer comprising silver halide grains prepared as described above.
The invention provides an improved manufacturing process for the preparation of high bromide silver halide cubical grain emulsion enabling concentrated emulsion batches to be prepared with desired photographic properties. In certain embodiments of the invention, further advantages are enabled in accordance with the discovery that when the exterior portion of high bromide silver halide cubic grains are grown under specific conditions of high molar addition rates, emulsions of enhanced sensitivity, improved contrast and radiographic curve shape may be produced while controlling the minimum fog level.
High bromide cubical silver halide grains precipitated in accordance with the invention contain greater than 50 mole percent bromide, based on silver. Preferably the grains contain at least 70 mole percent bromide and, optimally at least 90 mole percent bromide, based on silver. The balance of the halide not accounted for by bromide can be chloride and/or iodide. Silver bromide and silver chloride are miscible in all proportions; hence, any portion of the total halide not accounted for bromide, can be chloride. While chloride ions may be incorporated in high bromide grain emulsions at high levels, in order to maintain sensitivity advantages associated with high bromide emulsion versus high chloride emulsions, chloride inclusions are preferably limited to up to 5 mole percent, based on silver. Incorporation of iodide into high bromide grains is limited by iodide solubility levels (e.g., approx. 40 mole % iodide in silver iodobromide grains). Iodide even at relatively low levels (e.g., 0.25 to 10 mole percent), however, is well know in the art to provide increases in speed and other effects. The method of the invention can be employed to prepare high bromide cubical grain emulsions of any conventional mean grain size known to be useful in photographic elements. Mean grain sizes in the range of from 0.15 to 2.5 xcexcm are typical, with mean grain sizes of less than 2 xcexcm, and more preferably less than 1 xcexcm, generally being preferred to provide improved granularity results in photographic elements employing such emulsions.
The method of the invention can be viewed as a modification of conventional methods for preparing high bromide cubical grain emulsions, wherein after formation of a host grain emulsion grain population a substantial portion of total silver of the emulsion (i.e., at least 5 mole percent, preferably at least 10 mole percent, more preferably at least 20 mole percent, at least 30 mole percent, or at least 40 mole percent, even more preferably greater than 50 mole percent, and most preferably at least 60 mole percent) is added to the reaction vessel in the form of a silver salt solution at a relatively high normalized shell molar addition rate. Any convenient conventional silver halide seed or host grain precipitation procedure may be employed to form the host grain population, which in accordance with the invention accounts for at least 5 mole percent (preferably at least 10 mole percent, more preferably at least 15 mole percent) of total silver of the final emulsion to be formed. The host grain emulsions can have any halide concentrations consistent with the general halide requirement for high bromide grains. While levels of iodide and/or chloride consistent with the overall composition requirements of the grains can be included within the host grains, in one specifically contemplated preferred form the host seed grain emulsion is an essentially pure silver bromide cubical grain emulsion. The host grains are preferably cubic, but can include other cubical forms, such as tetradecahedral forms. Techniques for forming emulsions satisfying the host grain requirements of the preparation process are well known in the art. The rate at which silver nitrate and sodium bromide (or other silver and halide sources) are added into the reactor during precipitation of the host grains can be at any practical molar addition rate. The initially formed seed grains then serve as hosts for further grain growth. While the host grains prepared by conventional methods may form from 5 to 95 mole percent of the final emulsion, it is preferred that the host grains account for at least 10 percent and up to 80 percent, and more preferably at least 15 percent and less than 50 percent, of total silver forming the emulsions produced by the invention.
Once a host grain population has been prepared which will account for at least 5 mole percent (preferably at least 10 percent, and more preferably at least 15 percent) of total silver of the final emulsion, silver salt solution is added at a high normalized shell molar addition rate (i.e., Rs greater than 1.0xc3x9710xe2x88x923 minxe2x88x922, preferably greater than or equal to 2.0xc3x9710xe2x88x923 minxe2x88x922) in accordance with the invention to create an outer shell comprising at least 5 mole percent (preferably at least 10 percent, more preferably at least 20 percent, and most preferably greater than 50 mole percent) of total silver of the final emulsion. Where the reaction vessel contains excess halide ions, the silver salt solution may be added by itself to precipitate the outer shell. It is preferred, however, to simultaneously introduce a halide salt solution into the dispersing medium with the silver salt solution. Bromide salt may be added as the halide salt, either alone or in combination with chloride or iodide salts consistent with the overall composition requirements of the grains to be formed. The concentration of silver halide grains in the reaction vessel at the end of the precipitation of the shell is at least 0.5 mole/L, preferably at least 0.8 mole/L and more preferably at least 1.0 mole/L.
At the conclusion of grain precipitation the grains can take varied cubical forms, ranging from cubic grains (bounded entirely by six {100} crystal faces), grains having an occasional identifiable {111} face in addition to six {100} crystal faces, and, at the opposite extreme tetradecahedral grains having six {100} and eight {111} crystal faces. Formation of cubic grains during grain growth, e.g., may be favored by controlling the relative silver and halide ion solution concentrations as well known in the art (e.g., maintaining pAg at 8.10 or less, preferably 7.80 or less and more preferably 7.60 or less). In accordance with a particular embodiment, the method of the invention has surprisingly been found to improve the xe2x80x9ccubicityxe2x80x9d of cubic emulsion grains, especially for finer grain emulsions, as demonstrated by the preparation of emulsions comprising cubic grains having a lower average roundness index. The method of the invention is thus preferably employed to prepare high bromide cubic grain emulsions comprising grains having an average cubic edge length of less than 0.4 micrometers (more preferably less than or equal to 0.35 micrometers and most preferably less than or equal to 0.33 micrometers) and an average roundness index Q of less than 0.35 (more preferably less than or equal to 0.32 and most preferably less than or equal to 0.30). Such high cubicity grain emulsions have been found to provide improvements with respect to higher contrast, lower fog, and higher maximum densities when employed in photographic elements, particularly for radiographic photographic elements designed for rapid access processing.
It is surprising that the grains comprising shells formed using high rates of reagents addition as required in accordance with the invention not only contribute to a more productive manufacturing process, but are also compatible with achieving higher levels of photosensitivity. After examining the performance of emulsions exhibiting varied cubical grain shapes, it has been concluded that the performance of the improved cubicity emulsions obtained in accordance with preferred embodiments of the invention is principally determined by an improvement in the uniformity of grain size dispersity and cubicity enabled by the process of the invention, relative to emulsions prepared at conventional rates of reagent addition. The high bromide cubical silver halide grains prepared in accordance with the invention preferably exhibit a grain size coefficient of variation of less than 35 percent and optimally less than 25 percent. Much lower grain size coefficients of variation can be realized, but progressively smaller incremental advantages are realized as dispersity is minimized.
The normalized shell molar addition rate in accordance with the invention is substantially higher than critical crystal growth rates typically determined in accordance with prior art techniques. While reagent addition rates only slightly greater than that which would be associated with such conventionally determined critical crystal growth rates are believed to simultaneously result in both renucleation and growth of the pre-existing seeds as well as the renucleated seeds, and thus a decrease in grain size uniformity (i.e., increase in polydispersity), it has been surprisingly found that where the normalized shell molar addition rate is further increased to levels in accordance with the invention substantially all of the added reagent is precipitated into fine grains which then ripen primarily only onto the larger pre-existing seed or host grains, resulting a relatively monodisperse emulsion.
In the simplest form of silver halide grain preparation in accordance with the invention, nucleation and growth stages may occur in the same reaction vessel. Two or more separate reaction vessels can be substituted for the single reaction vessel, however. Nucleation and initial growth of seed grains can be performed in an upstream reaction vessel, e.g., and the dispersed grain nuclei can be transferred to a downstream reaction vessel in which the subsequent shell growth step occurs. Arrangements which separate grain nucleation from grain growth, e.g., are disclosed by Mignot U.S. Pat. No. 4,334,012 (which also discloses the useful feature of ultrafiltration during grain growth); Urabe U.S. Pat. No. 4,879,208 and published European Patent Applications 326,852; 326,853; 355,535 and 370,116, Ichizo published European Patent Application 0 368 275; Urabe et al published European Patent Application 0 374 954; and Onishi et al published Japanese Patent Application (Kokai) 172,817-A (1990).
It is specifically contemplated to incorporate dopants into the silver halide emulsion grains of the invention during precipitation. The use of dopants in silver halide grains to modify photographic performance is generally illustrated by Research Disclosure, Item 38957, cited above, I. Emulsion grains and their preparation, D. Grain modifying conditions and adjustments, paragraphs (3)-(5). Photographic performance attributes known to be affected by dopants include sensitivity, reciprocity failure, and contrast.
Once high bromide cubical grains have been precipitated as described above, chemical and spectral sensitization, followed by the addition of conventional addenda to adapt the emulsion for the imaging application of choice can take any convenient conventional form. These conventional features are illustrated by Research Disclosure, Item 38957, cited above, particularly:
III. Emulsion washing;
IV. Chemical sensitization;
V. Spectral sensitization and desensitization;
VII. Antifoggants and stabilizers;
VIII. Absorbing and scattering materials;
IX. Coating and physical property modifying addenda; and
X. Dye image formers and modifiers.
Some additional silver halide, generally less than 5 percent and typically less than 1 percent, based on total silver, can be introduced to facilitate chemical sensitization. It is also recognized that silver halide can be epitaxially deposited at selected sites on a host grain to increase its sensitivity. For the purpose of providing a clear demarcation, the term xe2x80x9csilver halide grainxe2x80x9d is herein employed to include the silver necessary to form the grain up to the point that the final major {100} crystal faces of the grain are formed. Silver halide later deposited that does not overlie the major crystal faces previously formed accounting for at least 50 percent of the grain surface area is excluded in determining total silver forming the silver halide grains. Thus, silver forming selected site epitaxy is not part of the silver halide grains while silver halide that deposits and provides the final major crystal faces of the grains is included in the total silver forming the grains, even when it differs significantly in composition from the previously precipitated silver halide.
The emulsions of the invention may be chemically sensitized as known in the art. Preferred chemical sensitizers include gold and sulfur chemical sensitizers. Typical of suitable gold and sulfur sensitizers are those set forth in Section IV of Research Disclosure 38957, September 1996. Preferred is colloid aurous sulfide such as disclosed in Research Disclosure 37154 for good speed and low fog. It is also possible to add dopants during emulsion finishing.
The emulsions can be spectrally sensitized in any convenient conventional manner. Spectral sensitization and the selection of spectral sensitizing dyes is disclosed, for example, in Research Disclosure, Item 38957, cited above, Section V. Spectral sensitization and desensitization. The emulsions used in the invention can be spectrally sensitized with dyes from a variety of classes, including the polymethine dye class, which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-, tetra- and polynuclear cyanines and merocyanines), styryls, merostyryls, streptocyanines, hemicyanines, arylidenes, allopolar cyanines and enamine cyanines. Combinations of spectral sensitizing dyes can be used which result in supersensitizationxe2x80x94that is, spectral sensitization greater in some spectral region than that from any concentration of one of the dyes alone or that which would result from the additive effect of the dyes. Supersensitization can be achieved with selected combinations of spectral sensitizing dyes and other addenda such as stabilizers and antifoggants, development accelerators or inhibitors, coating aids, brighteners and antistatic agents. Any one of several mechanisms, as well as compounds which can be responsible for supersensitization, are discussed by Gilman, Photographic Science and Engineering, Vol. 18, 1974, pp. 418-430.
The silver bromide emulsions are preferably protected against changes in fog upon aging. Preferred antifoggants can be selected from among the following groups:
A. A mercapto heterocyclic nitrogen compound containing a mercapto group bonded to a carbon atom which is linked to an adjacent nitrogen atom in a heterocyclic ring system,
B. A quaternary aromatic chalcogenazolium salt wherein the chalcogen is sulfur, selenium or tellurium,
C. A triazole or tetrazole containing an ionizable hydrogen bonded to a nitrogen atom in a heterocyclic ring system, or
D. A dichalcogenide compound comprising an -X-X- linkage between carbon atoms wherein each X is divalent sulfur, selenium or tellurium.
The above groups of antifoggants are known in the art, and are described in more detail, e.g., in U.S. Pat. No. 5,792,601, the disclosure of which is incorporated by reference herein.
In the simplest contemplated form a recording element in accordance with the invention can consist of a single emulsion layer satisfying the emulsion description provided above coated on a conventional radiographic support, such as those described in Research Disclosure, Item 38957, cited above, XVI. Supports. With a single emulsion layer unit a monochromatic image is obtained. It is, of course, recognized that the elements of the invention can include more than one emulsion. Where more than one emulsion is employed, such as in an element containing a blended emulsion layer or separate emulsion layer units, all of the emulsions can be high bromide silver halide emulsions prepared as contemplated by this invention. Alternatively one or more conventionally prepared emulsions can be employed in combination with the emulsions of this invention. For example, a separate emulsion, such as a silver chloride or bromochloride emulsion, can be blended with an emulsion prepared according to the invention to satisfy specific imaging requirements. For example, emulsions of differing speed are conventionally blended to attain specific aim radiographic characteristics. Instead of blending emulsions, the same effect can usually be obtained by coating the emulsions that might be blended in separate layers. It is well known in the art that increased radiographic speed can be realized when faster and slower emulsions are coated in separate layers with the faster emulsion layer positioned to receiving exposing radiation first. When the slower emulsion layer is coated to receive exposing radiation first, the result is a higher contrast image. Specific illustrations are provided by Research Disclosure, Item 36544, cited above Section I. Emulsion grains and their preparation, Subsection E. Blends, layers and performance categories.
The emulsion layers as well as optional additional layers, such as overcoats and interlayers, contain processing solution permeable vehicles and vehicle modifying addenda. Typically these layer or layers contain a hydrophilic colloid, such as gelatin or a gelatin derivative, modified by the addition of a hardener. Illustrations of these types of materials are contained in Research Disclosure, Item 36544, previously cited, Section II. Vehicles, vehicle extenders, vehicle-like addenda and vehicle related addenda. The overcoat and other layers of the photographic element can usefully include an ultraviolet absorber, as illustrated by Research Disclosure, Item 36544, Section VI. UV dyes/optical brighteners/luminescent dyes, paragraph (1). The overcoat, when present can usefully contain matting agents to reduce surface adhesion. Surfactants are commonly added to the coated layers to facilitate coating. Plasticizers and lubricants are commonly added to facilitate the physical handling properties of the photographic elements. Antistatic agents are commonly added to reduce electrostatic discharge. Illustrations of surfactants, plasticizers, lubricants and matting agents are contained in Research Disclosure, Item 36544, previously cited, Section IX. Coating physical property modifying addenda.
A specific preferred application of the invention is in the preparation of high bromide emulsions for use in medical diagnostic imaging radiographic elements, particularly elements that are sensitive to IR radiation. A number of varied photographic film constructions have been developed to satisfy the needs of medical diagnostic imaging. The common characteristics of these films is that they (1) produce viewable silver images having maximum densities of at least 3.0 and (2) are designed for rapid access processing.
Roentgen discovered X-radiation by the inadvertent exposure of a silver halide photographic element. The discovery led to medical diagnostic imaging. In 1913, the Eastman Kodak Company introduced its first product specifically intended to be exposed by X-radiation. Shortly thereafter it was discovered that the films could be more efficiently employed in combination with one or two intensifying screens. An intensifying screen is relied upon to capture an image pattern of the X-radiation and emit light that exposes the radiographic element. Elements that rely entirely on X-radiation absorption for image capture are referred to as direct radiographic elements, while those that rely on intensifying screen light emission, are referred to as indirect radiographic elements. Silver halide radiographic elements, particularly indirect radiographic elements, account for the overwhelming majority of medical diagnostic images.
In recent years, a number of alternative approaches to medical diagnostic imaging, particularly image acquisition, have become prominent. Medical diagnostic devices such as storage phosphor screens, CAT scanners, magnetic resonance imagers (MRI), and ultrasound imagers allow information to be obtained and stored in digital form. Although digitally stored images can be viewed and manipulated on a cathode ray tube (CRT) monitor, a hard copy of the image is almost always needed.
The most common approach for creating a hard copy of a digitally stored image is to expose a radiation-sensitive silver halide film through a series of laterally offset exposures using a laser, a light-emitting diode (LED) or a light bar (a linear series of independently addressable LED""s). The image is recreated as a series of laterally offset pixels. Initially, the radiation-sensitive silver halide films were essentially the same films used for radiographic imaging, except that finer silver halide grains were substituted to minimize noise (granularity). The advantages of using modified radiographic films to provide a hard copy of the digitally stored image are that medical imaging centers are already equipped for rapid access processing of radiographic films and are familiar with their image characteristics.
Rapid access processing can be illustrated by reference to the Kodak X-OMAT 480 RA(trademark) rapid access processor, which employs the following (reference) processing cycle: development 24 seconds at 35xc2x0 C.; fixing 20 seconds at 35xc2x0 C.; washing 20 seconds at 35xc2x0 C.; drying 20 seconds at 65xc2x0 C.; with up to 6 seconds being taken up in film transport between processing steps.
A typical developer employed in this processor exhibits the following composition:
hydroquinone 30 g
1-phenyl-3-pyrazolidone 1.5 g
KOH 21 g
NaHCO3 7.5 g
K2 SO3 44.2 g
Na2S2 O3 12.6 g
NaBr 35.0 g
5-methylbenzotriazole 0.06 g
glutaraldehyde 4.9 g
water to 1 liter at a pH 10.
A typical fixer employed in this processor exhibits the following composition:
Na2 S2 O3 in water at 60% of total weight
in water 260.0 g
NaHSO3 180.0 g
boric acid 25.0 g
acetic acid 10.0 g
water to 1 liter at a pH of 3.9-4.5.
Numerous variations of the reference processing cycle (including, shorter processing times and varied developer and fixer compositions) are known.
Rapid access processors are typically activated when an imagewise exposed element is introduced for processing. Silver halide grains in the element interrupt an infrared sensor beam in the wavelength range of from 850 to 1100 nm, typically generated by a photodiode. The silver halide grains reduce density of infrared radiation reaching a photosensor, telling the processor that an element has been introduced for processing and starting the rapid access processing cycle. Once silver halide grains have been developed, developed silver provides the optical density necessary to interact with the infrared sensors. When the processed element emerges from the processor, an infrared sensor placed near the exit of the processor receives an uninterrupted infrared beam and shuts down the processor until another element is introduced requiring processing.
The performance of radiographic films designed for such rapid access processing can be improved with advancements in the precipitation process of the invention used to manufacture high bromide silver halide cubical grain emulsions. Each emulsion layer unit of such films can contain one, two, three or more separate emulsion layers sensitized to the same regions of the spectrum. When more than one emulsion layer is present in the same emulsion layer unit, the emulsion layers typically differ in speed. Typically interlayers containing oxidized developing agent scavengers, such as ballasted hydroquinones or aminophenols, are interposed between the emulsion layer units to avoid color contamination. Ultraviolet absorbers are also commonly coated over the emulsion layer units or in the interlayers.
Silver halide emulsions satisfying the grain requirements described above can be present in any one or combination of emulsion layer units in a radiographic film element, wherein such emulsion layer units are employed in any convenient conventional sequence. The advantages of the current invention may be achieved by modifying any or all of the emulsion formulations of such conventional sequences to conform to the requirements set forth in the specification. The exact magnitude of the benefits achieved will, of course, depend on the exact details of the formulations involved but these will be readily apparent to the skilled practitioner. It is specifically contemplated, e.g., that the process of the invention will be useful in preparing highly cubic high bromide emulsions for use in radiographic photographic elements intended for rapid processing such as described in U.S. Pat. No. 5,089,379 and 5,981,161, the disclosures of which are incorporated by reference herein, in combination with the various specific useful iodide contents, sensitizing dyes, surface active agents, azaindene compound and dopants such as described therein.
The following examples illustrate the practice of this invention. They are not intended to be exhaustive of all possible variations of the invention. Parts and percentages are by weight unless otherwise specified.

Process for the preparation of high bromide cubic grain emulsions

Abstract: where Ms is the number of moles of silver halides added to the reaction vessel during the formation of the shell, ts is the run time, in minutes, of the silver salt solution for the formation of the shell, and Mt is total moles of silver halide in the reaction vessel at the end of the precipitation of the shell; wherein the concentration of silver halide grains in the reaction vessel at the end of the precipitation of the shell is at least 0.5 mole/L. The invention provides an improved manufacturing process for the preparation of high bromide silver halide cubical grain emulsion enabling concentrated emulsion batches to be prepared with desired photographic properties. In certain embodiments of the invention, further advantages are enabled in accordance with the discovery that when the exterior portion of high bromide silver halide cubic grains are grown under specific conditions of high molar addition rates, emulsions of enhanced sensitivity, improved contrast and radiographic curve shape may be produced while controlling the minimum fog level.


A tool for the primary shaping of a housing for a sensor which is designed to capture, via a sensing element, a physical area that is dependent on a variable to be measured, and to emit an electrical output signal on the basis of the captured physical area, including: —a mold cavity for receiving a material that molds the housing, and the sensing element, and —a box having a wall that bounds the mold cavity, wherein at least a part of the wall that bounds the mold cavity is mounted in a displaceable manner.

WO 2010/037 810 A1, which is incorporated by reference discloses housing a measuring element of a sensor in a housing by means of an injection molding method, said measuring element being configured so as to ascertain by way of the measuring element a physical field that is dependent upon a variable that is to be measured, and to output an electrical output signal based upon the physical field that is ascertained.

Tool for the primary shaping of a housing for a sensor


The present technology relates to the field of medical monitoring. Patient monitoring systems and associated devices, methods, and computer readable media are described. In some embodiments, a patient monitoring system includes one or more sensors configured to capture first data related to a patient and a monitoring device configured to receive the first data. In these and other embodiments, the patient monitoring system can include an image capture device configured to capture second data related to the patient. In these and still other embodiments, the one or more sensors can be configured to instruct the patient monitoring system to display the second data.

Many conventional medical monitors require attachment of a sensor to a patient in order to detect physiologic signals from the patient and to transmit detected signals through a cable to the monitor. These monitors process the received signals and determine vital signs such as the patient's pulse rate, respiration rate, and arterial oxygen saturation. For example, a pulse oximeter is a finger sensor that can include two light emitters and a photodetector. The sensor emits light into the patient's finger and transmits the detected light signal to a monitor. The monitor includes a processor that processes the signal, determines vital signs (e.g., pulse rate, respiration rate, arterial oxygen saturation), and displays the vital signs on a display.
Other monitoring systems include other types of monitors and sensors, such as electroencephalogram (EEG) sensors, blood pressure cuffs, temperature probes, air flow measurement devices (e.g., spirometer), and others. Some wireless, wearable sensors have been developed, such as wireless EEG patches and wireless pulse oximetry sensors.
Video-based monitoring is a field of patient monitoring that uses one or more remote video cameras to detect physical attributes of the patient. This type of monitoring can also be called "non-contact" monitoring in reference to the remote video sensor(s), which does/do not contact the patient. The remainder of this disclosure offers solutions and improvements in this field.

Attached sensor activation of additionally-streamed physiological parameters from non-contact monitoring systems and associated devices, systems, and methods


A cooking protective food support that includes a plurality of raised portions and a plurality of lower portions supports food to be cooked and collects cooking food juices. The support retains the cooking food juices so the food is self-basted or rehydrated. Additionally, the support retains the cooking food juices to prevent flare-ups that often occur when the cooking food juices come in direct contact with the heat source. The food support is invertible so that cooking food juices on the surface that is not supporting the food are burned away by the heat source.

In respect to often pleasant party times centering around an outdoor dinnertime, when a barbecuing time is involved, there are unpleasant times, when, for example, food juices and liquid fats drip into the fire below to cause flare-ups which often burn the food. Or, unwanted odors arise from the heating of previous barbecuing time residues, or from starter fluids. Many times, the grill of a barbecue cooker has not been thoroughly cleaned, if cleaned at all, from a previous barbecuing time, and an unhealthy appearance and/or condition continues on into the follow on barbecuing time. Then, after the party is over, the grill and the interior of the barbecue cooker often need extensive cleaning. Such cleaning generally waits until the next day or later, increasing the effort required to remove the food and grease residues.
Although these drawbacks or inconveniences associated with barbecuing time continue to haunt persons today in respect to their barbecuing time, and there is a need for a product to be marketed more aggressively today to eliminate essentially all these drawbacks or inconveniences, there have been prior products offered by others, which, if made available could be utilized by persons during their barbecuing time. In reference to U.S. patents:
In 1868, William Andrew in his U.S. Pat. No. 75,107 disclosed his gridiron, which was a combined gridiron and frying pan used for broiling or frying food. Spaced ribs or bars supported the food, and gutters located between the ribs directed the gravy, i.e. food juices and liquid fats, into a collecting basin, keeping them clear of the fire;
In 1876, George Cornwall in his U.S. Pat. No. 181,823 disclosed his gridiron which served like William Andrew's gridiron, and had an improved gravy collecting basin positioned away from the main heat of the cooking fire;
In 1963, Arnold G. Keppler in his U.S. Pat. No. 3,113,505 illustrated and described his disposable broiling tray formed of very light gauge sheet material, such as lightweight aluminum. Food to be broiled was placed on this tray, which was corrugated, with the food resting atop the corrugations. During the broiling time in an oven, the grease rendered from the foods being broiled collected in the lower portions of the corrugations. Following the broiling time and food serving time, the lightweight broiling tray was disposed of, while still containing the grease. The ends of the corrugations were formed to provide portions which kept the grease in the corrugations;
In 1966, David D. Jordon in his U.S. Pat. No. 3,256,806, disclosed his expandable pan made of an aluminum sheet material preformed and compacted, and sold compacted for convenient storage in a kitchen. When expanded for use, Mr. Jordon's pan served in a like manner to Mr. Keppler's disposable broiling tray;
In 1970, Carl Karapetian in his U.S. Pat. No. 3,509,814 illustrated and disclosed his disposable barbeque grill in circular and rectangular embodiments made from thin metallic material. The food during the barbecuing period, was supported on an integral grid work. Adjacent integral indentations directed the food juices and liquid fats to the integral side walls, then to a surrounding integral rim for collection, until poured into a collecting can, via an integral pour spout. Mr. Karapetian in his patent, noted that earlier, Mr. Hoke in his U.S. Pat. No. 3,082,757 disclosed a cover to fit on a permanent grill, protecting portions thereof, but not all portions of the permanent grill, from being contacted by dripping food juices and liquid fats;
In 1983, Harold Osrow in his U.S. Pat. No. 4,394,410 illustrated and described his disposable foil broiling sheet. He provided a roll of these preformed, interconnected disposable foil broiling sheets for storage in a kitchen. When needed one sheet was removed and arranged in a planar configuration over a primary grill of an oven. The food, while being broiled, was supported above the primary grill while resting on the top surface areas of the top layer of the disposable foil broiling sheet. The food juices and liquid fats were directed to recessed surface areas and then down through drains into an internal layer made of an originally dry bibulous material for containment of these dripping liquids, as the surrounding bottom layer was made of an impermeable foil to complete the capture of the food juices and liquid fats.
These inventors and others have provided reusable and disposable products to be used by persons broiling foods in ovens, over permanent grills, and in barbecuing cookers, to collect all the food juices and liquid fats keeping them from reaching the heating source and/or surrounding structure, and collecting them for convenient removal and disposal. Yet, there remains a need for another try at providing a product which will be used more extensively by persons preparing foods during broiling in oven times, barbecuing times, and/or camping times, which is lightweight, low cost, nestable, keepable, or disposable, depending on the selected embodiment, and which may have other features making its use more desirable.


An operation of a processor in respect to transactions is checked by simulating an execution of a test program, and updating a transaction order graph to identify a cycle. The graph is updated based on a value read during an execution of a first transaction and a second transaction that is the configured to set the memory with the read value. The test program comprises information useful for identifying the second transaction.

The present disclosure relates to processor verification in general, and to checking of a simulated execution of a processor for correct execution of transactions, in particular.
Computerized devices control almost every aspect of our life from writing documents to controlling traffic lights. However, computerized devices are bug-prone, and thus require a testing phase in which the bugs should be discovered. The testing phase is considered one of the most difficult tasks in designing a computerized device.
The cost of a bug may be enormous, as its consequences may be disastrous. For example, a bug may cause the injury of a person relying on the designated behavior of the computerized device. Additionally, a bug in hardware or firmware may be expensive to fix, as patching it requires call-back of the computerized device. Hence, many developers of computerized devices invest a substantial portion, such as 70%, of the development cycle to discover erroneous behaviors of the computerized device.
Correctness of a functionality of a processor, or similar electronic circuit or computing device, may be verified. The verification process may be performed based upon a description of the processor, such as provided using a descriptive language such as for example VHDL, Verilog, SystemC or the like. In order to verify the processor, a test program may be generated by a test generator and a simulator, configured to simulate an execution of the processor, also referred to as the target processor, based on the functionality described using the descriptive language, in respect to the test program. Correctness of the simulated execution may be checked in order to detect bugs in the processor. In some cases, several test programs may be generated. Each test program may be executed more than once.
Some processor design includes support for transactional memory model. A transaction is a construct in the machine language that can be used by parallel applications when a number of processes access a shared resource. Instructions of a transaction appear to be performed atomically. The instructions, performed by a processing entity of the processor, such as a hardware thread, a core or the like, are performed without any observable collisions with any memory access performed by other processing entities.
Some processors further require a serializability property of the transactions. The serializability property requires that an order between transactions be the same for all processing entities of the processor. In some exemplary embodiments, in case a first order between transactions, as observed by a first processing entity of the processor, is different than a second order between transactions, as observed by a second processing entity of the processor, the processor may be considered as not holding the serializability property.

Verifying correctness of processor transactions

International Business Machines Corporation