Plasticizers are purified by contact with a coalescing filter to effect removal of ions, metals, monohydric alcohols, and polyhydric alcohols. The resulting purified plasticizer compositions are suitable for use in PVC due to their low levels of impurities that reduce PVC utility.

The present invention relates generally to processes for purification of plasticizer compositions. More specifically, the present invention relates to processes for purification of epoxidized ester plasticizers.
Such epoxidized fatty acid esters have lately been of considerable interest for use as renewable source-based or—derived plasticizers for various plasticized polymer compositions and end uses, including for alkyd resins, amino resins, epoxy resins (usually phenolic materials), phenolic resins, polystyrene, polyurethane, poly (vinyl alcohol) and unsaturated polyesters. In particular, such materials have been investigated for use in polyvinyl halide compositions.
Polyvinyl chloride (PVC), the most common vinyl halide polymer, finds commercial application in a rigid, substantially unplasticized form and in a plasticized PVC form. Rigid PVC, with which the present invention is not concerned, is used for pipework, ducts and the like in which high chemical resistance is needed but not flexibility or pliability. Plasticized PVC, on the other hand, finds application in films, sheeting, wire and cable coverings, moldings, conveyor belting, toys and hose, in addition to serving as a leather substitute and as a fabric covering for upholstered furniture, automotive seating and other articles.
Broadly speaking, plasticizers are materials which are combined with polymers such as polyvinyl chloride (hereinafter, PVC) to impart flexibility, extensibility and workability or some combination of these attributes to the polymer, as needed for a particular end use. In 1951, the International Union of Pure and Applied Chemistry (IUPAC) developed a universally accepted definition for a plasticizer as a substance or a material incorporated in a material (usually a plastic or an elastomer) to increase its flexibility, workability, or distensibility. Frequently, a combination of primary and secondary plasticizers is used, with the secondary plasticizers not acting in and of themselves to impart the desired attributes to the PVC but serving to improve the effectiveness of the primary plasticizer(s) and optionally offer other characteristics to a PVC composition in which the materials are incorporated.
Historically, the majority of primary PVC plasticizers have been petroleum-derived phthalates and benzoate compounds, dioctyl phthalate and diisononyl phthalate being notable examples. However, such petroleum-derived plasticizers are frequently expensive to produce and use because of fluctuations in the pricing and availability of petroleum, and are increasingly likely to remain so as petroleum reserves are reduced and new supplies prove more costly and difficult to secure. Further, certain of the petroleum-derived phthalate plasticizers have raised concerns for their potential to disrupt human endocrine activity, and regulatory controls have been established in a number of countries to address these concerns.
Unmodified renewable source derived oils, such as triacylglycerol oils, are largely incompatible with PVC resin, but certain modified derivatives of renewable source derived oils, such as epoxidized soybean oil (ESO), are compatible with PVC resin and have been actively investigated for use as a lower cost, renewable source derived alternative to the petroleum-based plasticizers, both as primary and secondary plasticizers. The interest in developing useful plasticizers from renewable sources, such as renewable source derived animal, algal, microbial, or plant (including vegetable) oils, has developed partly also from the expectation that such materials would be less likely to cause physiological disturbances or other injuries to persons coming into contact with products which require plasticizers in their composition. In recent years, as a result, a number of different renewable source-based plasticizers for PVC have been introduced in the literature and in the marketplace. The plasticizer compounds can be used alone or in various mixtures, including many other plasticizers known in the art, such as esters of dicarboxylic acids, citric acid, and the esters of aromatic dicarboxylic acids (e.g., phthalic acid esters). Particularly useful are mixtures comprising plasticizer compounds prepared from epoxidized triglycerides with a high degree of epoxidation for plasticizing PVC. Such epoxidized triglycerides can be typically exemplified by epoxidized soybean oil and epoxidized linseed oil, while other epoxidized renewable source derived oils are also useful. In such formulations, the epoxidized fatty acid fragments provide a desired stabilizing effect by acting as scavengers of acidic polymer decomposition products. The plasticizer compounds are useful to make various industrial and consumer articles, including flooring materials, siding elements for exteriors and interiors of buildings, window frames, flexible and rigid pipes, tubing, reinforced hoses, artificial leather, packaging of consumer articles, interior and exterior automotive parts, electronic equipment cases, various single and multi-layered films, vinyl office supplies, plastisols, and the like.
The purified epoxidized ester plasticizers of the present invention can be made by either transesterification or interesterification and a purification process according to the present invention, for use subsequently as primary or secondary plasticizers in a variety of polymers, including halogenated polymers, acid-functionalized polymers, anhydride-functionalized polymers, and nitrile rubbers. An exemplary halogenated polymer is a PVC polymer, where "PVC" or "polyvinyl chloride" as used herein is understood to cover the range of homo—and copolymers of vinyl chloride with typically up to 20% of co-monomers such as vinyl acetate, propylene, ethylene, diethyl maleate, dimethyl fumarate and other ethylenically unsaturated co-monomers. Examples of other halogenated polymers include polyvinyl halide polymers, chlorinated polyolefins and chlorinated rubbers. Suitable acid-functionalized polymers include acrylic acid-functionalized polymers, as well as acrylic and other polymers in need of plasticization to reduce glass transitions or improve toughness.
Where used as primary plasticizers, the purified epoxidized fatty acid esters can comprise preferably at least 20 percent by weight of a polymer composition, more preferably will comprise at least 30 percent by weight of a polymer composition, and most preferably will comprise at least 50 percent by weight of a polymer composition. A suitable composition can comprise a plastisol.
The resultant plasticized polymer compositions can be formulated, it is noted, in all other respects in a conventional manner, including with incorporating various kinds of additives in addition to the inventive purified epoxidized esters. When the purified epoxidized esters are used in preferred embodiments as the primary plasticizers of a primary/secondary plasticizer system, for example, a renewably-based secondary plasticizer and thermal stabilizer such as epoxidized soybean oil can be added, or other secondary plasticizers (including petroleum-based plasticizers) or other additives for improving one or more properties of heat stability, lubricity or weathering resistance, as ultraviolet absorbers, fillers, anti-oxidants, anti-static agents, anti-fogging agents, pigments, dyestuffs, crosslinking aids and the like can be incorporated in the compositions. The inventive purified epoxidized esters may also be used in certain embodiments in combination with other primary plasticizers such as dioctylphthalate, other phthalates, citrates, benzoates, trimellitates, and other aliphatic diesters, though preferably the plasticized polymer compositions of the present invention will not include any added phthalates and will include substantially only renewably-based or biobased plasticizers.
The epoxidized ester plasticizers to be purified according to the present invention are synthesized by known routes. For example, in commonly-assigned, co-pending U.S. patent application Ser. No. 14/125,602, published Apr. 24, 2014 as US Pat. Appl. Pub. No. 2014/0113999 for "Reduced Color Epoxidized Esters from Epoxidized Natural Fats and Oils", the contents of which are hereby incorporated by reference in their entirety, reduced color epoxidized fatty acid esters (such as epoxidized methyl soyate, EMS) are made from an epoxidized natural fat or oil (such as epoxidized soybean oil, ESO) through the inclusion of borohydride in either a transesterification process or in an interesterification process.
In another example, in commonly-assigned, co-pending U.S. patent application Ser. No. 14/350,590, published Sep. 4, 2014 as US Pat. Appl. Pub. No. US 2014/0249322 for "Making Epoxidized Esters from Epoxidized Natural Fats and Oils", the contents of which are hereby incorporated by reference in their entirety, epoxidized esters are made by a transesterification process using low moisture fats and oils. The products undergo phase separation, and reduced molar excesses of alcohol may be employed compared to processes not employing a low moisture feedstock.
In another example, in commonly-assigned U.S. Pat. No. 8,703,849, "Processes for Making High-Purity Renewable Source-Based Plasticizers and Products Made Therefrom", issued Apr. 22, 2014, the contents of which are hereby incorporated by reference in their entirety, we described processes for making certain high purity unsaturated fatty acid esters from alcohols including 5 to 7 members in a ring structure, whether cyclic, heterocyclic or aromatic in character, which esters could then be epoxidized (according to a second aspect) to yield renewable source-based plasticizers for polyvinyl halide polymers, and in particular, for PVC. The plasticizers could be incorporated easily into PVC as primary plasticizers at even plastisol levels, and provided plasticized PVC compositions in turn that exhibited improved and unexpected performance in certain respects.
While epoxidized benzyl esters of unsaturated fatty acids had been described or suggested previously for plasticizing PVC, see for example, U.S. Pat. No. 3,377,304 (epoxidized benzyl soyate) and British patent No. GB 1,049,100, the known methods of making those benzyl esters and subsequent plasticizers resulted in PVC compositional limitations and performance characteristics which had unfortunately limited the use of such materials only to be secondary plasticizers and thermal stabilizers.
We found that by preparing the indicated unsaturated fatty acid esters (including, of course, benzyl soyate esters), whether by reacting alcohols including 5 to 7 members in a ring structure with unsaturated fatty acid lower alkyl esters having low residual monoglycerides and diglycerides or by reacting the alcohols with an unsaturated fatty acid feed having a correspondingly low monoacylglycerol and diacylglycerol content, these limitations could be overcome.
One very important attribute of plasticizers is the degree of purity of the plasticizer. After plasticizer synthesis, common impurities include metals, ions, monohydric alcohols, such as methanol or benzyl alcohol, and polyhydric alcohols, such as glycerol. Impurities in plasticizers present several problems in the plasticizer and products made therefrom. Impurities may impart odors or colors to plasticizers. Metals and ions are especially problematic plasticizer impurities; they can interfere with the electrical properties of plastics that they are incorporated into, such as their electrical insulating ability. Nonhomogeneity of the polymer crystallite interstices is a result of contaminating ions in plasticized PVC: "The ions move through free spaces which exist in the non-crystalline part between polymer crystallites. The free spaces have nonhomogeneous size distribution depending on a property of polymers or crystallization conditions. The homogeneity or nonhomogeneity of the size of the free space affects the ionic motion, and consequently it also affects the electrical properties of polymer solids." ("Study of motion of impurity ions making influence on electrical properties of polymer solids in low frequency range," Anada, Y., Advanced Materials Research, 740, 630-635, 2013 (Trans Tech Publications Ltd.)). In PVC plastisols, the electrochemical potential (zeta potential) of PVC particles is related to plasticizer exudation. ("An attempt to describe nonspecific interactions of polymer-polymer type in the plastisol dispersions of poly(vinyl chloride)," Makarewicz, E., Colloid and Polymer Science 267(9), 803-7, 1989). The zeta potential of PVC particles is in turn influenced by the ionic impurities contained in the particles, which originated from additives. This can be very important in the final product, because the presence of even small amounts of acid or alcohol impurities in plasticizers can reduce the efficiency of the plasticizer. (http://www.plastemart.com/Plastic-Technical-Article.asp?LiteratureID=1602&Paper=essential-compounding-chemicals-used-with-PVC-resin-primary-secondary-plasticiser-heat-light-stabilisers, accessed Jul. 3, 2014).
Another potential source of impurities in epoxidized ester plasticizers is the characteristic oxirane ring. The labile nature of the epoxide functionality in the epoxidized renewable source derived fats or oils contemplated as starting materials for epoxidized esters renders the epoxides susceptible to formation of undesired by-products. This highly reactive ring is easily opened, and shows the typical reactions of ethylene oxide. Oxirane ring compounds are highly sensitive to acid-catalyzed reactions. They are also susceptible to reacting with alcohols, amines, carboxyl groups, imines, phenols, and inorganic cyanates. ("Epoxidation Products of Fatty Acids, Alkyl Fatty Acid Esters and Glycerides, etc. as Chemical Intermediates and Plasticizer/Stabilizers for Polymers, Resins and Rubbers, Part I" Lower, E. S., SOFW Journal 121(4) 278, 280-2 1995).
The problem of by-products arising from hydrolysis or rearrangement of epoxides and from cross-linking of the fatty acid chains is a recognized source of impurities in epoxidized ester plasticizers (U.S. Pat. No. 8,436,042, issued May 7, 2013, the contents of which are hereby incorporated by reference in their entirety).
Therefore, considerable effort is often expended to remove impurities from plasticizers due to the disproportionate negative effect of impurities on the properties of compositions, including PVC plastics, they are incorporated into. Unfortunately, the known approaches to plasticizer purification are cumbersome and costly. Plasticizers are often slightly acidic due to the presence of small amounts of organic acids. Acids in plasticizers, even at low concentrations, attack the plasticizer and will cause discoloration of PVC on exposure to slight heating. Washing (extraction with water) is often carried out on an industrial scale in the reactor vessel used to synthesize a plasticizer. The washing process is expensive, and consumes valuable reactor time that could be used in plasticizer production. Ironically, the water washing also generates large amounts of waste wash water, thus reducing process sustainability by running counter to the very values promoted by the use of renewable source derived plasticizers.
Metal ions and their corresponding salts are notoriously problematic in PVC for causing degradation, including photodegradation, of the PVC. Metal salt contaminants increase the light-sensitivity of PVC by acting as sensitizers of the decomposition of peroxide groups or by generating free radicals under UV irradiation. Typical ionic and metal contaminants in plasticizers include sodium, iron, calcium, phosphorus, zinc, boron, molybdenum, and aluminum.
One example of plasticizer purification is taught in U.S. Pat. No. 3,070,608 (issued Dec. 25, 1962, assigned to Swift & Company), which required extraction of methyl esters of epoxy acids with "a large volume of water" (Example 1, Col 3 line 4); the washing removed "excess alcohol, glycerine, and sodium methylate catalyst" (Example 4, Col 4 lines 20-23. Subsequent drying was also necessary. The use of a large volume of water is believed to be cumbersome and costly.
Another example of plasticizer purification is taught in U.S. Pat. No. 8,802,877 (issued Aug. 12, 2014; assigned to NPC Industrias Quimicas Ltda). In this application, product mixture purification required several steps:                "At the end of the transesterification reaction a purification step occurs through which the formed glycerin is decanted and separated. The reaction mixture is then neutralized with acid, washed and stripped (alcohol removal process), with steam and under a discreet vacuum (up to about 600 mmHg [80 kPa]), at temperatures varying from 120 to 220° C., depending on the type of alcohol which is retrieved and re-used in subsequent production. After the alcohol removal process, the product is filtered." (Col. 7 lines 4-12)The high-temperature stripping with steam can cause formation of heat-related defects, such as color defects, and the execution of so many steps is believed to be cumbersome and costly.
Yet another example of plasticizer purification is set forth in European Patent Application Publication No. EP2 070 980 (published Jun. 17, 2009, assigned to Nexoleum Bioderivados Ltda.). After the formation of epoxidized ethyl soyate plasticizer, phase separation was carried out in a separation funnel as follows:                "At the end of the reaction, the water phase is separated from the oil phase in a separation funnel. The oil phase contains the epoxidized ester and the formic acid. The wash of the oil phase is processed according to the procedure described for the wash of the ethyl ester after the transesterification; although the water needs to be preheated to 50° C. and the wash procedure shall be repeated until all the formic acid has been eliminated." Page 3 lines 47-51The execution of repeated washings with water preheated to 50° C. is believed to be cumbersome and costly.
Another example of plasticizer purification is taught in United States Patent Application Publication No. US2013/203907 (published Aug. 8, 2013, assigned to Arkema, Inc.). Residual sodium, calcium and/or magnesium ions, contaminants, and detrimental reaction by-products were removed from epoxidized plasticizers with one or two water-washing steps to remove hydrogen peroxide and formic acid. The compositions are then subjected to steam-stripping and drying under full vacuum (Example 1, [0043] of US2013/203907). The high-temperature stripping with steam can cause formation of heat-related defects, such as color defects.
In commonly-assigned United States Patent Application Publication No. US2014/113999, epoxidized methyl soyate having a Pt—Co Hazen color of 90 or less as determined by ASTM D1209 was obtained after neutralization with a solution of citric acid, three or four iterative water washes, drying over anhydrous magnesium sulfate, filtration, and vacuum drying overnight.
In another example of plasticizer purification, double distillation is proposed to remediate odor problems in plasticizers at (http://www.plastemart.com/Plastic-Technical-Article.asp?LiteratureID=1602&Paper=essential-cornpounding-ehemicals-used-with-PVC-resin-primary-secondary-plasticiser-heat-light-stabilisers, accessed Jul. 3, 2014). However, subjecting the plasticizer to double distillation can cause the formation of heat-related defects, such as color defects.
The present invention in one aspect addresses this need, in providing a process for purifying epoxidized ester plasticizer compositions. The process is simple and continuous, and does not require the high temperatures used in distillation.


The invention relates to a new method of determining the presence, absence, number or position(s) of one or more post-translational modifications in a peptide, polypeptide or protein. The invention uses transmembrane pores.

The functional properties of most proteins are regulated by post-translational modifications (PTM) of specific residues. Up to now, phosphorylation at serine, threonine or tyrosine is the most frequent experimentally determined PTM1 (http://selene.princeton.edu/PTMCuration). In eukaryotes, 30% (S. cerevisiae) to 50% (mouse) of protein species are phosphorylated2,3. Proteins of critical importance may have multiple phosphorylation sites, serving to activate or inactivate a protein, promote its degradation, or modulate interactions with protein partners4. For example, p53 has at least 18 phosphorylation sites4,5. Importantly, multi-site modifications can occur in different combinations, leading to different functional forms of a protein6.
Early studies of protein phosphorylation relied on 2D gel electrophoresis, which is based on changes in protein electrophoretic mobility and isoelectric point caused by the incorporation of phosphate groups7. 2D gel electrophoresis cannot resolve different phosphorylation sites within the same protein8,9. Recently, mass spectrometry (MS) of the phosphoproteome has come to the fore for studies of phosphorylation in vivo. Through the use of protease digestion and high-resolution MS, thousands of phosphoprotein species can be identified9,10. When samples from different sources (e.g. treated and control) are differentially labelled with isotopes, changes in the levels of phosphorylation at specific sites in specific proteins can be estimated11. Despite these advances, the determination of patterns of phosphorylation within individual protein molecules remains challenging2. For example, proteins monophosphorylated on one of two adjacent sites are difficult to distinguish. The occupancy and connectivity of phosphorylation sites is a problem ideally suited for single-molecule approaches.
Engineered protein nanopores have been used for the stochastic detection of a wide variety of molecules in solution12,13, ranging from divalent metal cations14 to organic molecules15 to chemically reactive substances16. Nanopore technology has also been investigated as an ultra-rapid, low-cost platform for single-molecule sequencing of DNA and RNA17,18. For example, single-stranded DNA can be ratcheted through protein pores with enzymes19-22 and the sequence read23-27 from base-dependent transitions in the ionic current28-31.

Method of analyzing post-translational modifications


A cross member unit for universal joints has a cross member (6) with four trunnions (17). Each two trunnions define a common longitudinal axis (7). Each trunnion (17) has an end face (18), a first sealing face (21) and a pre-sealing face (24). The pre-sealing face (24) is remote from the end face 18 and has a diameter increasing relative to the first sealing face (18). A bearing bush (9) is on each trunnion (17). Each bearing bush (9) has an open end 29 and has rolling contact members 27 rotatably supporting the trunnion (17) around the longitudinal axis (7) of the trunnion (17). An annular seal (30) is provided in each bearing bush 9. The annular seal (30) is held in the bearing bush 9 by a press fit. The annular seal (30) includes an annular carrier (31) which projects from the open end (29) of the bearing bush (9). The annular seal includes at least one first sealing lip (35) which is in contact with the first sealing face (18) of the trunnion (17). The annular seal has a pre-seal (38) in the form of a sealing lip or bead which is in contact with the pre-sealing face (24) of the trunnion 17. An end face (32) is on the carrier (31). The end face (32) is remote from the end face (18) of the trunnion (17). An annular gap (26) is formed between the end face (32) and a radial face (40) of a shoulder (39) of the trunnion (17).

This application claims priority to German Patent Application Nos. 10140372.0 filed Aug. 23, 2001 and 10204684.0 filed Jun. 2, 2002, which applications are herein expressly incorporated by reference.
The invention relates to a cross member unit for universal joints having a cross member with four trunnions. Each two of the trunnions have a common longitudinal axis. A bearing bush, per trunnion, supports the trunnions via rolling members. A sealing assembly, per bearing bush, effectively seals between the bearing bush and the trunnion. The sealing assembly ensures that lubricating grease for the rolling members cannot leave the bearing bush.
DE 196 22 444 C1 discloses a cross member unit. A main seal with a carrier is firmly positioned in an open end of the bearing bush. The carrier, to provide axial security, is formed into an annular groove which is arranged coaxially relative to a longitudinal axis of the trunnion. The main seal has two sealing lips which are formed onto the carrier. The lips are in sealing contact with sealing faces of the trunnion. The carrier projects axially from the open end of the bearing bush. A pre-seal is firmly slid onto a seat portion of the trunnion. The cross-section of the pre-seal has a U-shaped profile which embraces the projecting carrier of the main seal. A sealing lip is provided at one radially outer limb of the U-profile. The sealing lip is in sealing contact with a conical face of the bearing bush. A further sealing lip is in sealing contact with the metallic carrier of the main seal. The two sealing lips of the pre-seal ensure that even under the influence of a water jet of a high-pressure cleaning device, dirt cannot easily enter the region of the main seal. However, the pre-seal sealing lip which stops against the conically shaped sealing face of the bearing bush is directly subjected to external influences. In addition, it is necessary to provide two separate seals. Furthermore, the cross member unit according to DE 196 22 444 C1 has a stop disc between the main seal and the rolling members. The stop disc axially supports the rolling members.
It is an object of the present invention to provide a cross member unit for universal joints which includes a sealing assembly with a small number of parts. Also, the trunnion is stronger with respect to its diameter.
In accordance with the invention, a cross member unit for universal joints has a cross member with four trunnions. Each two trunnions define a common longitudinal axis. Each trunnion has an end face, a first sealing face and a pre-sealing face. The pre-sealing face is remote from the end face. The diameter of the pre-sealing face is increased relative to the first sealing face. A bearing bush is present per trunnion. The bearing bush has an open end and rotatably supports, via rolling members, the trunnion around the longitudinal axis of the trunnion. An annular seal is provided per bearing bush. The annular seal is held in the bearing bush by a press-fit. The annular seal includes an annular carrier which projects from the open end of the bearing bush. The annular seal includes at least one first sealing lip which is in contact with the first sealing face of the trunnion. The annular seal includes a pre-seal in the form of a sealing lip or bead which is in contact with the pre-sealing face of the trunnion. An end face of the carrier, remote from the end face of the trunnion, forms an annular gap together with a radial face of a shoulder of the trunnion. The cross member unit includes only one seal with at least one first sealing lip which acts as a main seal, and a pre-seal, in the form of a sealing lip or bead, which prevents dirt from penetrating into the region of the first sealing lip.
There is no need to provide a seat portion on the trunnion so that the pre-seal is in contact with a pre-sealing face of the trunnion. The diameter of the pre-sealing face of the trunnion can be greater than the diameter of a seat portion for a separate pre-seal. This means that the trunnion is reinforced in the critical region where the highest stresses occur. Since only one seal is provided, which is inserted into the open end of the bearing bush, the number of necessary assembly stages is reduced.
Furthermore, there is no need to provide a sealing face at the bearing bush. Thus, the bearing bush can be produced more easily and more cost-effectively. Further, it is not necessary to provide an inner circumferential groove in the bearing bush. The groove receives the carrier to axially secure the seal. The axial distance which the seal can be displaced inside the bearing bush, due to external forces, is delimited by the rolling members and by the radial face of the shoulder of the trunnion. In addition, the press fit ensures that, under normal loads, the seal is firmly positioned inside the bearing bush. The annular gap between the seal carrier and the radial face of the trunnion shoulder is dimensioned to compensate for any tolerances in the axial length of the seal and in the length of the rolling members. Therefore, in extreme case, the width of said annular gap can assume a zero value. The carrier can be metal or plastics, such as PA 6.6 for example.
Furthermore, the annular gap acts as a labyrinth seal. Thus, the pressure of a water jet of a high-pressure cleaning device is reduced when the water jet enters the annular gap. The pre-seal is protected by the carrier from direct external influences.
To increase the sealing effect, the seal may include a second sealing lip. The second sealing lip is in contact with a second sealing face of the trunnion. The second sealing lip is arranged in the direction of the longitudinal axis of the trunnion between the pre-seal and the first sealing lip. The first sealing lip and the first sealing face are designed so that the first sealing lip is pressed radially against the first sealing face. The second sealing lip and the second sealing face are designed so that the second sealing lip is axially pressed against the second sealing face.
In addition, it is possible to provide a third sealing lip. The third sealing lip is in contact with a third sealing face of the trunnion. The third sealing lip is arranged between the first sealing lip and the second sealing lip.
The carrier includes a radial annular portion to eliminate a stop disc between the seal and the rolling members. The radial annular portion remote from its end face includes a stop face for the rolling members which faces a way from the end face. The annular portion of the carrier thus takes on the function of a stop disc. The stop face includes a friction-reducing coating to reduce the friction between the radial annular portion of the carrier and the rolling members. Accordingly, since there is no need for a stop disc, the rolling members can be longer. Thus, the rolling members length prolongs the service life of the rolling member bearing.
The cross-section of the radial annular portion can be convex towards the rolling members. The rolling members, in the region of their axis of rotation, stop against the radial annular portion.
An outer seal is circumferentially secured to an outer face of the carrier portion to prevent any spray water from entering the region between the carrier of the seal and the bearing bush. The outer seal projects from the open end of the bearing bush. The outer seal is in sealing contact with an outer sealing face of the bearing bush. The outer seal effectively prevents spray water from entering the region between the carrier and the inner circumferential face of the bearing bush even when the universal joint is cleaned by a high-pressure cleaning device.
In a preferred embodiment, the outer sealing face includes a chamfer. The chamfer starts from an end face at the open end of the bearing bush and extends to an inner circumferential face of the bearing bush. The outer seal is in sealing contact with the chamfer.
The outer seal includes an outer sealing lip to increase the sealing effect of the outer seal. The sealing lip is in contact with the outer sealing face of the bearing bush. The outer sealing face may include an end face at the open end of the bearing bush. The outer seal is in sealing contact with the bearing bush.
Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.

Cross member unit for universal joints having a trunnion seal


The present invention provides a crystal of reduced glutathione having excellent powder properties and a method for producing the same. The present invention relates to a crystal of reduced glutathione, wherein the average crystal thickness is 10 μm or more.

Reduced glutathione (γ-L-glutamyl-L-cysteinyl-L-glycine) is a reducing compound widely existing in organisms and is known to have a detoxification effect in the liver. Therefore, reduced glutathione has been widely used as a product such as a pharmaceutical product, a health food, and a cosmetic product, or a raw material or an intermediate thereof. A crystal of reduced glutathione is known to have two types of polymorphisms: α crystal and β crystal (Non-Patent Document 1) and, a crystal which is generally utilized as a product is the α crystal because of its physical properties.
However, the α-type crystal of reduced glutathione is likely to become a needle-like or elongated columnar crystal because the crystal growth in directions other than the long-axis (longitudinal) direction is slow. The ratio of the crystal length to the crystal width becomes large because of this property, and as a result, there arises a problem that the specific volume is increased and the powder flowability is deteriorated. In order to improve the powder properties, it is necessary to allow the crystal to grow not only in the longitudinal direction, but also in the lateral direction and the height direction.
Patent Document 1 describes the improvement of the powder properties of reduced glutathione and discloses a method in which a crystal of reduced glutathione is added as a seed crystal to an aqueous solution in which reduced glutathione is dissolved, followed by stirring, thereby precipitating reduced glutathione in the aqueous solution.

Crystal of reduced glutathione and method for producing same


Disclosed is a method for manufacturing a transistor in a semiconductor device, which can improve a device's refresh characteristics. The method includes: providing a silicon substrate having active and field regions; performing a channel ion implantation into the substrate; sequentially forming a hard mask film and a photoresist pattern exposing a gate formation region where the channel ion implantation occurred; performing a second, higher concentration channel ion implantation using the photoresist pattern as a mask, forming doped regions in the substrate at the gate formation region and sides; etching a hard mask using the photoresist pattern as a barrier; removing the photoresist pattern; etching the substrate using a portion of the remaining hard mask as a barrier forming a groove; removing the remaining hard mask; forming a gate in the groove where the hard mask was removed; and forming source and drain regions at both sides of the gate.

1. Field of the Invention
The present invention relates to a method for manufacturing a semiconductor device, and more particularly, to a method for manufacturing a transistor in a semiconductor device, which can improve the refresh characteristics of the device.
2. Description of the Prior Art
Recently, as the design rule of a device pattern shrinks below 100 nm, the channel length of a cell transistor corresponding thereto is also very reduced. As a result, the existing planar transistor structures encounter limitations in realizing the Vt target of the cell transistor required in a specific device. For this reason, a method for forming a transistor with a recessed channel structure was proposed. This transistor with the recessed channel structure has a channel length secured by selectively etching a portion of the active region of a substrate, which corresponds to a region where a gate is to be formed.
FIG. 1 is a cross-sectional view for explaining a method for manufacturing a transistor in a semiconductor device according to the prior art. As shown in FIG. 1, the silicon substrate 10 is first provided which has active and field regions defined thereon and the device isolation film 11 in the field region. Then, a portion of the substrate 10 corresponding to a gate formation region, is recessed by selective etching to form the groove 12 (recessed channel structure). Following this, well ion implantation, channel ion implantation processes and the like are sequentially performed in a state where a screen oxide film (not shown) has been formed on the surface of the substrate 10 including the groove 12. The channel ion implantation process is performed with an ion implantation dose of about 1E13 atoms/cm2.
Thereafter, on the surface of the substrate 10 including the groove 12, a gate oxide film (not shown), a gate conductive film (not shown) and a gate hard mask film (not shown) are sequentially formed and then selectively etched to form the gate 16 in the groove 12. In FIG. 1, the reference numeral 13 designates a gate oxide film remaining after the etching, the reference numeral 14 designates a gate conductive film remaining after the etching, and the reference numeral 15 designates a gate hard mask film remaining after the etching. Next, low-concentration impurity ions are implanted into the substrate 10 at both sides of the gate 16 so as to form lightly doped drains (LDDs). Subsequently, a spacer 18 are formed on both sidewalls of the gate 16, and then, high-concentration impurity ions are implanted into the substrate 10 at both sides of the gate 16 including the spacer 18 so as to form the source and drain regions 19.
FIG. 2 shows problems occurring in the prior art and shows the simulation results for potential distribution in the cell transistor having the recessed channel structure. The simulation results were obtained under conditions where gate voltage is referenced to ground and a bias voltage of 1.0 V is applied to a storage node. In the method for manufacturing the transistor of a semiconductor device according to the prior art, as shown in FIG. 2, depletion regions in the channel regions corresponding to the sides of the gate 16 are greatly enlarged so as to cause leakage current. Thus, the data retention time of the device is shortened, resulting in deterioration in the refresh characteristics of the device. In FIG. 2, the reference character "A" designates a region with the most severe depletion.

Method for manufacturing transistor in semiconductor device


A liquid crystal display device includes first and second substrates facing each other; a liquid crystal layer between the first and second substrates; and a seal pattern between the first and second substrates surrounding the liquid crystal layer, wherein the seal pattern is made of one of frit glass and glass paste.

1. Field of the Invention
The present application relates to a liquid crystal display device and, more particularly, to a liquid crystal display device and a fabrication method thereof.
2. Description of the Related Art
Display devices used in the past have typically been cathode-ray tubes (CRT). Presently, however, much effort has been made to study and develop various types of flat panel displays, such as liquid crystal display (LCD) devices, plasma display panels (PDP), field emission displays, and electro-luminescence displays (ELD), as substitutes for CRTs. Of these flat panel displays, LCD devices have advantages, such as high resolution, light weight, thin profile, compact size, and low power supply requirements.
An LCD device typically includes two substrates that are spaced apart and face each other with a liquid crystal material interposed between the two substrates. The two substrates include electrodes that face each other such that a voltage applied between the electrodes induces an electric field across the liquid crystal material. Alignment of the liquid crystal molecules in the liquid crystal material changes in accordance with the intensity of the induced electric field, thereby changing the light transmissivity of the LCD device. Thus, the LCD device displays images by varying the intensity of the induced electric field.
FIG. 1 is a schematic plan view of an LCD device according to the related art, and FIG. 2 is a cross-sectional view of an LCD device of FIG. 1.
As shown in FIGS. 1 and 2, the related art LCD device 1 includes a first substrate 11, a second substrate 61 and a liquid crystal layer 90 between the two substrates 11 and 61.
On the first substrate 11, a plurality of gate lines 13 and a plurality of data lines 30 cross each other to define a plurality of pixel regions P. A plurality of thin film transistors Tr are disposed at crossing portions of the gate and data lines 13 and 30. A pixel electrode 50 is connected to the thin film transistor Tr, in each pixel region P. The thin film transistor Tr includes a gate electrode 15, a semiconductor layer 23 having an active layer 23a and an ohmic contact layer 23b, a source electrode 33 and a drain electrode 35. A gate insulating layer 20 is disposed on the gate electrode 15, and a passivation layer 40 has a drain contact hole 43 exposing the drain electrode 35.
On the second substrate 61, a black matrix 63, including a first black matrix 63a and a second black matrix 63b are disposed. The first black matrix 63a has a lattice shape surrounding each pixel region P to shield the gate and data lines 13 and 30 and the thin film transistor Tr. The second black matrix 63b is disposed at a peripheral region of the second substrate 61 and is connected to end portions of the first black matrix 63a.
A color filter pattern 66 including red (R), green (G) and blue (B) color filter patterns 66a, 66b and 66c fills openings of the first black matrix 63a and corresponds to each pixel region P. A common electrode 70 is disposed on the color filter pattern 66.
A spacer 56 is disposed between the first and second substrates 11 and 61 to maintain a cell gap.
A seal pattern 85 is disposed along the second black matrix 63b to surround a display region AA. The seal pattern 85 prevents leakage of the liquid crystal and attaches the first and second substrates 11 and 61.
A gate pad region GPA and a data pad region DPA are disposed at a non-display region that is outside the seal pattern 85 of the first substrate 11. In the gate and data pad regions GPA and DPA, gate and data pads are formed, respectively. The gate pad includes a gate pad electrode 12 and a gate pad electrode terminal 52. The data pad includes a data pad electrode (not shown) and a data pad electrode terminal 54. The data pad electrode may be made of the same material as the data line 30 in a process of forming the data line 30, and the data pad electrode terminal 54 is made of the same material as the pixel electrode 50 in a process of forming the pixel electrode 50.
The gate and data pads are connected to a PCB (printed circuit board) having driving circuits through a TCP (tape carrier package) film. A gate driver GD or a data driver is disposed on the TCP film.
A connection part 80 of an end portion of the TCP film contacts the gate or data pads i.e., the gate pad electrode terminal 52 or the data pad electrode terminal 54. A protecting film 87 covers the connection part 80. The protecting film 87 functions to prevent detachment of the TCP film and the gate and data pads.
In the related art LCD device, the seal pattern, the protecting film and the spacer are made of a heat-cured or UV-cured organic material including epoxy or acrylic. However, when such material is used, there are some problems. For example, when the seal pattern 85 is made of such material, breakdown of the seal pattern increases due to heating, and thus the drawbacks increase. In addition, epoxy and acrylic are expensive. Therefore, productivity decreases and product cost increases.

Liquid crystal display device with protection film at connection of TCP and therminal and fabrication method thereof


A catalytic reactor or heat exchanger includes a monolith defining a plurality of leaves, the monolith having a generally annular cross-section. The monolith is disposed within a generally cylindrical outer tube, and around a corrugated inner tube. The reactor includes a device for urging the monolith radially outward, so as to maintain contact between the monolith and the outer tube. Such device may include a coned washer, or it may be defined by a folded flap that is integral with the inner tube. In either case, the reactor compensates for metal creep, and virtually insures continued contact between the monolith and the outer tube.

This invention relates to the field of surface catalytic reactions and/or heat exchange. The present invention provides a reactor which fits within a cylindrical outer tube, and which effectively transfers heat from the exterior of the outer tube to the reactor, or from the reactor to the outer tube.
The reactor of the present invention achieves the same objectives as those of the catalyst supports described in copending U.S. patent application Ser. No. 11/132,691, filed May 19, 2005, Ser. No. 10/896,302, filed Jul. 21, 2004, and Ser. No. 11/105,973, filed Apr. 14, 2005. The disclosures of the above-mentioned applications are incorporated by reference herein.
One of the objectives of the reactors described in the above-cited applications is to avoid the problems associated with the use of ceramic materials in the manufacture and operation of catalytic reactors. Packed bed ceramic catalysts have the disadvantage that they have low thermal conductivity, making it difficult to transfer heat from the periphery of the reactor to the inside, or vice versa. Also, the thermal mismatch between the metal and ceramic portions of prior art reactors eventually leads to pulverization of the ceramic material, thus limiting the useful life of the reactor. Like the devices described in the above-cited applications, the present invention also comprises an all-metal structure which inherently avoids these problems.
A reactor having radial leaves, as described in application Ser. No. 11/132,691, has shown good heat transfer, and therefore good overall performance, not only when simulated in a computer model, but also when evaluated as a prototype in a heat transfer rig. However, the prototype has proved quite difficult to build, and is not believed to be an optimum solution, from the standpoint of ease of manufacture.
The reactors shown in the above-cited applications, and others reactors of the prior art, occupy substantially all of the space within a cylindrical outer tube. An inherent problem with reactors of this kind is that they do not perform particularly well near the center of the reactor. It has been found that most of the catalytic reactions occur near the outer portions of the reactor, i.e. near the outer tube. This problem reduces the efficiency of the reactor, and makes it very difficult or impossible to achieve the desired level of conversion.
The present invention provides a reactor structure which solves the above problem. The reactor of the present invention is substantially more efficient than reactors of the prior art, and is also relatively easy to manufacture.
Another problem encountered with reactors installed in cylindrical tubes is that of metallic creep. The reactors described in the above-cited applications, as well as the reactor of the present invention, are intended to be stuffed into a large metallic outer tube and operated at high temperatures (in the range of 850-900° C.) and high pressures (in the range of 20-30 bar). The pressure creates a large hoop stress, which the tube material has difficulty resisting at the high temperature. Over a period of years, creep in the metal outer tube causes the diameter of the tube to grow. Even a few millimeters of growth in the tube diameter creates an undesirable gap between the reactor and the surrounding tube. A typical reactor which has been stuffed into a new tube, such that the reactor is initially in good contact with the tube, will lose contact with the tube when the tube creeps over the years. Such creep will cause a significant drop in performance.
The present invention provides structure which avoids the above problem. The invention includes a device that continuously compensates for creep, insuring proper contact between the reactor and the surrounding outer tube.
The reactor of the present invention can be used, for example, in the field of catalytic fuel reforming, to make hydrogen, which is then used to generate electricity through a fuel cell, or in other industrial processes such as oil and gas refining, ammonia and fertilizer production, hydrogenation of oils and chemicals, and iron ore reduction. The reactor could be used as a catalytic or non-catalytic combustor, or as a simple heat exchanger.


A user-defined virtual private cloud computing network is provided that includes a user interface for selecting a plurality of network connectivity features for designing the user-defined virtual private cloud computing network. The virtual private cloud computing network includes tangible storage elements and tangible computing elements selected from a cloud computing network service provider using the user interface, using the user interface each network. The tangible storage elements and tangible computing elements are connected in accordance with network element configuration statements that instantiate actions particular to defined network connectivity features in accordance with defined usage rules. The virtual provide cloud computing network is configured and implemented in accordance with the selected network connectivity features using the tangible storage elements and tangible computing elements.

1. Field of the Disclosure
The present disclosure relates to cloud computing networks. More particularly, the present disclosure relates to a network connectivity wizard for designing customized virtual private cloud computing networks.
2. Background Information
Cloud computing networks provide network customers with on-demand network resources from the existing network of a cloud computing network service provider. Customers can request cloud computing network resources to support customer applications that might otherwise only be implemented on the customers' internal network resources. Configuration management for cloud computing networks is automated. Service providers predefine selectable standardized configuration templates, and customers select a predefined configuration template when network resources are to be requested to support a customer application. The selected predefined configuration template is populated to generate a configuration of network elements sufficient to support the customer application.

This patent is subject to a terminal disclaimer.

Network connectivity wizard to support automated creation of customized configurations for virtual private cloud computing networks


A line-of-sight analysis method, performed by a computer, includes: identifying, when a selection event with respect to a first object out of a plurality of objects is detected, a second object different from the first object, based on a detection status of line-of-sight relative to the objects in a most recent time period of the selection event; and outputting information indicating the identified second object.

Proposed is a technology in which the number of times that a user gazes at a commodity from a start to an end of a buying behavior by the user is counted, and a commodity the number of times for which is not less than a given number of times is estimated as a gazed commodity. Herein, it is determined that the user has certain interests in all the commodities the number of gazed times for which is not less than the given number of times, or vacillates whether to purchase the commodities.
Examples of the related art include Japanese Laid-open Patent Publication No. 2009-42956.

Non-transitory computer-readable storage medium for storing line-of-sight analysis program, line-of-sight analysis method, and line-of-sight analysis apparatus


A handcart includes a main body section, a pair of wheels provided to the main body section, and operation sections provided at the rear in the traveling direction of the main body section. A holding section is rotatably fitted to a vertical portion of an arm section of each of the operation sections. A user can change the direction of the handcart by making a pushing-forward motion or a pulling-back motion while holding the holding sections. This saves the user from having to move his or her body when making a direction change, thereby allowing the user to easily change the direction of the handcart in a narrow space as well as reducing labor necessary for making the direction change.

1. Field of the Invention
The present invention relates to a handcart, and more specifically, to a handcart allowing a user to easily change of its direction.
2. Description of the Related Art
As handcarts, a variety of types have been hitherto known, such as a shopping cart, a carriage, a cultivator used for agricultural work, a lawn mower, and so forth.
An example of such conventional handcarts is disclosed in Japanese Unexamined Patent Application Publication No. 11-139315. As shown in FIG. 8, this handcart 30 includes a luggage carrier 31, wheels 32 provided to the luggage carrier 31, and operation sections 33 on the right and left sides at the rear of the luggage carrier 31. The handcart 30 is configured so that its movement in the traveling direction or its change in direction can be performed by a user applying a force to the handcart while holding the operation sections 33.
Such a conventional handcart 30 is adapted to have its direction changed by a degree of θ1 from a line I-I to a line II-II, by the user applying a force to the handcart while holding the operation sections 33. That is, the user moves his or her body by the degree of θ1 from the line I-I to the line II-II, and thereby, for example, relative to the left-side wheel 32, both wheels 32 are moved from the positions on a line A1-A1 to the positions on a line B1-B1.
In this manner, the conventional handcart needs labor for moving the user's body when he or she attempts to change the direction of the handcart. In addition, the conventional handcart requires a space for moving the user's body. This has undesirably made it difficult to change the direction of the handcart, e.g., on a narrow passage or at a place with an obstruction such as a wall.


Techniques, systems, architectures, and methods for reducing peak power during an Analog-to-Digital Conversion (ADC) process, in embodiments on a Focal Plane Array (FPA).

Digital detection of images is a very widely used technology, having applications ranging from consumer-oriented cameras and video apparatuses to law enforcement and military equipment. For virtually all of these applications, there is a growing demand for higher image pixel counts, higher pixel density, increased sensitivity, improved dynamic range, lower power consumption, faster image processing, and the ability to switch between modes offering different balances of these characteristics, dependent on the requirements present at a given time.
At the heart of all digital imaging systems, which may be referred to generally as Solid State Area Array Imaging Devices (SSAAIDs), is the Focal Plane Array ("FPA"), which is a two-dimensional array of elements upon which an image is focused, whereby each of the FPA elements or "pixels" develops an analog output "signal charge" that is proportional to the intensity of the electromagnetic radiation that is impinging on it after a given interval of time. This signal charge can then be stored (integrated), measured (counted), and used to produce an image.
The storage and measurement of the electromagnetic radiation that has impinged on a pixel over a given amount of time is typically accomplished using a Read-Out Integrated Circuit (ROIC). In some ROICs, the signal charge is integrated in the pixel, typically onto a capacitor, and then the analog voltage representing the integrated signal is readout out of the array. The signal can then be sent off the ROIC, in the case of all analog ROICs, or can be converted to a digital signal by Analog-to-Digital Converting (ADC) circuitry. Digital pixel Read-Out Integrated Circuits (DROICs), such as that shown in FIG. 1, both integrate and convert (ADC) the signal charge inside each pixel. This simultaneous conversion of every pixel results in very high current requirements at the start of the Analog-to-Digital Conversion (ADC) process, which may also be herein referred to simply as conversion, that taper down to no current flow as conversion completes, as shown in FIG. 2A. The aforementioned high current requirement limits at least the achievable pixel count, pixel density, sensitivity, dynamic range, and conversion speed of the imaging device.
What is needed, therefore, are systems and methods to reduce the peak power required for a pixel-array during the analog to digital conversion process.

Low power in-pixel single slope analog to digital converter (ADC)

BAE Systems Information and Electronic Systems Integration Inc.


An abnormality detecting apparatus includes an air/fuel ratio sensor that detects an air/fuel ratio within a range including the stoichiometric air/fuel ratio, an admittance detector for detecting an admittance of the sensor, and a temperature detector for detecting a temperature of the sensor. This apparatus detects an abnormality of the sensor when the detected temperature is at a first temperature which is higher than an activation temperature of the sensor and the detected admittance is less than a first determining value. The apparatus also detects a disconnection abnormality of the sensor when the detected temperature is at a second temperature, which is higher than a minimum temperature at which admittance can be detected for a normally operation and lower than the first temperature, and the detected admittance is less than a second determining value for determining disconnection of the sensor which is less than the first determining value.

1. Field of the Invention
This invention relates to an abnormality detecting apparatus and an abnormality detecting method for an air/fuel ratio sensor, which is capable of detecting an air/fuel ratio within a wide range that includes the stoichiometric air/fuel ratio.
2. Description of the Related Art
A typical internal combustion engine burns a mixture of air and fuel in a combustion chamber and discharges exhaust gas produced by that combustion to the outside through an exhaust passage. The exhaust passage is provided with an oxygen sensor or an air/fuel ratio sensor to detect the air/fuel ratio of the mixture from the oxygen concentration in the exhaust gas. In the internal combustion engine, feedback control is performed by adjusting the fuel quantity so that the air/fuel ratio detected by this air/fuel ratio sensor becomes a target air/fuel ratio (usually the stoichiometric air/fuel ratio) that is set in advance.
If an abnormality occurs in the air/fuel ratio sensor, however, this type of air/fuel ratio feedback control is no longer able to be appropriately performed, so various measures (such as switching to open loop control) are performed in response to a detected abnormality.
More specifically, abnormality detection for an air/fuel ratio sensor is performed by detecting the temperature of the sensor and the reciprocal of the sensor's resistance value, i.e., the admittance indicative of the ease with which current flows, and comparing that with a determining value.
As shown in the routine illustrated in the flowchart in FIG. 6, the abnormality detecting apparatus for this air/fuel ratio sensor detects the admittance of the sensor when a period of time T has passed after startup of the internal combustion engine (steps S210, S220, and S230). This period of time T is the time required to ensure output from the air/fuel ratio sensor after the engine is started, and is longer than a period of time SA required for the air/fuel ratio sensor to be heated to an activation temperature by a heater. This period of time T is obtained by testing or the like beforehand.
Next, an abnormality in the air/fuel ratio sensor is detected by comparing the detected admittance with a determining value YJ (step S240). Here, there is a tendency for the admittance at the same temperature to drop when there is a decline in performance of the air/fuel ratio sensor due to, for example, deterioration over time. Therefore, as shown in FIG. 7, a decline in performance of the sensor can be detected when the detected admittance is less than the determining value YJ.
When an abnormality is detected (i.e., YES in step S240), a warning lamp indicating an abnormality in the sensor is illuminated and the control system of the fuel quantity is switched to abnormality response control (steps S250 and S260).
When a disconnection abnormality has occurred in the air/fuel ratio sensor, current stops flowing to the sensor so the admittance of the sensor becomes "0". Thus, in both the case in which there is a decline in performance of the sensor as well as the case in which there is a disconnection abnormality in the sensor, the admittance of the sensor becomes lower than the determining value YJ. Therefore, the abnormality detecting apparatus for the air/fuel ratio sensor detects these abnormalities by comparing the admittance with the determining value.
However, while it is necessary to determine the output's precision after the temperature of the sensor reaches the activation temperature in order to detect a decline in performance of the air/fuel ratio sensor, it is not always necessary to make that determination in order to detect a disconnection abnormality. Notwithstanding, the abnormality detecting apparatus for the air/fuel ratio sensor is unable to detect a disconnection abnormality until the temperature of the sensor reaches the activation temperature. As a result, a disconnection abnormality cannot be detected early on, so that measures in response to that abnormality cannot be taken at an early stage.

Abnormality detecting apparatus and abnormality detecting method for an air/fuel ratio sensor


A foamed axial cable includes a pair of signal conductors, an insulation covering a periphery of the signal conductor and formed of a foamed material, a skin layer covering a periphery of the insulation and formed of a non-foamed material, and a shield conductor on a periphery of the skin layer. An outer surface of the skin layer or an inner surface of the shield conductor includes a fine groove formed thereon so as to have a void between the skin layer and the shield conductor.

1. Field of the Invention
This invention relates to a foamed coaxial cable and a multicore cable using an insulation formed of a foamed material.
2. Description of the Related Art
A high speed transmission foamed coaxial cable is known that uses a low-permittivity insulation formed of a foamed material (See e.g. JP-A-2003-141944).
For example, a foamed coaxial cable 21 as shown in FIG. 2 is known that is composed of a pair of signal conductors 2, an insulation (or formed insulation) 3 which is of a foamed material for collectively covering the periphery of the signal conductor 2, a non-foamed skin layer (or outer skin layer) 4 which covers the periphery of the insulation 3, and a shield conductor 5 disposed on the periphery of the skin layer 4.
The other related art may be JP-A-2010-080097 and JP-A-2008-293862.

Foamed coaxial cable and multicore cable


The present invention provides transparent film sheets for use in projection by an OHP which can be used both in dry copying and in the ink-jet printing of characters and/or pictures, can be directly printed with a jet printing ink without the intervention of a layer receptive to the jet printing ink, can be disposed of in a state capable of maintaining secrecy after use without the necessity of being shredded, and can be disposed of as a class of recycling waste like common white paper. Specifically, the present invention provides transparent film sheets formed of a cellulose ether derived from cellulose which is the basic component of common paper.

1. Field of the Invention
This invention relates to film sheets for use in projection by an overhead projector (hereinafter abbreviated as xe2x80x9cOHPxe2x80x9d) which is used in a meeting, conference or the like.
2. Description of the Related Art
As transparent film sheets for use with OHPs, transparent film sheets formed of polyesters such as polyethylene terephthalate are being widely used.
These polyester films have surface properties and heat-resisting properties which permit characters and/or pictures to be easily printed thereon by dry copying techniques such as xerography and, moreover, have high strength and excellent shelf stability.
In recent years, the spread of personal computers has made it easy to prepare materials for presentation in a conference or meeting. In particular, even diversely colored materials may be easily prepared.
Recently, there are some cases in which materials prepared with a personal computer are used for purposes of presentation by direct projection by a liquid crystal projector or the like. However, it is still common practice to prepare materials for use with an OHP by printing colored materials on common white paper with a printer of the ink-jet printing type and then copying them onto special-purpose polyester film sheets by means of a color copying machine, or by printing characters and/or pictures directly on such polyester film sheets by means of a printer designed for direct printing thereon. The reason for this is that polyester film sheets cannot be directly printed with a jet printing ink. Recently, a multilayer transparent film obtained by forming a polyvinyl alcohol-containing layer receptive to a jet printing ink over a polyester film is available. This film makes it possible to prepare materials for use with an OHP directly by means of an ink-jet printer which is less expensive than color copying machines.
As described above, such films formed of a polyester alone have high transparency and excellent shelf stability. However, when it is desired to dispose of the films having become unnecessary after use, highly secret materials must be treated by shredding or the like. Thus, they must be disposed of in a way different from recycling waste such as materials prepared from common white paper.
The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide transparent film sheets for use in projection by an OHP which can be used both in dry copying and in the ink-jet printing of characters and/or pictures, can be directly printed with a jet printing ink without the intervention of a layer receptive to the jet printing ink, can be disposed of in a state capable of maintaining secrecy after use without the necessity of being shredded, and can be disposed of as a class of recycling waste like common white paper.
As a result of intensive investigations carried out with a view to solving the above-described problems, the present inventors have now found that film sheets formed of a cellulose ether derived from cellulose which is the basic component of common paper can be printed with characters and/or pictures by means of either an ink-jet printer or a dry copying machine, are not liable to curling during use, enable the projection of sharp images because of direct printing with a jet printing ink without the intervention of a layer receptive to the jet printing ink, and are stable because of their low hygroscopicity. The reason why the OHP film sheets formed of a cellulose ether can be directly subjected to ink-jet printing is believed to be that a cellulose ether generally has a surface-active effect owing to the balance between the ether substituent groups and the hydrophilic and hydrophobic groups inherently present in the molecule of the cellulose and, therefore, a film formed of the cellulose ether exhibits an improvement in the adhesion of an ink. Moreover, it has also been found that, when the sheets have become unnecessary after use, they can be dipped in water to make the printed characters and/or pictures undiscernible, and then disposed of, and that the sheets can be disposed of as a class of combustible or recycling waste like paper, because an aqueous solution of a water-soluble cellulose does not constitute a source for BOD (biochemical oxygen demand) upon disposal. The present invention has been completed on the basis of these findings.
The OHP film sheets of the present invention can be printed with characters and/or pictures by means of either an ink-jet printer or a dry copying machine, are not liable to curling during use, enable the projection of sharp images because of direct printing with a jet printing ink without the intervention of a layer receptive to the jet printing ink, and are stable because of their low hygroscopicity. Moreover, since cellulose which is the basic component of paper is used as a raw material, the sheets which have become unnecessary after use can be dipped in water to make the printed characters and/or pictures undiscernible, and then disposed of. On that occasion, the sheets can be disposed of as a class of combustible or recycling waste like paper, because an aqueous solution of a water-soluble cellulose does not constitute a source for BOD upon disposal. Furthermore, conventional OHP film sheets are inconvenient in that only the surface-treated side must be chosen and used. In contrast, the OHP film sheets of the present invention have the advantage that either side may be chosen and used, depending on the manner of use.
The present invention is more specifically described hereinbelow. However, it is to be understood that the present invention is not limited to the embodiments described below.
Preferred examples of the cellulose ether used in the present invention include, but are not limited to, alkylcelluloses such as water-soluble methylcellulose (MC); hydroxyalkyl alkylcelluloses such as hydroxypropyl methylcellulose (HPMC), hydroxyethyl methylcellulose (HEMC) and hydroxyethyl ethylcellulose (HEEC); hydroxyalkyl celluloses such as hydroxypropyl cellulose (HPC) and hydroxyethyl cellulose (HEC); and carboxymethylcellulose sodium (CMC-Na). There may be used any cellulose ether that is derived by etherifying cellulose to make it water-soluble and can be formed into a film by casting an aqueous solution thereof to a certain thickness and then drying it.
Specifically, useful alkylcelluloses include, for example, methylcellulose having 19 to 33% by weight of the methoxyl group, and ethylcellulose having 7 to 25% by weight of the ethoxyl group.
Useful hydroxyalkyl alkylcelluloses include, for example, hydroxypropyl methylcellulose having 19 to 30% by weight of the methoxyl group and 13 to 20% by weight of the hydroxypropoxyl group, hydroxyethyl methylcellulose having 19 to 30% by weight of the methoxyl group and 9 to 20% by weight of the hydroxyethoxyl group, and hydroxyethyl ethylcellulose having 11 to 21% by weight of the ethoxyl group and 40 to 57% by weight of the hydroxyethoxyl group.
Useful hydroxyalkyl celluloses include, for example, hydroxypropyl cellulose having 50 to 70% by weight of the hydroxypropoxyl group, and hydroxyethyl cellulose having 30 to 60% by weight of the hydroxyethoxyl group.
A useful example of carboxymethylcellulose sodium (CMC-Na) is that having 15 to 53% by weight of the carboxymethoxyl group.
The contents of the methoxyl, ethoxyl, hydroxypropoxyl and like groups can be determined according to the methods described in the Pharmacopoeia of Japan. On the other hand, the content of the hydroxyethoxyl group can be determined according to the method described in P. W. Morgan, Eng. Chem. Anal. Ed., 1946, 18, pp. 500-504 or in Merz, Z. Anal. Chem., 1967, 232, pp. 82-93.
The film prepared from a cellulose ether according to the present invention needs to have high transparency. If its transparency is low, the film will have a problem in that the images projected by an OHP may not be sharp. Such a cellulose ether may be prepared by mixing cellulose with NaOH or the like to form a homogeneous alkali cellulose, and reacting it with an etherification reagent until a degree of ether substitution required to making it water-soluble is achieved.
If the cellulose ether has an insufficient degree of substitution or is not uniformly substituted, a lot of undissolved fibrous matter having a length of 8 to 200 xcexcm will remain when it is dissolved in water.
The amount of such undissolved fibrous matter may be determined by dissolving the cellulose ether in ISOTON II (an aqueous electrolyte solution for use with Coulter counters; manufactured by Coulter, Inc.) within a thermostatic chamber at 20xc2x0 C. so as to give a 0.1 wt % aqueous solution, and counting the number of undissolved fibers present in 2 ml of the solution and having a length of 8 to 200 xcexcm by means of a Model TAII Coulter Counter (manufactured by Coulter, Inc.) or multisizer using an aperture tube having a diameter of 400 xcexcm.
For a cellulose ether capable of forming a film with which very sharp images can be projected when it is used for purposes of projection by an OHP, it is preferable that the number of undissolved fibers determined in the above-described manner be not greater than 1,000 (inclusive of zero).
Preferably, the cellulose ether used in the present invention is characterized in that, when 100 g of the cellulose ether is shaken on a sieve having an opening of 150 xcexcm, the amount of cellulose ether remaining on the sieve is not greater than 25% by weight. If the amount is greater than 25% by weight, the solubility of the cellulose ether may be reduced to cause an increase in the amount of undissolved fibers and, therefore, the transparency of the resulting film sheet may be reduced.
Specifically, using a Model 429 Low-Tap Sieve Shaker (manufactured by Kansai Kana-Ami Co., Ltd.) fitted with a No. 100 standard sieve (having an opening of 150 xcexcm) as prescribed by JIS Z8801, 100 g of the cellulose ether is shaken for 30 minutes under conditions including 200 shakes per minute, 156 strokes per minute, and an amplitude of 50 mm. Thereafter, the amount of residue on the sieve is weighed.
No particular limitation is placed on the molecular weight of the cellulose ether used. However, it is generally preferable that a 2 wt % aqueous solution of the cellulose ether have a viscosity of not less than 3 mPa.s at 20xc2x0 C. This viscosity corresponds to a weight-average molecular weight of not less than 10,000 which can provide a film-forming ability. The aforesaid viscosity can be measured according to the viscosity measuring method described in the Pharmacopoeia of Japan.
A film of the cellulose ether described herein may be formed by casting a solution of the cellulose ether and then drying it, or by extruding a thick solution of the cellulose ether into a film and then drying it, as described in Japanese Patent Publication (JP-B) No. 45-2116/""70.
In the case of alkylcelluloses and hydroxyalkyl alkylcelluloses which are not soluble in water having a high temperature, films thereof may be formed by dispersing a powdered cellulose ether in hot water at a high concentration, casting this dispersion, cooling it to dissolve the cellulose ether, and then drying it to form a film.
No particular limitation is placed on the thickness of the OHP sheet of the present invention. However, if the sheet is unduly thin, it may have poor durability, and if the sheet is unduly thick, it may have low transparency and be hard to handle. Accordingly, its thickness is preferably in the range of 5 to 200 xcexcm and more preferably about 10 to 100 xcexcm.
Moreover, various additives may be added to the cellulose ether, so long as they do not interfere with the objects of the present invention and they permit the cellulose ether to be formed into a film. Such additives include inorganic fillers such as ceramics; colorants such as Food Red, Methyl Orange and Methyl Red; polyhydric alcohol type plasticizers and surfactants such as glycerol; organic binders such as polyvinyl alcohol, sodium polyacrylate and polyacrylamide; and the like.
The present invention is more specifically explained with reference to the following examples and comparative example. However, these examples are not to be construed to limit the scope of the invention.

Film sheet for use with overhead projectors


A blowout preventer with a body having a central bore and aligned, opposed guideways extending outward from said central bore, a ram in each of said guideways, means for moving the rams in the guideways, each ram having a ram body with a pair of vertical face recesses and a face slot for receiving an improved packer including a packer body of resilient material with two vertical recesses aligned with the ram body recesses, said packer body also having tubing supporting means and a tubing sealing means.

Blowout preventers are used on wells to control the pressure which may build within the well. They have been used on wells to close on dual tubing strings. It is desirable that when running or pulling such strings that they be supported by the blowout preventer rams. Normal support of a tubing string by a blowout preventer is accomplished by resting the joint enlargement on the rams. With dual strings in more recent wells which are much deeper, such support of both strings on the rams is not possible because the joints are normally vertically staggered and the length of the strings are such that both would not be supported adequately with only one resting on the rams. Additionally, tubing strings have safety valves installed therein and require the running of their control lines, often in encapsulated form along the exterior of the strings. Supporting the dual strings with their encapsulated control lines on a blowout preventer has not been possible with existing structures.
One prior blowout preventer structure was suitable for handling dual strings. It included an upper set of rams which sealed on the dual strings after they had been properly oriented by the lower set of rams. This structure is shown in U.S. Pat. No. 4,215,747. Another prior structure includes shear rams in an upper preventer and slip bowl rams in the lower preventer as shown in U.S. Pat. No. 4,043,389.
A blowout preventer structure shown in U.S. Pat. No. 4,057,887 includes upper and lower rams for a single string which has its shoulder supported on the lower ram, the upper and lower rams provide sealing on the string and intermediate rams are used for unthreading the string at the joint resting on the lower ram.
U.S. Pat. Nos. 2,746,710, 2,855,172, 2,947,508 and 4,229,012 all disclose blowout preventer structures in which the packing includes a series of inserts which support the packing material and which can move inwardly in varying degrees to accommodate the shape of the string on which the rams close. None of these structures are suitable for supporting dual strings and their encapsulated control lines and sealing about the dual strings and the control line.


Dental retraction and isolation devices disclosed herein simultaneously isolate at least a portion of a maxillary dental arch and at least a portion of an opposing mandibular dental arch, along with the gingivae near the gumline, while gently retracting a patient's tongue, cheek and lips. All procedures in operative dentistry and fixed prosthodontics can be performed using these devices, but they are particularly useful where access to the gingiva is necessary or desirable, where a dry field is crucial for bonding success, and/or where occlusion and masticatory movement in a dry field are advantageous. The devices can be deployed in seconds and stay in place without clamps, ligatures or wedges, and because the devices are fabricated from soft, pliable materials, they reduce tissue damage and conform to oral surfaces.

In dental procedures requiring isolation, the use of rubber dams held in position by tooth clamps and stretched across rigid or semi-rigid frames is the current industry standard. Rubber dams are, however, susceptible to tearing in the presence of sharp instruments, and they may obstruct breathing and/or press a patient's tongue into a position that activates the gag reflex. Rubber dams also do not allow access to the gingivae, making them unsuitable for crown and bridge, restorations near the gum line, and other procedures involving the gingivae or root surfaces.
For soft tissue procedures, retraction is typically accomplished using a hard metallic or plastic device. But such devices prevent occlusion and masticatory movement, making it necessary to insert and remove the retractor multiple times during a procedure to evaluate and adjust a patient's bite, whereby a dry field cannot be maintained. Also, this repetitive intrusion and removal increases the chance that the soft tissues of the oral cavity will be abraded or cut, which increases the risk of infection. Infection risk is exacerbated when the retraction device includes ports, orifices, channels or other non-sterilizable features.
In addition to commercially available products, US Patent Pub. No. 2016/0270880 and U.S. Pat. Nos. 9,387,054, 6,213,772 and 5,199,872 disclose dental isolation and/or retraction devices. However, all of these products suffer from one or more of the disadvantages discussed above.


Through-the-wash automatic dishwashing detergent compositions, especially detergent compositions comprising zinc-containing materials, are provided for protecting glassware from surface corrosion during automatic dishwashing.

Automatic dishwashing detergents constitute a generally recognized distinct class of detergent compositions whose purpose can include to break down and remove food soils; to inhibit foaming; to promote the wetting of wash articles in order to reduce or eliminate visually observable spotting and filming; to remove stains such as might be caused by beverages such as coffee and tea or by vegetable soils such as carotenoid soils; to prevent a buildup of soil films on washware surfaces; and to reduce or eliminate tarnishing of flatware without substantially etching or corroding or otherwise damaging the surface of glasses or dishes. The problem of glassware corroding during washing the cycle of an automatic dishwashing appliance has long been known. Current opinion is that the problem of corrosion in glassware is the result of two separate phenomena. On one hand, the high pH needed for cleaning causes silica hydrolysis. This dissolved silica/silicate, together with silicates added purposely to prevent china and metal corrosion, deposit on the glass surface leading to iridescence and clouding. On the other hand, builder removal of chelate metal ions from the glass surface, and the subsequent metal ion leaching that follows renders a less durable and chemical resistant glass. After several washes in an automatic dishwashing appliance, both phenomena can cause damage to glassware such as cloudiness, scratches, and streaks.
Most consumers agree that corrosion of glassware from use of detergent compositions in automatic dishwashing (ADW) is one of their most serious unmet needs. ADW detergent compositions containing zinc or magnesium salts of organic acids for improved protection against glass corrosion are known. As these salts are sparingly soluble, they are used for controlled release of reactive zinc species. The performance of soluble zinc salts in detergent compositions is difficult to control as precipitates of insoluble zinc salts with other ions in the wash liquor will occur. Yet insoluble zinc salt precipitates may deposit on both the glassware and on the ADW appliance elements itself. Furthermore, some insoluble zinc salts may be too inert to deliver the needed Zn2+ ions, as for example zinc oxide (ZnO). Aluminum sulfate salts have also shown promise, but formulatabilty issues remain. For example, flocculation with a polymer thickener and a slight negative on oxygen bleach performance requires an encapsulation approach, which can add formulation costs. Rinse aids containing zinc or magnesium salts are also known but are used by only a small number of consumers, therefore, it is desirable to be able to deliver Zn2+ ions through-the-wash. Thus, there is a continuing need to develop alternative automatic dishwashing detergent compositions containing Zn2+ ions that provide the abovementioned benefits yet reduce the problem of glassware surface corrosion experienced in through-the-wash applications.

Compositions for protecting glassware from surface corrosion in automatic dishwashing appliances


In an optical beam riding guidance for missiles according to the beam rider method, a definite recognition of the roll attitude and the location assignment is carried out in dependence on the expiring time in a simple manner and without previous synchronization with the launching installation.

Optical beam riding guidance for missiles which are guided from launching to the target along a line of sight of a sighting device, wherein the launching device comprises at least one light source whose sharply focused light beam is deflected with reference to the line of sight so that the light beam impinges on a receiver at the missile and a location assignment and tracking of the missile on a line of sight is performed in an evaluating circuit, wherein either the reference of the location assignment to the expiring time is produced by means of a time base which follows in the evaluating circuit and is synchronized with the launching device until the moment of launching, or a time base can be triggered by means of using a second pulse-modulated reference light source arranged parallel to the line of sight.
Optical guide beam systems, in which modulated light waves are used for guiding a missile, are known from various publications.
DE-AS 16 23 391 describes a system for the optical beam riding guidance of vehicles, in which a guide beam runs over a fixed angle of space in a periodically alternating direction. In addition, a reference signal transmitter is provided which marks a determined position of the guide beam at determined points in time. In order to produce the modulated and deflected guide beams in the launching installation and for the reception and evaluation in the missile this system requires considerable expenditure in terms of circuit technology if a great accuracy of the tracking is to be achieved. Moreover, an evaluation of the roll attitude of the missile is not possible.
A device for guiding a missile by means of a light beam which is deflected in a spiraling manner is known from DE-OS 26 58 689. This guiding device enables the detection of the roll attitude of the missile, however it requires a synchronization of the time clock in the missile with the time clock of the deflecting device in the launching installation. In addition, a high-precision timing pulse generator synchronized before the launch is required in the evaluating circuit of the missile, which timing pulse generator could previously only be used in missiles with relatively low starting accelerations, since the high initial accelerations of approximately 50,000 g occurring, for example, in shells lead to a compulsory outage of the time clock.

Optical guide beam steering for projectiles


A monitoring camera and a method of controlling the monitoring camera are provided. The monitoring camera includes: a data receiving unit receiving a signal from a terminal; an image acquiring unit having a zoom lens and an imaging device generating first image data of an original image, and further, generates second image data of a user-selected region by performing at least one of zooming, panning and tilting based on control data; a data transmitting unit transmitting the first image data and the second image data generated by the imaging device to the terminal; a control unit including at least one of a zoom control unit controlling the zoom lens according to a zoom value, a pan control unit panning the image acquiring unit according to a pan value and a tilt control unit tilting the image acquiring unit according to a tilt value; a memory storing the control data.

1. Field of the Invention
Apparatuses and methods consistent with the present inventive concept relate to a monitoring camera and a method of controlling the same, and a computer readable recording medium storing a program for executing the method.
2. Description of the Related Art
In general, when a monitoring camera is connected to a terminal via a network, the monitoring camera transmits acquired image data to the terminal via the network, and the terminal displays a live-view video image corresponding to the acquired image data. The live-view video image, which is a real-time video image, is displayed on a display unit of the terminal. The monitoring camera may be controlled by receiving a control signal from the terminal via the network.
When using the monitoring camera, a user may select a certain region of the live-view video image displayed on the display unit of the terminal to enlarge the certain region, and allow the enlarged certain region to be fully displayed on the display unit of the terminal. In this case, the monitoring camera receives information about the certain region from the terminal, and performs zooming on the certain region. However, the monitoring camera often fails to perform zooming on the certain region, and may perform zooming on a region other than the certain region due to an error.

Monitoring camera, method of controlling the same, and recording medium storing program for executing the method