A reversibly thermochromic light-transmitting laminate member which has a satisfactory thermochromic function and undergoes alternate color changes between a colorless transparent state and a colored transparent state.

The present invention relates to a reversibly thermochromic light-transmitting laminate member. More particularly, the invention relates to a reversibly thermochromic light-transmitting laminate member comprising a substrate and a reversibly thermochromic layer formed thereon, which undergoes alternate color changes between a colorless transparent state and a colored transparent state with temperature.
A laminate member which undergoes alternate color changes between a colorless transparent state and a colored transparent state with temperature is disclosed in U.S. Pat. No. 5,721,059. This laminate member comprises a substrate and formed thereon a reversibly thermochromic layer comprising a vinyl chloride/vinyl acetate copolymer resin matrix and dispersed therein a reversibly thermochromic composition comprising (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium determining the temperatures at which the color reactions of component (a) with component (b) take place.
The thermochromic composition contained in the reversibly thermochromic layer is not encapsulated, i.e., of the so-called non-capsule type. Because of this, not only the thermochromic layer has a factor contributing to chemical instability, but also the substrate is limited in material. With respect to thermochromic properties, the laminate member has such color-memorizing properties that it is wide hysteretic and memorizes and retains a color-changed state resulting from a temperature change.
Furthermore, a composition which contains a microencapsulated pigment containing a reversibly thermochromic composition and has excellent transparency in a decolored state is disclosed in JP-A-3-290467 (the term xe2x80x9cJP-Axe2x80x9d as used herein means an unexamined published Japanese patent application). This composition is a thermochromic resin composition containing a microencapsulated pigment which has a particle diameter of 1 xcexcm or smaller and which itself has light transmission.
This resin composition is intended to have transparency imparted thereto by the light transmission of the pigment itself. However, the small capsule particle diameter may cause troubles concerning thermochromic function, e.g., difficulties in determining a color change temperature.
An aim of the invention is to eliminate the disadvantages of the reversibly thermochromic laminate member which undergoes alternate color changes between a colorless transparent state and a colored transparent state. Namely, the aim is to provide a reversibly thermochromic light-transmitting laminate member which has a satisfactory thermochromic function and is free from the factor contributing to chemical instability inherent in the system employing a non-capsule type reversibly thermochromic composition.
The invention provides a reversibly thermochromic light-transmitting laminate member which comprises a substrate and formed thereon a reversibly thermochromic layer comprising a transparent resin and fixedly dispersed therein a reversibly thermochromic microencapsulated pigment containing a reversibly thermochromic composition comprising (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium determining the temperatures at which the color reactions of component (a) with component (b) take place, the reversibly thermochromic microencapsulated pigment being a deformable pigment which has an average particle diameter of from 1.0 to 5.0 xcexcm, the transparent resin having a tensile elongation at break of 400% or higher. In the laminate member of the invention, the proportion of the reversibly thermochromic microencapsulated pigment to the transparent resin is preferably from 1/0.5 to 1/20 (in terms of weight ratio on a solid basis) and the reversibly thermochromic layer preferably has a thickness of from 1 to 100 xcexcm. Furthermore, the transparent resin is preferably a resin selected from the group consisting of ethylene/vinyl acetate copolymer resins, polyurethane resins, and polyamide resins. In one embodiment of the invention, the laminate member has, formed over the reversibly thermochromic layer, a metallic glossy layer containing a metallic luster pigment having transparency. This metallic glossy layer preferably has a light transmittance of 5% or higher.
The laminate member of the invention, which undergoes alternate color changes between a colorless transparent state and a colored transparent state with temperature, is obtained based on a combination of a reversibly thermochromic microencapsulated pigment having an average particle diameter of from 1.0 to 5.0 xcexcm with a transparent resin having a tensile elongation at break of 400% or higher, as stated above.
More particularly, the reversibly thermochromic layer comprising a combination of a microencapsulated pigment having an average particle diameter of from 1.0 to 5.0 xcexcm with a transparent resin having a tensile elongation at break of 400% or higher is presumed to undergo the following phenomena.
The microencapsulated pigment has different capsule shapes depending on whether the reversibly thermochromic composition contained therein is in a solid state, i.e., a colored state, or is in a dissolved state, i.e., a decolored state. Specifically, when the encapsulated composition is in a dissolved state (decolored state), then the capsules have a degree of freedom and are deformable because the reversibly thermochromic composition is liquid. However, when the encapsulated composition is in a solid state (colored state), the capsules have recesses in the surface thereof, which were formed upon solidification of the reversibly thermochromic composition, and are hard and less apt to be deformed.
On the other hand, the transparent resin used in the invention has an elongation as high as 400% or above and is capable of conforming to capsule shape changes with temperature. Namely, at any time when the capsules change in shape with temperature, the resin surrounding the capsules is capable of deforming so as to conform to the capsule shapes. As a result, formation of spaces between the capsule surface and the resin is inhibited and a bleaching phenomenon can be prevented. Consequently, the reversibly thermochromic layer can undergo alternate color changes between a colorless transparent state and a colored transparent state with temperature over long without impairing the light transmission of the microencapsulated pigment.
Requirements for enabling the color changes to occur include the particle diameter of the capsules which is regulated to 1.0 to 5.0 xcexcm. The reasons for this are as follows. In case where the particle diameter of the capsules is smaller than 1.0 xcexcm, not only satisfactory thermochromic properties cannot be obtained, but also such capsules should have a reduced wall thickness and hence have poor durability in secondary processing, making it difficult to satisfy suitability for practical use. In case where the particle diameter thereof exceeds 5.0 xcexcm, the microencapsulated pigment itself has reduced light transmission and, hence, the reversibly thermochromic layer in a colored state has reduced light transmission. The particle diameter of the capsules is preferably from 1.0 to 3.0 xcexcm, more preferably from 1.0 to 2.0 xcexcm. Use of such capsules enables the reversibly thermochromic layer to show transparency and a sufficient color density in a colored state, be reduced in a residual color in a decolored state, and have excellent sharpness in color change. Namely, the reversibly thermochromic layer can have an excellent balance among thermochromic functions.
The proportion of the microencapsulated pigment to the transparent resin in terms of weight ratio on a solid basis is preferably from 1/0.5 to 1/20, more preferably from 1/1 to 1/10. The thickness of the reversibly thermochromic layer is preferably from 1 to 100 xcexcm, more preferably from 10 to 80 xcexcm. In case where the proportion of the microencapsulated pigment to the transparent resin in terms of weight ratio on a solid basis exceeds 1/0.5, transparency is reduced and the reversibly thermochromic coating layer has a reduced strength. In case where the proportion thereof is lower than 1/20, i.e., the proportion of the transparent resin exceeds the upper limit, then an excessively large film thickness is necessary for obtaining a satisfactory color density and this leads to insufficient drying and to problems concerning coating period, etc. Thus, such too high proportions of the transparent resin are unsuitable for practical use.
Thicknesses of the reversibly thermochromic layer smaller than 1 xcexcm result in difficulties in obtaining a satisfactory color tone in a colored state. On the other hand, thicknesses thereof exceeding 100 xcexcm may impair the transparency of the layer.
The reversibly thermochromic composition comprises three ingredients, i.e., (a) an electron-donating compound, (b) an electron-accepting compound, and (c) a reaction medium determining the temperatures at which the color reactions between components (a) and (b) take place. As this composition can be used, for example, the compositions proposed by the applicant which are disclosed in U.S. Pat. Nos. 4,028,118 and 4,732,810.
This composition changes in color at a given temperature (color change point) in such a manner that the composition is in a decolored state at temperatures not lower than the color change point and is in a colored state at temperatures lower than the color change point. At ordinary temperature, the composition exists only in specific one of the two states. Namely, the other state is maintained only during the period in which heat or cold required for the development of this state is kept being applied, and the composition returns to the original ordinary-temperature state upon removal of the heat or cold. This composition is a reversibly thermochromic composition of the heating decoloration type which shows such a thermochromic behavior in which the hysteresis range is relatively narrow.
Also usable is the thermochromic composition which is disclosed in U.S. Pat. No. 4,720,301. This composition shows enhanced hysteresis. Namely, plotting the color density against temperature gives a curve showing that the composition changes in color along routes which differ considerably between the case where the composition is heated from a temperature on the lower-temperature side of the color change temperature range and in the reverse case where the composition is cooled from a temperature on the higher-temperature side of the color change temperature range. This composition is a thermochromic color-memorizing composition of the heating decoloration type in which the colored state in the range of temperatures not higher than the lower color change point and the decolored state in the range of temperatures not lower than the higher color change point can be alternately memorized and retained even after the heat or cold required for the color change has been removed.
Furthermore, a reversibly thermochromic composition of the heating coloration type can also be used which contains as an electron-accepting compound (b) a specific alkoxyphenol compound having a linear or branched alkyl group having 3 to 18 carbon atoms.
The reversibly thermochromic composition is microencapsulated and used as a microencapsulated pigment. This microencapsulation enables the composition to develop a bright color having a high density and satisfy practical properties such as homogeneity, dispersion stability, chemical resistance, and heat resistance.
For the microencapsulation, known techniques can be used. Examples thereof include interfacial polymerization, in-situ polymerization, in-liquid curing coating, phase separation from an aqueous solution, phase separation from an organic solvent, melt dispersion cooling, air-suspension coating, and spray drying.
Before the microencapsulated pigment is subjected to practical use, the surface properties of the microcapsules may be modified according to purposes.
The microencapsulated pigment is dispersed into a medium containing the transparent resin to prepare a coloring material such as an ink or coating composition. This coloring material is applied to a substrate to thereby form a reversibly thermochromic layer.
Adding a non-thermochromic dye or pigment enables a color change from a colored transparent state (1) to another colored transparent state (2).
For forming the thermochromic layer, known techniques can be used. Examples thereof include printing techniques such as screen printing, offset printing, gravure printing, coater printing, tampon printing, and transfer printing and coating techniques such as brush coating, spray coating, electrostatic coating, electrodeposition, curtain coating, roller coating, and dip coating.
Examples of the material of the substrate include papers, synthetic papers, artificial leathers, natural leathers, plastics, glasses, porcelains and pottery, woods, stones, and metals.
The substrate may have a flat shape or may have recesses and protrusions.
Since the reversibly thermochromic layer of the laminate member of the invention undergoes alternate color changes between a colorless transparent state and a colored transparent state with temperature, it is preferred that the substrate be made of a transparent material. This is because in the laminate member employing a transparent substrate, the condition on the opposite side of the substrate can be perceived regardless of whether the thermochromic layer is in a colorless transparent state or a colored transparent state. This laminate member can be applied, for example, to a reversibly thermochromic three-dimensional object comprising a three-dimensional substrate made of a transparent resin, the reversibly thermochromic layer formed on the substrate, and an appropriate shaped article enclosed in the three-dimensional substrate. In this reversibly thermochromic object, not only the shaped article placed inside can be always perceived but also the thermochromic object can have such unexpected color-changing properties that the reversibly thermochromic layer undergoes color changes with temperature.
Examples of the shaped article include dolls and toys modeled on, e.g., animals, vehicles, buildings, plants, foods, or stones.
The shaped article enclosed in the three-dimensional object is preferably in close contact with the three-dimensional object. Namely, the reversibly thermochromic three-dimensional object preferably has such a constitution that it has no space at the interface between the outer surface of the shaped article and the three-dimensional object. This is because the absence of spaces enables the shaped article to be clearly perceived.
The substrate may be one having an optical property selected from iridescence, suitability for use as a hologram-recording material, metallic luster, pearlescence, and fluorescence. In this constitution, not only the optical property can be always perceived but also the layered object can have such unexpected color-changing properties that the reversibly thermochromic layer undergoes color changes with temperature.
Examples of materials having those optical properties include: a film bearing an optical interference pattern and comprising one or more of oxides, sulfides, and fluorides; an iridescent, transparent, multilayer film causing light interference which has a hundred or more interlayers made of two or more polymers differing in refractive index; a hologram film formed by pressing a hologram master bearing a hologram against any of various resins to obtain an embossed film and then vapor-depositing a metal such as Al, Cr, Ni, Sn, Fe, Co, Cu, Pb, Sb, Mg, Cd, or Bi on the embossed resin layer in a thickness of from 200 to 2,000 xc3x85; metal pieces; and materials obtained by suitably adhering a metal foil or a pearlescent pigment, e.g., a mica coated with titanium dioxide, mica coated with iron oxide and titanium dioxide, mica coated with iron oxide, guanine, sericite, basic lead carbonate, acid lead arsenate, or bithmuth oxychloride, to a surface of a support.
The metallic glossy layer which may be formed on the reversibly thermochromic layer will be explained next.
The metallic glossy layer is a layer comprising a binder resin and, fixedly dispersed therein, a metallic luster pigment based on a transparent material, as a core material, selected from natural micas, synthetic micas, flat pieces of glasses, and flaky aluminum oxide.
The metallic glossy layer not only imparts any of various colors with a metallic luster to the reversibly thermochromic layer, but also functions as a light-shielding layer. Namely, due to its light-absorbing (or light-reflecting) function and light-shielding function, the metallic glossy layer absorbs or reflects at least part of ultraviolet and visible rays, which may adversely influence the functions of the reversibly thermochromic layer. Thus, the metallic glossy layer further has the effect of improving the light resistance of the reversibly thermochromic layer.
Effective metallic luster pigments based on a natural mica as a core material include one obtained by coating the surface of natural-mica particles with titanium oxide, one obtained by coating the surface of natural-mica particles with titanium oxide and then further coating the coated particles with iron oxide, and one obtained by coating the surface of natural-mica particles with titanium oxide and then further coating the coated particles with a non-thermochromic dye or pigment (preferably in an amount of from 0.5 to 10% by weight). Specific examples thereof include: a gold metallic luster pigment having a particle size of from 5 to 50 xcexcm obtained by coating the surface of a natural mica with 41 to 44% by weight titanium oxide; a gold metallic luster pigment having a particle size of from 5 to 60 xcexcm obtained by coating the surface of a natural mica with 30 to 38% by weight titanium oxide and further coating the coated particles with 0.5 to 10% by weight non-thermochromic color pigment; a silver metallic luster pigment having a particle size of from 5 to 100 xcexcm obtained by coating the surface of a natural mica with 16 to 39% by weight titanium oxide; a metallic luster pigment obtained by coating the surface of a natural mica with 45 to 58% by weight titanium oxide; and a metallic luster pigment obtained by coating the surface of a natural mica with 45 to 58% by weight titanium oxide and then further coating the coated particles with 0.5 to 10% by weight non-thermochromic color dye or pigment. The xe2x80x9c% by weightxe2x80x9d used above is based on the total weight of the metallic luster pigment.
Metallic luster pigments based on a synthetic mica as a core material have a lower impurity content and a lower content of iron and other metal ions, which are a coloring factor, as compared with the metallic luster pigments based on a natural mica. Because of this, the pigments based on a synthetic mica have excellent transparency and is highly lustrous and glittering. Effective examples thereof include a pigment which is obtained by coating the surface of a synthetic mica with one or more metal oxides comprising titanium oxide as the main component and has an average particle thickness of from 0.1 to 5 xcexcm and an average particle diameter of from 2 to 1,000 xcexcm. This pigment has a metallic luster of a gold, silver, or another color depending on the degree of coating with the metal oxides. It is so transparent that the color tone of the underlying reversibly thermochromic layer can be clearly perceived.
Examples of the synthetic mica include ones represented by the following formula. One example is KMg3(AlSi3O10)F2.
X1/3xe2x88x921Y2xe2x88x923Z4O10F2xe2x80x83xe2x80x83(1)
(In formula (1), X represents Na+, Li+, K+, Ca2+, Sr2+, or Ba2+; Y represents one or more members selected from Mg2+, Li+, Ni2+, Co2+, Zn2+, Mn2+, Al3+, Cr3+, and Ti3+; and Z represents one or more members selected from Al3+, Si4+, Ge4+, and B3+.)
The shape of the mica is not particularly limited, and examples thereof include flat shapes and flaky shapes.
Examples of the metal oxides with which the surface of the synthetic mica is coated include oxides of metals such as titanium, zirconium, chromium, vanadium, and iron. However, it is preferred to use one or more metal oxides comprising titanium oxide as the main component.
The metallic luster pigments based on a synthetic mica as a core material are effective when the average particle thickness thereof is generally from 0.1 to 5 xcexcm and the average particle diameter thereof is generally from 2 to 1,000 xcexcm, preferably from 2 to 500 xcexcm, more preferably from 2 to 200 xcexcm. This average particle diameter means the average particle diameter which is determined by laser diffractometry and is the particle diameter corresponding to the 50% point in a cumulative median diameter distribution on a volume basis.
Specific examples of the metallic luster pigments comprising a synthetic mica whose surface is coated with a metal oxide include xe2x80x9cUltimicaxe2x80x9d (trade name) SB-100 (5-30 xcexcm; silver), SD-100 (10-60 xcexcm; silver), SE-100 (15-100 xcexcm; silver), SF-100 (44-150 xcexcm; silver), SH-100 (150-600 xcexcm; silver), YB-100 (5-30 xcexcm; gold), YD-100 (10-60 xcexcm; gold), YE-100 (15-100 xcexcm; gold), YF-100 (44-150 xcexcm; gold), RB-100 (5-300 xcexcm; metallic red), RD-100 (10-60 xcexcm; metallic red), RE-100 (15-100 xcexcm; metallic red), RF-100 (44-150 xcexcm; metallic red), RBB-100 (5-30 xcexcm; metallic purple), RBD-100 (10-60 xcexcm; metallic purple), RBE-100 (15-100 xcexcm; metallic purple), RBF-100 (44-150 xcexcm; metallic purple), VB-100 (5-30 xcexcm; metallic violet), VD-100 (10-60 xcexcm; metallic violet), VE-100 (15-100 xcexcm; metallic violet), VF-100 (44-150 xcexcm; metallic violet), BB-100 (5-30 xcexcm; metallic blue), BD-100 (10-60 xcexcm; metallic blue), BE-100 (15-100 xcexcm; metallic blue), BF-100 (44-150 xcexcm; metallic blue), GB-100 (5-30 xcexcm; metallic green), GD-100 (10-60 xcexcm; metallic green), GE-100 (15-100 xcexcm; metallic green), and GF-100 (44-150 xcexcm; metallic green), all manufactured by Nihon Kokenkogyo K.K.
Examples of the metallic luster pigments obtained by coating the surface of flat glass pieces as a core material with titanium oxide include such metallic luster pigments which have a gold, silver, or another metallic color depending on the degree of coating with titanium oxide. Specific examples thereof include the pigments obtained by coating glass flakes with titanium oxide which are manufactured by Nippon Sheet Glass Co., Ltd. and sold under the trade name of xe2x80x9cMetashinexe2x80x9d RCFSX-5450TS(6041) (average thickness, 5xc2x12 xcexcm; average particle size, 450xc2x1145 xcexcm; gold), RCFSX-5200TS(6042) (average thickness, 5xc2x12 xcexcm; average particle size, 200xc2x170 xcexcm; silver), RCFSX-5140TS(6043) (average thickness, 5xc2x12 xcexcm; average particle size, 140xc2x145 xcexcm; silver), RCFSX-5080TS(6044) (average thickness, 5xc2x12 xcexcm; average particle size, 80xc2x130 xcexcm; silver), RCFSX-2080TS(6046) (average thickness, 2xc2x11 xcexcm; average particle size, 80xc2x130 xcexcm; silver), RCFSX-K120TS(6043) (average thickness, 20xc2x15 xcexcm; average particle size, 120xc2x120 xcexcm; silver), RCFSX-5090RC(8052) (average thickness, 5xc2x12 xcexcm; average particle size, 90xc2x130 xcexcm; gold), RCFSX-5090RC(8053) (average thickness, 5xc2x12 xcexcm; average particle size, 90xc2x130 xcexcm; metallic green), RCFSX-5090RC(8069) (average thickness, 5xc2x12 xcexcm; average particle size, 90xc2x130 xcexcm; metallic blue), RCFSX-5090RC(8070) (average thickness, 5xc2x12 xcexcm; average particle size, 90xc2x130 xcexcm; metallic purple), RCFSX-5090RC(8071) (average thickness, 5xc2x12 xcexcm; average particle size, 90xc2x130 xcexcm; metallic red), RCFSX-1040RC(9543) (average thickness, 1 xcexcm; average particle size, 40 xcexcm; silver), RCFSX-1040RC(9544) (average thickness, 1 xcexcm; average particle size, 40 xcexcm; gold), RCFSX-1040RC(9546) (average thickness, 1 xcexcm; average particle size, 40 xcexcm; metallic red), RCFSX-1040RC(9548) (average thickness, 1 xcexcm; average particle size, 40 xcexcm; metallic blue), RCFSX-1040RC(9549) (average thickness, 1xcexcm; average particle size, 40 xcexcm; metallic green), RCFSX-1020RC(9550) (average thickness, 1 xcexcm; average particle size, 20 xcexcm; silver), RCFSX-1020RC(9551) (average thickness, 1 xcexcm; average particle size, 20 xcexcm, gold), RCFSX-1020RC(9553) (average thickness, 1 xcexcm; average particle size, 20 xcexcm; metallic red), and RCFSX-1020RC(9555) (average thickness, 1 xcexcm; average particle size, 20 xcexcm; metallic blue).
The metallic luster pigments obtained by coating the surface of flaky aluminum oxide as a core material with a metal oxide will be explained below.
Because the core material is flaky aluminum oxide, this kind of metallic luster pigment has a lower impurity content and is more lustrous than the pigments based on a natural mica.
Examples of the metal oxide with which the surface of the aluminum oxide is coated include oxides of metals such as titanium, zirconium, chromium, vanadium, and iron. However, it is preferred to use one or more metal oxides comprising titanium oxide as the main component. Examples of the metallic luster pigments include ones which have a gold, silver, or another metallic color depending on the degree of coating with the metal oxide.
These metallic luster pigments preferably have an average thickness of from 0.1 to 5 xcexcm and an average particle diameter of from 2 to 200 xcexcm.
By using a metallic luster pigment having a thickness and average particle diameter within the respective ranges shown above, it is possible to obtain a metallic glossy image which is evenly lustrous and a thermochromic image undergoing distinct color changes. This average particle diameter means the average particle diameter which is determined by laser diffractometry and is the particle diameter corresponding to the 50% point in a cumulative median diameter distribution on a volume basis.
Specific examples of the metallic luster pigments obtained by coating the surface of flaky aluminum oxide with a metal oxide include the pigment manufactured by Merck and Co., Inc. and sold under the trade name of xe2x80x9cXirallicxe2x80x9d T50-10 (10-30 xcexcm; silver).
The metallic luster pigments obtained by coating a core material selected from natural micas, synthetic micas, flat pieces of glasses, and flaky aluminum oxide with a metal oxide have transparency as well as a metallic luster. Of these metallic luster pigments, those obtained by coating a core material selected from synthetic micas, flat pieces of glasses, and flaky aluminum oxide with a metal oxide are suitable for use in the invention because they are superior in transparency.
The metallic glossy layer in the invention has a light transmittance of preferably 5% or higher, more preferably 10% or higher.
Such a light transmittance produces the following effect. When the reversibly thermochromic layer is in a colored state, the metallic glossy layer is transparent and a metallic lustrous color is perceived. When the reversibly thermochromic layer is in a decolored state, no metallic lustrous color is perceived and the metallic glossy layer shows excellent transparency.
In the case where the substrate has transparency, an article placed on the back side of the laminate member can be clearly perceived through the laminate member when the light transmittance of the laminate member itself is 3% or higher or 5% or higher at the time when the reversibly thermochromic layer is in a colored state or in a decolored state, respectively.
In producing the reversibly thermochromic light-transmitting laminate member of the invention, a reversibly thermochromic ink is suitably applied to a substrate. The ink comprises a reversibly thermochromic microencapsulated pigment containing a reversibly thermochromic composition comprising (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium determining the temperatures at which the color reactions of component (a) with component (b) take place and a vehicle containing a transparent resin having a tensile elongation at break of 400% or higher. The resultant coating is dried to form a reversibly thermochromic layer, whereby the laminate member of the invention is obtained.
In the case where a metallic glossy layer is to be formed on the reversibly thermochromic layer, a metallic luster ink comprising a vehicle containing a metallic luster pigment is applied to the thermochromic layer to form the metallic glossy layer.

Reversibly thermochromic light-transmitting laminate member


A substrate processing system has a housing that defines a process chamber, a gas-delivery system, a high-density plasma generating system, a substrate holder, and a controller. The housing includes a sidewall and a dome positioned above the sidewall. The dome has physically separated and noncontiguous pieces. The gas-delivery system introduces e a gas into the process chamber through side nozzles positioned between two of the physically separated and noncontiguous pieces of the dome. The high-density plasma generating system is operatively coupled with the process chamber. The substrate holder is disposed within the process chamber and supports a substrate during substrate processing. The controller controls the gas-delivery system and the high-density plasma generating system.

One of the primary steps in the fabrication of modern semiconductor devices is the formation of a film, such as a silicon oxide film, on a semiconductor substrate. Silicon oxide is widely used as an insulating layer in the manufacture of semiconductor devices. As is well known, a silicon oxide film can be deposited by a thermal chemical-vapor deposition ("CVD") process or by a plasma-enhanced chemical-vapor deposition ("PECVD") process. In a conventional thermal CVD process, reactive gases are supplied to a surface of the substrate, where heat-induced chemical reactions take place to produce a desired film. In a conventional plasma-deposition process, a controlled plasma is formed to decompose and/or energize reactive species to produce the desired film.
Semiconductor device geometries have decreased significantly in size since such devices were first introduced several decades ago, and continue to be reduced in size. This continuing reduction in the scale of device geometry has resulted in a dramatic increase in the density of circuit elements and interconnections formed in integrated circuits fabricated on a semiconductor substrate. One persistent challenge faced by semiconductor manufacturers in the design and fabrication of such densely packed integrated circuits is the desire to prevent spurious interactions between circuit elements, a goal that has required ongoing innovation as geometry scales continue to decrease.
Unwanted interactions are typically prevented by providing spaces between adjacent elements that are filled with an electrically insulative material to isolate the elements both physically and electrically. Such spaces are sometimes referred to herein as "gaps" or "trenches," and the processes for filling such spaces are commonly referred to in the art as "gapfill" processes. The ability of a given process to produce a film that completely fills such gaps is thus often referred to as the "gapfill ability" of the process, with the film described as a "gapfill layer" or "gapfill film." As circuit densities increase with smaller feature sizes, the widths of these gaps decrease, resulting in an increase in their aspect ratio, which is defined by the ratio of the gap's height to its depth. High-aspect-ratio gaps are difficult to fill completely using conventional CVD techniques, which tend to have relatively poor gapfill abilities. One family of electrically insulating films that is commonly used to fill gaps in intermetal dielectric ("IMD") applications, premetal dielectric ("PMD") applications, and shallow-trench-isolation ("STI") applications, among others, is silicon oxide (sometimes also referred to as "silica glass" or "silicate glass").
Some integrated circuit manufacturers have turned to the use of high-density plasma CVD ("HDP-CVD") systems in depositing silicon oxide gapfill layers. Such systems form a plasma that has a density greater than about 1011 ions/cm3, which is about two orders of magnitude greater than the plasma density provided by a standard capacitively coupled plasma CVD system. Inductively coupled plasma ("ICP") systems are examples of HDP-CVD systems. One factor that allows films deposited by such HDP-CVD techniques to have improved gapfill characteristics is the occurrence of sputtering simultaneous with deposition of material. Sputtering is a mechanical process by which material is ejected by impact, and is promoted by the high ionic density of the plasma in HDP-CVD processes. The sputtering component of HDP deposition thus slows deposition on certain features, such as the corners of raised surfaces, thereby contributing to the increased gapfill ability.
Even with the use of HDP and ICP processes, there remain a number of persistent challenges in achieving desired deposition properties. These include the need to manage thermal characteristics of the plasma within a processing chamber, particularly with high-energy processes that may result in temperatures that damage structures in the chamber. In addition, there is a general desire to provide deposition processes that are uniform across a wafer. Nonuniformities lead to inconsistencies in device performance and may result from a number of different factors. The deposition characteristics at different points over a wafer result from a complex interplay of a number of different effects. For example, the way in which gas is introduced into the chamber, the level of power used to ionize precursor species, the use of electrical fields to direct ions, and the like, may ultimately affect the uniformity of deposition characteristics across a wafer. In addition, the way in which these effects are manifested may depend on the physical shape and size of the chamber, such as by providing different diffusive effects that affect the distribution of ions in the chamber.
There is accordingly a general need in the art for improved systems for improving deposition uniformity across a wafer in HDP and ICP processes.

Two-piece dome with separate RF coils for inductively coupled plasma reactors


The instant invention is related to a novel solid form of ceftolozane sulfate (the DMAc solvate of ceftolozane sulfate (Form 3)), compositions comprising ceftolozane sulfate DMAc solvate (Form 3), synthesis of Form 3 and an improved crystallization process using Form 3 to prepare ceftolozane sulfate Form 2. Novel compositions also include ceftolozane sulfate solid Form 3 and/or other crystalline and amorphous solid forms of ceftolozane.

Ceftolozane sulfate is an example of a pharmaceutically acceptable salt of ceftolozane, which is a cephalosporin antibacterial agent, and has the chemical names (6R,7R)-3-[(5-amino-4-{[(2-aminoethyl)carbamoyl]amino}-1-methyl-1H-pyrazol-2-ium-2-yl)methyl]-7-({(2Z)-2-(5-amino-1,2,4-thiadiazol-3-yl)-2-[(1-carboxy-1-methylethoxy)-imino]acetyl}amino)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate, or 70-[(Z)-2-(5-amino-1,2,4-thiadiazol-3-yl)-2-(1-carboxy-1-methylethoxyimino)acetamido]-3-{3-amino-4-[3-(2-aminoethyl)ureido]-2-methyl-1-pyrazolio}methyl-3-cephem-4-carboxylate. It has also been referred to as CXA-101 or FR264205. The structure of ceftolozane sulfate is shown below.

Ceftolozane and the process for synthesizing are described in U.S. Pat. No. 7,129,232. Compositions comprising ceftolozane sulfate and tazobactam sodium (ZERBAXAV®) are used for intravenous administration or infusion to treat bacterial infections.
The current manufacturing process for ceftolozane involves a 3-step purification sequence consisting of column chromatography, nanofiltration, and crystallization to afford the active pharmaceutical ingredient (API) ceftolozane, which is also known as Form 2 of ceftolozane (WO 2015/048217 and WO 2016/109259). Although the column chromatography and nanofiltration steps afford Form 2 of ceftolozane in high purity, the overall process is time-consuming, volume inefficient, low yielding, and requires special manufacturing equipment. Additionally, the process suffers from slow filtration rates, which significantly reduces the productivity of the process.
There remains a need for a simplified and improved manufacturing process for the production of ceftolozane sulfate. As described herein, a new solid form of ceftolozane sulfate (Form 3) provides the foundation for a simplified purification process. This solid form, the DMAc solvate of ceftolozane sulfate (known herein as "Form 3"), enables a crystallization-based purification process which replaces the existing column chromatography and nanofiltration processes. The new process provides a higher yield, significant reduction in solvent usage, shorter cycle times, and utilizes standard manufacturing equipment, thereby affording a more productive, greener, and portable manufacturing process. Additionally, the streamlined purification process reduces overall manufacturing time, culminating in cost savings and a reduction in energy consumption.

Solid forms of ceftolozane and processes for preparing


A control circuit is provided that can be used to compensate for pinch off voltage sensitive circuits. The control circuit comprises a control FET (26) having a gate (27), a drain (29), and a source (28). The control FET source (28) is connected to a tracking potential (23) through control FET source resistor (31) in series with a constant voltage drop element (32). A control voltage input (22) is applied to the control FET drain (29). A current flow through the control FET (26) results in a transfer function that is substantially linear for linear changes in control voltage input below a voltage pinch off value of the control FET (26). As the voltage control output (23) approaches the pinch off voltage value of the control FET (26), smaller changes in control voltage output (23) are realized for the same change in control voltage input (22).

A known passive voltage variable attenuator design, referred to as a "T Structure" attenuator, comprises two series Field Effect Transistors ("FETs") and a shunt FET connected between a point common to the series FETs and reference potential as shown in FIG. 1 of the drawings. An RFin port is an input for RF energy to be attenuated. The attenuated output appears at an RFout port. The RFin port and RFout port are opposite ends of the series FET circuit. The series FETs and the shunt FET are controlled by an attenuation control voltage source. The point common to the series FETs is held substantially at the FETs pinch off voltage. The attenuation control voltage varies the gate voltage of the series FETs. The attenuation control voltage varying the gate voltage of the series FETs controls the gate to source voltage differential causing them to operate as variable resistors over a desired attenuation range. The attenuation control voltage concurrently varies the drain voltage and source voltage of the shunt FET, while the gate of the shunt FET is connected to reference potential. Therefore, the varying attenuation control voltage also causes the shunt FET to operate as a variable resistor over the same range, but in opposite relationship with respect to the attenuation control voltage value as the series FETs. The circuit is particularly well adapted for use in a radio frequency voltage variable attenuator using GaAs MESFETs.
In the T structure voltage variable attenuator circuit, attenuation is lowest at a five volt control voltage value and highest at a zero volt control voltage value. A control voltage input biases a resistive divider network. A control voltage output of the resistive divider network is the attenuation control voltage and varies from zero to approximately pinch off voltage of the FETs as the control voltage input ramps from zero to a maximum voltage, typically five volts. A point common to the series FETs is held at the pinch off voltage by a voltage regulator circuit biased by a fixed voltage source typically five volts.
In operation a zero volt control voltage input is applied to the resistive divider network resulting in a zero volt attenuation control voltage value. The attenuation control voltage is applied to the gates of the series FETs resulting in a gate to source voltage to both series FETs at approximately a pinch off voltage value. With the gate to source voltage of the series FETs held at approximately pinch off voltage, the series FETs are essentially turned off and are in a high resistance state. The zero volt control voltage input and, therefore, the attenuation control voltage output of the resistive divider network is concurrently applied to the drain and source of the shunt FET while the gate of the shunt FET is held at reference potential. This results in a zero or very small gate to source voltage differential on the shunt FET, thereby turning it on and producing an effective low resistance in the shunt FET. The low resistance in the shunt FET creates a low resistance path to ground. RF energy applied to the RFin port is effectively shorted to ground through the low resistance shunt FET permitting very little RF energy to appear at the RFout port of the voltage variable attenuator.
At a maximum control voltage input level, typically five volts, the voltage variable attenuator is in its lowest attenuation state. A five volt control voltage input ideally produces an attenuation control voltage at or near pinch off which is applied to the gate of the series FETs. The drain and source of the series FETs held at pinch off voltage causes the gate to source voltage differential of the series FETs to be approximately zero. A zero voltage differential between the gate and source of the series FETs turns them on and places them in an effective low resistance state. Concurrently, the five volt control voltage input results in an attenuation control voltage near pinch off to the drain and source of the shunt FET. The gate of the shunt FET is held at reference potential causing the gate to source voltage differential of the shunt FET to be approximately the pinch off voltage value. The pinch off voltage differential between the gate and source of the shunt FET, turns it off and places it in an effective high resistance state. In this state, most of the RF energy applied to the RF input port of the attenuator flows through the two series FETS and appears at the RF output port because the shunt FET is an effective open circuit.
As can be appreciated by one of ordinary skill in the art, proper operation of the voltage variable attenuator requires that the attenuation control voltage ramp from zero volts to approximately pinch off voltage. It is common, however, that FETs made by the same process exhibit some variations in performance characteristics and in particular pinch off voltage. In circuits that are sensitive to pinch off voltage variations for example the attenuator, shown in FIG. 1 of the drawings variations in pinch off voltage vary the transfer function of the circuit and can adversely affect yield and repeatability. In order to compensate for the variations in pinch off voltage and improve yield in the voltage variable attenuator, a resistive divider network having three bond pads therein is included in the circuit as illustrated in FIG. 1. The resistive divider network scales the zero to five volt control voltage input of the attenuator. After determining the pinch off voltage of the FETs in the circuit, electrical connection is made to one of the three bond pads in the resistive divider network. The appropriate bond pad is the one that scales the attenuation voltage control range from the zero to five volt control voltage input range most closely to the zero to the pinch off voltage range that is used internal to the attenuator circuit. Use of the resistive divider network requires measurement of the pinch off voltage, a decision regarding the most desirable bond pad to use in the resistive divider network, and wire bonding to the appropriate bond pad in order to achieve the zero to pinch off voltage scaled control voltage output for attenuation control. This operation is time consuming, costly, and prone to error. It is also coarse and inexact in that only three variations are realizable. There is a need therefore, for an apparatus that can compensate for pinch off voltage variations and is less time consuming and more reliable than prior art solutions. The ability of the manufacturer to produce parts within a narrow performance range over time and temperature is also highly desirable and effects repeatability of the part. It is known that pinch off voltage can vary over time and temperature in some devices. For circuits that are sensitive to pinch off voltage variations, there is also a need for a circuit that will adjust and compensate for variations in pinch off voltage over time and temperature.

Compensation network for pinch off voltage sensitive circuits


A skin pattern classification system extracts ridge line data and valley line data from image data of a skin pattern. Minutiae are extracted from the ridge line data and the valley line data. Subsequently, minutia correspondence information is obtained by detecting mutual correspondence among the minutiae from the ridge line data, valley line data and the minutiae. Skin patterns are obtained by finding and tracing characteristic lines referring to the minutia correspondence information, the ridge line data and the valley line data, and the characteristic lines and the minutia correspondence information serve to provide pattern classification.

This invention relates to a skin pattern and fingerprint classification system for tracing and classifying features of skin patterns such as palm prints or fingerprints.
A method of fingerprint classification according to features extracted from thinned pattern lines obtained from fingerprint pictures is disclosed in a paper entitled "An Algorithm for Classification of Fingerprints Based on the Core" by Shinichiro Ito, et al., transactions of the Institute of Electronics, Information and Communication Engineers (IEICE), D-II, Vol. J73-D-II No. 10, pp. 1733-1741 (October 1990). Ito, et al., discloses a method wherein a core of a fingerprint is detected in a fingerprint image after thinning, then ridge lines around the core point are traced for obtaining features of the ridge lines. According to kinds (i.e., types) and distributions of the ridge line features, the fingerprint image can be classified, e.g., into one of four categories, Whorl, Arch, Right Loop or Left Loop.
In the prior art, a core is detected first, on an assumption that a scanning line passing on the core point should have a largest number of cross points with ridge lines. So, at a first step, cross points with ridge lines in an appropriate region of a fingerprint image, after thinning, are counted for each of a certain number of scanning lines drawn on the region. The scanning lines are drawn in a horizontal and a vertical direction and in directions rotated .pi./4 from them. At a second step, coordinates of a temporary core point are calculated from coordinates of the scanning lines having more than a certain number of cross points with ridge lines. At a third step, a region smaller than the region applied at the former steps is settled around the temporary core point thus calculated, and the first and the second steps are repeated concerning the smaller region. Thus, the core point of the fingerprint image is finally detected by repeating the first, the second and the third steps a certain number of times.
Then, in the prior art, a certain number of beginning points are considered on ridge lines around the core point thus detected. From each of the certain number of beginning points, each ridge line is traced in both directions. The tracing continues for a certain length along the ridge line for extracting feature data as coordinates of the beginning point and both ending points. The end points are determined by each of the directional tracings of the ridge line segments. By referring to the distribution of these feature data concerning the beginning points around the core, the fingerprint image is classified.
FIG. 23 is a schematic diagram illustrating the tracing of ridge lines around a core having features to be classified as a Whorl. First, a pair of beginning points are considered on a horizontal line passing through the core of the fingerprint. Then, each of a pair of ridge lines crossing with the horizontal line at the beginning points are traced in both directions for a predetermined length, and two pairs of ending points are obtained. When the distances between the ending points of the two pairs are both shorter than the distance between the beginning points, the core is defined to have a certain value of features to be classified into the Whorl.
Although a method of ridge line tracing is not specified in the above prior art, it is performed as follows. For example, when a gap is found on a ridge line, the following steps can be used.
For example, an end point is detected along a directional tracing of a ridge line, another ridge line is searched along a vertical line having the same x-coordinates as the detected end point. The ridge line trace is then continued on a ridge line found nearest from the detected end point. An example of this method of ridge line tracing is described in a paper entitled "Feature Extraction for Fingerprint Classification," by T. Ch. Malleswara Rao, Pattern Recognition, Vol. 8, pp. 181-192 (1976).
The prior art described above is based on the assumption that a scanning line on the core point has the largest number of cross points with ridge lines. However, because ridge line image is not always so clear, the scanning line having a largest number of cross points may not always pass through the core point. So, some errors may occur in the core point detection, resulting in a wrong classification of fingerprints. This classification error is a problem.
Also, in order to reject indefinite data to avoid a wrong classification that is caused by image degradation, methods of fingerprint classification based on ridge line tracing generally need complicated devices. These complicated devices have parameters that are difficult to control as to defining the rejection level and therefore is another problem. Further, when a second possibility of classification is desired to be assigned to a fingerprint image that is classified in a category with a low reliability, the assignment itself is hardly possible to be done in the prior art. In order to perform the assignment, the method is to instead use a human operator who knows the classification system very well.
Still further, as described above, there is indeterminacy in the method of ridge line tracing when, e.g., an end-point or a bifurcation of a ridge line is found in the ridge line tracing. Therefore, when a classification system based on ridge line tracing is applied for fingerprint classification, its analyzing performance is not sufficient, because it is easily affected by the curvature or the inclination of the fingerprint.

Skin pattern and fingerprint classification system


The present technique relates to a method and apparatus for managing voltage buses. In a memory device, such as SRAM or DRAM, a periphery voltage bus may supply voltage to periphery circuitry and an array voltage bus may supply voltage to array circuitry. A bridge circuit may be utilized to isolate the buses from each other and couple the buses together, depending on the control signals are received by the bridge circuit. As such, the bridge circuit enhances the operation of the memory device by reducing duplicative circuits and equalizing the voltage that are applied to the buses. In addition, the bridge circuit isolates the buses from each other to protect sensitive circuitry in the array and periphery circuitry from noise on the other bus.

1. Field of the Invention
The present invention relates generally to semiconductor devices and, more particularly, to the distribution of power in array and periphery sections of a semiconductor device, such as a memory device.
2. Description of the Related Art
This section is intended to introduce the reader to various aspects of art which may be related to various aspects of the present invention which are described and/or claimed below. This discussion is believed to be helpful in providing the reader with background information to facilitate a better understanding of the various aspects of the present invention. Accordingly, it should be understood that these statements are to be read in this light, and not as admissions of prior art.
Microprocessor-controlled integrated circuits are used in a wide variety of applications. Such applications include personal computers, telephones, vehicle control systems, networks, and a host of other consumer products. Typically, microprocessors are essentially generic devices that perform specific functions under the control of a software program. This program is stored in a memory device that is coupled to the microprocessor. Not only does the microprocessor access one or more memory devices to retrieve the program instructions, but it also stores and retrieves data created during execution of the program in the memory devices.
It should be understood that memory devices, which may be a semiconductor chip, include integrated circuits that are typically mass produced through fabrication processes. In forming the chip, different materials are layered together to form various structures or circuitry within the chip. These structures are connected together to exchange signals, distribute power within the chip and receive power from external devices, among other things. Additionally, the semiconductor chip may be divided into different sections, such as the array section and the periphery section. The array section may include memory structures, such as memory cells and banks that are used to store data, while the periphery section may include larger structures that support the array section, such as drivers, interconnects between circuitry, decoders or other similar circuitry.
Regardless of the specific structures within the semiconductor chip being fabricated, it is often desirable to conserve power and to ensure that the power distributed to various circuits is provided in a consistent and steady manner. For instance, in a personal computing device, the configuration and layout of components may affect the operation and efficiency of the device. During a power-up phase, different sections of the chip, such as the periphery and array sections, may not reach a specified voltage at the same time. This variation in time may result in the chip taking longer to power up from an initialization or standby mode to an operation mode because one of the sections takes longer to reach the operational voltage. As a result, these inefficiencies may reduce the amount of time that the device is able to operate in an active or standby mode.

Apparatus and method for managing voltage buses


The traditional trade-off between performance and shelf-life of processless thermal printing plates can be eliminated by using reactive chemicals which are mixed during (or just prior to) application to the plate and imaged shortly thereafter. The utility of high power thermal exposure heads combined with the advantages of mixing two reactive chemicals, allows the generation of high performance processless thermal printing plates on-site, effectively eliminating the requirements of shelf-life and robustness. Furthermore, the process of mixing the reactive chemicals is ideally suited for on-press imaging.

In lithographic offset printing, printing plates are typically made of a thin aluminum sheet (the substrate) overlaid with a thin coat of polymer. The polymer is normally photo-sensitive or thermally sensitive. The sensitivity of the polymer is exploited to expose the plate with the desired image using light or laser. Photo-sensitive polymers are exposed with U.V. or visible light whereas thermally sensitive polymers are typically exposed using relatively high powered I.R. lasers. After being exposed imagewise, the plate traditionally requires chemical development before being used on a press. However, recent technologies are "processless" meaning that they require no chemical development or other intermediate steps other than possibly wiping off ablated residue and can be used directly on a press after imaging.
This invention is particularly concerned with processless plates exposed by a laser source, either in a Computer-To-Plate system (C.T.P.) or directly on the printing press (on-press imaging). The polymer coating is either hydrophobic or hydrophilic and changes its water attraction properties with exposure to the laser. Alternatively, the plate can be a dry (or waterless) offset plate. Processless plates exposed on the press may be single use or reusable (i.e. where the same plate is cleaned, re-coated with polymer and used multiple times). (See related application, Ser. No. 08/490,361, now U.S. Pat. No. 5,713,287).
Printing plate performance is typically determined by the "I.R. sensitivity" (i.e. amount of laser power required for imaging) and "imaging resolution" (i.e. the hydrophobic/hydrophilic differential between the irradiated and non-irradiated areas). At odds with plate performance are the requirements for a long shelf-life and robustness. Time combined with the stresses of handling and transport cause the performance of a printing plate to degrade. As such, the performance criteria of I.R. sensitivity and image resolution distinctly determine the required shelf-life and robustness. These conflicting goals are particularly important for processless plates, because it is extremely difficult to create a processless thermal plate combining performance criteria with shelf-life and robustness.
Pre-coated plates, also known as pre-sensitized plates, are manufactured at central locations and distributed to many users. The time between the making and the using of the plate is several months. Accordingly, the chemicals used to coat the plates must be sufficiently robust and durable to withstand transport and handling, and to endure a relatively long shelf-life (typically on the scale of twelve months). In order to achieve such a shelf-life, the chemicals employed on pre-coated plates must be relatively stable and non-reactive. As such, pre-coated plates sacrifice performance, particularly I.R. sensitivity, for robustness and shelf-life. If plates could be coated on-site at the printing plant, then this sacrifice could be effectively eliminated because the required shelf-life would only be the duration of the printing run (typically on the scale of hours or days) and there would be relatively little handling and transportation involved. Consequently, more aggressive coating chemicals, which tend to react with one another, may be used to create plates with superior I.R. sensitivity and imaging resolution at the expense of diminished shelf-life and robustness.
On-site coating has been used in the printing industry before. The best known examples are the "Wipe-On" plates in which a photo-sensitive composition is spread on the aluminum plate by hand or machine. The coated plate is then treated by mechanical, chemical or electrical processes to improve the hydrophilic properties and adhesion of the polymer coating. "Wipe-On" plates are used less frequently now, because their chemistry is the same as that of pre-coated plates, but their performance is inferior; their only advantage is lower cost. In this invention a different chemistry is used for on-site coating which cannot be used on pre-coated plates due to the strong reactive nature of the chemicals involved. The high degree of chemical activity generates plates superior to pre-coated plates at the expense of shelf-life and robustness which are of reduced importance for on-site coating.
European patent EP-0-652-483-A1, hereinafter referred to as Ellis, discloses a heat sensitive coating for use on a pre-coated processless lithographic plate. The coating consists of three chemicals:
(i) a hydrophobic polymer which reacts under the action of heat and/or acid to become hydrophilic (Page 2, lines 51-52); PA1 (ii) a photo-thermal converter which is capable of absorbing I.R. radiation and converting it to heat and/or acid (Page 2, lines 43-44 and Page 4, lines 35-36); PA1 (iii) a thermal acid generator which releases acid under the action of heat generated by irradiation of the photo-thermal converter (Page 5, lines 22-24).
Ellis does not teach direct addition of acid to the mixture because the Ellis invention is concerned about the detrimental effects on the shelf-life and robustness of the coating which are essential requirements of a pre-coated plate.

On-site generation of processless thermal printing plates using reactive materials


An object of the invention is to provide a depressurizing valve mounted to a common rail for a fuel injection device, in which a direction of a connector for the depressurizing valve can be adjusted, without affecting an air gap and a sealing performance. The depressurizing valve has a valve unit and a coil unit which is detachably assembled to the valve unit by a mounting member, such as a retaining nut. A valve housing has an inside space, which is fluid tightly separated into first and second spaces by a connecting member, which is fluid tightly connected to the valve housing and a stator core. A valve body and a spring are arranged in the first space for closing a flow control port. A cylindrical coil is accommodated in the second space, such that the coil is rotatable with respect to the valve housing.

A conventional fuel injection device for an internal combustion engine has; a common rail for storing a high pressure fuel; fuel injection valves for injecting the high pressure fuel from the common rail into respective cylinders of the engine; a fuel pump for sucking and pressurizing the fuel and supplying the high pressure fuel to the common rail; a fuel return path for returning a portion of the high pressure fuel from the common rail to a low pressure side (a fuel tank); an electromagnetic type depressurizing valve which will be operated to open the fuel return path when the vehicle is decelerated in order to quickly reduce the fuel pressure in the common rail.
The depressurizing valve is mounted to, for example, the common rail. In the fuel injection device, however, as disclosed in Japanese Patent Publication No. 2001-59459, the depressurizing valve is mounted to the fuel pump. The depressurizing valve has a flanged portion, at which a through hole is formed for inserting a bolt therethrough, and the depressurizing valve is fixed to the fuel pump by the bolt.
In the fuel injection device, as disclosed in Japanese Patent Publication No. H11-141428, a solenoid portion is fixed to a body member of a fuel injection valve by a retaining nut, wherein an electromagnetic valve portion thereof can be used as a depressurizing valve.
The depressurizing valve mounted to the common rail has a connector for receiving driving current. The connector is electrically connected to a driving circuit through a wire harness, when the common rail is mounted to the engine. It is, however, necessary to adjust a direction of the connector when the depressurizing valve is mounted to the common rail, because the common rail must be mounted to the engine in a limited space and thereby a position (direction) of the connector must be selected to a predetermined position (direction) with respect to the common rail. Nothing has been proposed so far, wherein a direction of the connector is adjusted in the depressurizing valve to be mounted to the common rail.
If the fixing structure of the depressurizing valve, as disclosed in the above mentioned prior art (No. 2001-59459), in which the flanged portion of the valve is fixed to the fuel pump by the bolt, was intended to be applied to a fixing structure for a depressurizing valve to be mounted to the common rail, a bolt hole should be formed in the common rail of a cylindrical shape. In such a fixing structure, the direction of the connector provided in the depressurizing valve can be adjusted to a predetermined desired direction. However, it is actually difficult to form the bolt hole in the common rail, because the common rail is generally formed as the cylindrical shape, and thereby there is no sufficient space for the bolt hole.
In the fuel injection device disclosed in Japanese Patent Publication No. H11-141428, a direction of a connector portion can be adjusted by loosening a retaining nut. However, if the retaining nut was loosened, positions of inside parts, such as a spacer for adjusting an air gap, an armature, and so on would be changed. As a result, there would be a problem that the air gap would be changed after the retaining nut was once loosened and then tightly screwed again. Furthermore, if the retaining nut was loosened, a position and a contacting condition of a sealing member which is disposed between the retaining nut and the valve housing would be also changed. Accordingly, it would be necessary to check a sealing performance once again after the retaining nut was tightly screwed again.
In the case that the structure of the above prior art (Japanese Patent Publication No. H11-141428) for fixing the solenoid portion of the electromagnetic coil to the valve housing was applied to the depressurizing valve to be mounted to the common rail, the direction of the connector portion can be adjusted by loosening the retaining nut. However, there are still problems in that the air gap might be changed and/or the sealing performance should be checked again, as in the fuel injection device of the above mentioned prior art.

Depressurizing valve and fuel injection device


A two-phase asynchronous print tracking system and method is described. The separation of detection of print activity and billing of print activity is accomplished by means of a quota-based message queue. Print jobs sent by a user are allowed to print without interruption until a quota number of print jobs for which no billing information has been entered are reached. When the quota is exceeded, the user may not continue until appropriate billing information is entered.

In recent years, it has become increasingly desirable for businesses to quantify their printing and print media costs, both for the purpose of cost allocation and to allow them to recoup related expenses. This is of particular concern for professionals such as architects and engineers, since the services provided by such professionals may require the printing of blueprints and other large-format technical documents. The printing of such documents is costly, and thus the ability to recoup these costs through a print tracking system is of great value.
Prior to describing the attributes of existing print tracking systems, the general layout of a computer network in which such a system may be installed will be described. An office computer network generally contains each of the following elements:                1. a plurality of client computers from which print jobs originate;        2. a network through which the client computers and other system components are interconnected;        3. one or more users who generate print jobs while logged in to the computer network through a client computer;        4. print jobs, which possess inherent attributes such as quantity and page dimensions;        5. a printer, from which printed physical media is physically printed; and        6. a server computer, which is responsible for queuing and directing traffic to the printer.In addition, many office computer networks that include print tracking also include the following additional components:        1. a component designed to detect print activity and extract relevant print job information;        2. A graphical user interface (GUI) for providing billing information (the billing dialog) to each user;        3. a central database to which data about print activity is recorded;        4. a management interface from whence the print tracking system can be controlled; and        5. a reporting interface through which print activity data can be viewed.
Any print tracking system must both detect print activity and bill print activity or, in other words, both quantify and qualify print activity. Maintaining a factual record describing all print activity on a computer network is the first requirement of a print tracking solution. This record generally includes all of the defining data for each print job that is submitted to the server. This data generally includes, but is not limited to, the name of the print server that directed the document to the printer; the name of the software application from which the print job originated; the filename of the document to be printed; the name of the computer from which the print job originated; the username of the individual who submitted the print job; the name of the printer to which the print job was sent; the number of printed pages per copy; the number of copies to be made; the height and width of the printed document; and the date and time of the print job request. This type of data is considered factual and inherent to a print job, and can be extracted automatically from a print job without user intervention.
Once reliable print activity detection has been established, it is necessary to elaborate on the resultant data records for accounting purposes. These records are factual, but lack information pertinent to accounting or "qualification." Data not inherent to a print job must be supplied by a user and then appended to an existing factual record. Such data may include, but is not limited to, the related project number; the related client number; the sub-project or phase number; the status of the project; and any additional user comments. These appended data fields allow the office administration or accounting personnel to generate invoices, cost estimates, and other business metrics to assist in the overall efficiency of the office and to allow the office to recoup what would otherwise be overhead costs.
Although the proper entry of qualification (billing-related) data is necessary in order for a print tracking system to achieve its goals, users are generally reluctant to enter such data. Users may see the process of entering such data as time-consuming or as a distraction from their immediate goals of completing a technical or professional project. Print tracking systems must therefore employ some sort of enforcement mechanism in order to ensure that users supply the qualification data in a complete and timely manner. Two enforcement methods have generally been used in existing print tracking systems.
The first enforcement method, which may be referred to as the "hostage" method, is to interrupt the print job and prevent it from completing until the user has adequately complied with the print tracking system's qualification data requirements. Thus for example a user who requests a print job may immediately be presented with a GUI (graphical user interface) in which to provide the necessary qualification data. If the user does not enter all required data, the user's print job will not be sent to the server for execution.
The second enforcement method, which may be referred to as the "quarantine" method, allows the print job to leave the client machine in an apparently normal manner. At the server, however, the print job is interrupted and placed in a holding area. A GUI at the client computer allows the user to inspect the contents of the holding area and bill the print jobs that are waiting. When the user has adequately complied with the print tracking system, the server then completes the print job. As with the enforcement method, the user's print job will not be completed until the required qualification data has been entered.
Another means by which existing print tracking systems may be distinguished is by the location at which they process data related to the print job, either at the client computer or at the server. These may be referred to as "client-side" and "server-side" (or "network-based") models. On the client-side model, the acts of extracting the factual information describing a print job and writing that information to a database occur on the client computer from which the print job originated. On the server-side model, the acts of extracting the factual information describing a print job and writing that information to a database occur on the server. It may be noted that using the client-side model, the process of extracting and writing this information must reside on each of what is typically a plurality of client computers, whereas when using the server-side model the process resides on what is typically a single server.
In a print-tracking system using the client-side model, print tracking occurs entirely at the client computer. The software installed at the client computer detects print activity and extracts its data as it leaves the client computer. The software will then initiate a billing dialog, which includes a GUI. This GUI allows the user logged in at that client computer to enter the appropriate billing information for that particular print job. A record of the print job and all of its pertinent data may then be written to a central database for later review.
One limitation of the client-side model print tracking systems is that they include no means of accounting for cases where a print job fails to complete. Since all information has been entered at the point where the print job is forwarded to the server, the client computer software will not know if problems occur during the actual printing of the job. The result may be a cost record in the central database where in fact no print job was actually completed. Where a print job is sent but fails due to a technical problem with the printer, network, or server, and that print job is later resent after the problem is corrected, the central database may contain a double entry for this print job.
Another limitation of the client-side print tracking systems is that they generally use the "hostage" enforcement model, thereby requiring the billing action to occur before the print job is sent. In order to accomplish this, the print tracking system will interrupt the print job to allow the user to enter billing information. The user cannot proceed until this information has been entered. If for any reason the user does not supply billing information about a print job, then the user's print job will not be recorded. Thus a dilemma of user enforcement with the system arises. If the print tracking system were to allow the print job to print before the user has supplied the billing information, then the user may opt not to comply with the system by entering the required information. The result would be factual discrepancies in the recorded data and missed opportunities to recoup costs associated with printing.
Still another limitation of client-side tracking is that the process of print detection is delegated to the individual client computers, which results in a limited, one-to-one tracking method. This means that by installing one instance of the print tracking program, the office has the ability to track only one user's print jobs. Two installed instances will track print jobs issuing from two client computers, and so on. Whenever new software upgrades or patches become available, they must be installed separately on every client computer.
Finally, many client-side print tracking systems are subject to problems arising from other computer applications that use non-standard printing routines. For example, on computers running the popular Windows operating system from Microsoft Corporation of Redmond, Washington, a number of Computer Aided Drafting (CAD) and other graphics applications bypass the Windows standard printing system. A client-side print tracking system cannot track printing from these nonstandard applications without the use of a "plug-in" application. A plug-in uses the Application Programming Interface (API) of the relevant software program (for example, a CAD application) to detect printing within that application, then completes the billing process in the manner previously described. If an application does not use standard printing techniques and its vendor does not offer an API, then the system will be unable to track print jobs originating from within that application. In any event, both the use of a plug-in and the development of an API increase the cost and complexity of any such print tracking system even if it can be made operable. Systems that use plug-ins, moreover, are more susceptible to changes in the various APIs of the applications they seek to track. As new versions of the APIs are released, new plug-ins must be created, tested and distributed, further increasing the cost of building and maintaining such a tracking system, and increasing system downtime as new plug-in versions are installed.
AEG:AutoTRACK, which is sold by AEG:Technologies, Inc. of Richardson, Tex., is an example of a print tracking software system that requires a plug-in for each application for which print tracking is desired. SmartPlot, another print tracking software package that is sold by Technesis, Inc. of Mountain View, Calif., has taken the client side tracking solution a bit further than AutoTrack by detecting prints on the client computer operating system. SmartPlot is, therefore, able to detect print activity on most Windows-based programs without application plug-ins. There are, however, a great many applications that do not use the native operating system print process on the client computer. As a result, a great many application-specific plug-ins must be continually developed and updated in order for SmartPlot to offer "comprehensive" print tracking. Even with these stop-gap solutions, there are any number of applications that circumvent the operating system print process for which SmartPlot's developer offers no plug-in.
The network-based, or server-side, model of print tracking is an alternative approach that is implemented in some existing print tracking systems. Because a typical office has only a few print devices shared via a network, but has a multitude of client computers through which users may wish to share these resources, it is common for a user to send a print job to a printer that is physically attached to another computer. Compared to client-side print tracking, network-based print tracking offers a reliable method for detecting such print jobs and accurately recording them. In such a scenario, the onus of detection is on the server rather than the various client computers.
In the network-based print tracking process, the application plug-in of the client-side system is no longer required. Instead, the more scalable method of remote print queue monitoring may be applied. Such systems may transcend the "one-to-one" tracking ratio offered by client side tracking. This means that because the software is installed on the computer that is directly attached to the physical printer, any print jobs going to the printer will be tracked. In essence, the network-based tracking system facilitates a "one-to-many" relationship of users tracked to installed software sets.
While the network-based approach offers certain benefits over client-side print tracking, it also poses several new hurdles for the system architecture. The core design dilemma in this scenario is to first detect the print job at the server computer to which the printer is connected, then to discover the computer from which it originated, and finally to initiate the billing dialog at this originating computer. It is this last step of initiating the billing dialog that poses the most problems and in turn the widest range of attempted solutions.
All existing solutions to the problem of initiating the billing log in a network-based tracking system extract the factual information at the print server, only to relay it back to the originating machine. While the server waits for information from the user to be entered at the client computer, it must keep the print job "quarantined" to ensure that users comply with the system and supply required billing information. Thus network-based print tracking systems use the "quarantine" method of enforcement. Only after the user supplies the required billing information is the record placed into the database and the print job released to the printer. While this method is a marginal improvement over preceding client-based solutions, it still marries the act of billing a print job with the act of tracking a print job. Therefore, you will only be able to track those computers that have a current version of the required client software installed. If, for example, client computers without the necessary client billing software were to print to a monitored printer, they will be unable to free their print job from the quarantine and will thereby lock up system resources.
PrintLog Manager, which is sold by Equitrac Corporation of Coral Gables, Fla., is a popular network-based print tracking system. PrintLog Manager quarantines print jobs until users supply the proper billing information. The act of billing a print is, therefore, synonymous with the act of recording a print job. If for any reason the system fails to function, however, printing is disabled and all work must be halted. PrintSuite, which is sold by Infinity Squared Technologies, Inc. of Burnaby, British Columbia, Canada, also uses a quarantine methodology for tracking and billing prints. The server-installed component of the PrintSuite software halts print activity and prompts a user for billing information before releasing the print job to a printer.
A critical limitation of all existing print tracking systems, both client-side and server-side, is that they operate in what may be termed a "synchronous" mode. In a synchronous print tracking system, the act of writing data about a print job to a central database takes place when the print is detected and information is extracted and stored. The processes of detection of the print job and billing are thus tightly coupled together; in other words, the act of supplying billing information is also the act of placing a record in the database from the user's point of view. Such systems treat both tracking and billing as an integral part of the printing process. The desirability of decoupling the tracking and billing processes to create an "asynchronous" print tracking system, and the advantages that result from such decoupling, have gone unrecognized.
The limitations of the prior art are overcome by the present invention as described below.

System and method for asynchronous tracking and quantifying of printing events


A method for estimating the composition of a fuel within an engine, comprises performing the following steps under ambient conditions: (a′) determining the ambient temperature of the fuel; (a) monitoring the fuel pressure inside a fuel rail of the engine over a period of time; (b) calculating at least one frequency component of the change in fuel pressure; (c) calculating the speed of sound transmission c on the basis of the at least one frequency component; and (d) estimating the composition of the fuel on the basis of the calculated speed of sound transmission at said ambient temperature. Suitably, the speed of sound transmission in the fuel is calculated using the equation: c=fλ, where the wavelength λ of the standing wave with frequency f is 2L, where L is the length of the fuel rail. Also described are methods for estimating the temperature of the fuel at a non-ambient temperature, and determining a fuels physical properties. Methods for controlling a fuel injection system in an engine according to the determined physical properties of the fuel and the resultant fuel injection system are also described.

In a fuel injection system for a diesel-powered engine, fuel at high pressure is injected rapidly, and usually directly, into the fuel combustion chamber. Inside the combustion chamber the fuel mixes with air and combusts with the available oxygen to generate the power that is used to drive the vehicle.
One of the advantages of current fuel injection systems is that the amount of fuel entering the combustion chamber can be precisely controlled so as to improve the performance and emissions of the engine. For instance, better emissions can be achieved by matching the amount of fuel entering the combustion chamber in response to a signal indicating the amount of air flowing in to the engine.
In order to optimise the emissions performance of an engine (e.g. minimise NOx and particulates), extensive calibration and testing is performed on an engine, typically during engine development, under controlled conditions (for example, known fuel composition and fuel temperature). Hence, information such as: the optimum amount of fuel required to match a certain volume of air from a turbo charger, or to control the temperature of an after-treatment system such as a diesel particulate filter (DPF), is typically found by experimentation and programmed into an engine management computer or engine control unit (ECU).
However, it is known that the physical properties of a fuel (e.g. the viscosity, isoentropic bulk modulus and density) can vary quite considerably according to factors such as temperature and fuel composition. These properties in turn affect how the fuel behaves in a fuel injection system: for example, how quickly it flows; what its pressure is; and consequently, how much fuel is injected at each fuel injection event (stroke). This variation can be particularly significant for diesel engines (as opposed to gasoline engines), because diesel engines can often run on a relatively wide variety of fuel compositions, including biodiesels and biodiesel blends. By way of example, it is not uncommon for commercially available diesel fuel to have different compositions in winter and summer for optimal performance in different extremes of ambient temperature.
Biodiesel is considered to be an environmentally friendly alternative to traditional fuels such as diesel. It is derived from renewable resources such as vegetable and animal fats and waste cooking greases, and importantly, it can be mixed with petroleum-based diesel to create a blend, without causing damage to a diesel engine. Due to its wide variety of possible compositions, biodiesel can cause changes in engine performance and emissions. For example, Tat, M. E. & Van Gerpen, J. H. (ASAE paper no. 026084, ASAE Annual International Meeting, USA, Jul. 28-31, 2002) reported an approximately linear correlation between the biodiesel blend composition (i.e. the proportion of biodiesel and diesel in a blend) and the physical properties of density, isoentropic bulk modulus and the speed of sound transmission within the fuel.
Variations in the physical properties of a fuel can significantly impact on the actual amount of fuel that is injected into a combustion chamber in a single fuel injection event. When it is then considered that there could be over 70 injection events into the engine every second, the actual amount of fuel injected in any period of time could be considerably higher or lower than the actual fuel demand. Such a difference between fuel supply and demand can cause an engine to operate considerably differently to when it was first calibrated, with a consequential reduction in engine performance, perhaps in terms of one or more of power output, fuel economy and engine emissions.
Prior art fuel injection systems have fuel temperature sensors that use a thermocouple to measure fuel temperature. However these are both an additional expense and a potential point of failure. Moreover, such temperature sensors only measure the temperature in the vicinity of the sensor, and not across the bulk of the body of fuel. Composition sensors also exist that measure gasoline/ethanol blends (see Tat, M. E. and Van Gerpen, J. H. supra.). Again these are separate components, which introduce additional expense and potential point of failure issues.
Therefore, in order to accurately control a fuel injection system it would be advantageous to be able to mathematically model the behaviour of fuel under any set of conditions. For this reason, it would be beneficial for a fuel injection system to be able to estimate the composition of fuel within the engine/system and then compensate for its specific physical properties to optimise fuel injection events, for example, at engine start-up. Also it would be advantageous to estimate (or calculate) the temperature of fuel within the engine/system and then compensate for any changes in the physical properties of the fuel as the temperature of the fuel changes during engine use, i.e. under non-ambient conditions. Advantageously, the methods of the system operate without the need for additional temperature/composition sensors: for example, by using existing pressure sensors.
Accordingly, there is a need for a method of estimating the physical properties of fuel in an engine in real time, and under both ambient and non-ambient (i.e. operating) conditions. In addition, there is a need for an improved fuel injection system that is capable of responding to changes in fuel physical properties, engine conditions and/or fuel composition so as to accurately satisfy a specific (or change in) fuel demand under operating conditions.
This invention aims to overcome or alleviate some of the problems associated with the prior art.

Fuel composition estimation and control of fuel injection


According to one embodiment of the disclosure, an annular seal generally includes a hollow member having two ends and an inner surface. The hollow member has a number of depressions formed in and extending around its inner surface. Each of the depressions having a depth that is a function of its distance from one of the two ends.

Annular seals have been implemented on turbomachinery to prevent leakage of compressible or incompressible fluids such as gases or liquids, respectively. These annular seals generally incorporate a hollow member having a number of depressions formed in its inner surface that is dimensioned to extend around a rotor portion having a relatively smooth surface. In operation, the physical relationship of the rotor surface to the stator surface causes a dynamic resistance to the movement of the fluid through the seal such that a sealing action occurs.
Common types of annular seals include hole pattern (HP) seals and honeycomb (HC) seals. Hole pattern seals generally include depressions in the form of a number of generally round-shaped holes that are formed in the inner surface of its stator portion. Honeycomb seals generally include depressions in the form of generally hexagonal-shaped holes that are formed into a lattice-shaped structure. The inner surface of the hollow member is configured in a spaced apart relation relative to the outer surface of the rotor portion so that no contact is made between the hollow member and rotor portion. In this manner, relatively little wear may be caused to the inner surface of the hollow member or outer surface of the rotor during operation.

Annular seals for non-contact sealing of fluids in turbomachinery


An electrode-provided sheet-like pressure-sensitive resistance member includes a sheet-like pressure-sensitive resistance member which includes conductive particles arranged such that the conducting direction of the conductive particles intersects a surface of the sheet-like pressure-sensitive resistance member, a sheet-like protective member for protecting the sheet-like pressure-sensitive resistance member, and a sheet-like electrode member composed of a substrate and electrodes formed thereon. Accordingly, it becomes possible to sufficiently increase the durability of the electrode-provided sheet-like pressure-sensitive resistance member and to form it into an arbitrary shape. Also, needle-shaped conductive particles and spherical non-conductive particles are dispersed within a resin material in a state in which the needle-shaped conductive particles are in close contact with the surface of the spherical non-conductive particles, whereby the conducting direction of the conductive particles intersects the surface of the sheet-like pressure-sensitive resistance member. Accordingly, it becomes possible to effectively transmit variations in externally applied pressure, thereby greatly increasing the transmission sensitivity for information about the applied pressure.

1. Field of the Invention
The present invention relates to a sheet-like pressure-sensitive resistance member having electrodes (hereinafter referred to as an "electrode-provided sheet-like pressure-sensitive resistance member"), a method of manufacturing the electrode-provided sheet-like pressure-sensitive resistance member, and a sheet-like pressure-sensitive resistance member itself.
2. Description of the Related Art
Conventionally, sheet-like pressure-sensitive resistance members having electrodes (hereinafter referred to as "pressure-sensitive resistance film") are formed by bonding together a sheet-like pressure-sensitive resistance member (hereinafter referred to as "conductive film") formed by using a conductive material such as carbon, and a sheet-like electrode member (hereinafter referred to as "electrode film") having a desired electrode pattern of silver formed thereon by, for example, printing a silver material. The pressure-sensitive resistance film thus formed changes its resistance value at a portion where a pressure is applied externally.
However, since the conventional pressure-sensitive resistance film uses an electrode film on which a silver material is printed, it has the drawbacks that cracks are generated in the electrodes after the printed silver material has been dried, resulting in poor durability, and that the pressure-sensitive resistance film cannot be formed into a desired shape.
Furthermore, connection between individual electrodes on the electrode film and resistance-value-information takeout leads, which is normally made or completed by soldering, is very difficult to attain due to the electrodes made of silver.
The conventional sheet-like pressure-sensitive resistance member, which is one structural component of the pressure-sensitive resistance film, includes a particulate conductive material. Since the particles are not uniformly arranged in such a manner that the direction of electrical conduction (hereinafter referred to as the "conducting direction") of the conductive material (particles) intersects the sheet surface, the resistance value on the surface of the sheet-like pressure-sensitive resistance member tends to vary depending on the position on the sheet surface. Therefore, a constant sensitivity in transmitting externally applied pressures cannot be maintained. More particularly, when the external pressure is very small, it is normally impossible to obtain information about the applied pressure with fidelity.

Sheet-like pressure-sensitive resistance member having electrodes, method of making the same, and sheet-like pressure-sensitive resistance member