An organic light emitting device, and a method of fabricating the same, has a cathode electrode that can prevent oxygen or moisture from infiltrating. The organic light emitting device of the present invention has a lower electrode, an organic thin film layer and an upper electrode successively formed on the substrate. The upper electrode has at least two-layered thin films having different grain density and grain size. A lower film of the at least two-layered thin films of the upper electrode has a first Al thin film having a lower grain density and larger grain size than an upper of the at least two-layered thin films. The upper film has a second Al thin film having relatively higher grain density and smaller grain size than the first Al thin film.

1. Field of the Invention
The present invention relates to flat panel display devices and, more particularly, to organic light emitting devices and methods of fabricating the same having cathode electrodes to prevent oxygen and/or moisture from infiltrating.
2. Description of the Related Art
An organic light emitting device is a flat panel display device that is an emissive display device in which an organic compound is electrically excited to emit light. The organic compound has characteristics such as a low driving voltage and a thin type. Moreover, since the organic light emitting device has features such as a wide viewing angle, quick response time, and the like, which are required in a liquid crystal display that is a flat panel display device, the organic light emitting device has attracted attention as a next generation display device.
For the organic light emitting device, a problem has arisen as to a life span of a device depending on a passivation method. To solve this problem, Japanese patent publication No. 4-334895, for example, discloses a dual passivation method for a long life span of the display device.
FIG. 1 shows a cross-sectional structure of a flat panel display device made with the conventional dual passivation method. Referring to FIG. 1, in the conventional organic light emitting device, an organic light emitting (hereinafter, referred to as "organic EL") element 20 has an anode electrode 21, an organic thin film layer 22, and a cathode electrode 23, which are laminated on a glass substrate 10. An inorganic encapsulating layer 30 is formed to cover the organic EL element 20, and the organic EL element 20 and the inorganic encapsulating layer 30 are encapsulated with an encapsulating substrate 50. Here, the encapsulating substrate 50 encapsulates by using an adhesive resin layer 40 such as a light-curing adhesive with a low moisture absorption property in order to prevent moisture infiltration.
The conventional display device used the inorganic encapsulating layer 30 to passivate the organic EL element 20. The inorganic encapsulating layer 30 was formed by using a Chemical Vapor Deposition (CVD) method or a Physical Vapor Deposition (PVD) method, where an organic thin film that is an underlying layer is susceptible to heat and mechanical stresses. As such, the inorganic encapsulating layer 30 does not have a good film quality. Moreover, the inorganic encapsulating layer 30 has a porous structural property so that the inorganic encapsulating layer 30 is susceptible to moisture infiltration. Thus, a perfect passivation could not be performed. Therefore, in the conventional art, the life span of the device cannot be guaranteed only with the inorganic encapsulating layer 30, so that there was a problem that a second passivation must be performed with the adhesive resin and the encapsulating substrate.

This patent is subject to a terminal disclaimer.

Flat panel display device and method of fabricating the same


A color filter substrate according to the present invention includes a transparent substrate; at least three colors of colored layers provided on the transparent substrate; first columnar structure bodies 101 provided in pixel outskirts within a display region, the first columnar structure bodies 101 defining a cell gap; and second columnar structure bodies 102 provided in the pixel outskirts within the display region or outside the display region, the second columnar structure bodies 102 having a smaller height than that of the first columnar structure bodies 101, such that a difference from the height of the first columnar structure bodies 101 exceeds a range of elastic deformation of the first columnar structure bodies 101.

1. Field of the Invention
The present invention relates to a color filter substrate and a liquid crystal display panel including the same.
2. Description of the Related Art
Liquid crystal display devices are characterized by their small size, thinness, low power consumption, and light weight, and therefore are currently in wide use for various electronic devices. In particular, active matrix-type liquid crystal display devices having switching elements are widely adopted in OA devices such as personal computers, AV devices such as television sets, mobile phones, and the like. Moreover, the recent years have seen rapid improvements in display quality, e.g., increase in the size and increase in the definition of liquid crystal display devices, improvements in the pixel effective area ratio (higher aperture ratio), wider viewing angles, or improvements in color purity.
A liquid crystal display device generally includes: a liquid crystal display panel having a pair of opposing substrates (e.g., an active matrix substrate and a color filter substrate) and a liquid crystal layer interposed between the pair of substrates; and driving circuitry for supplying predetermined signals and voltages to the liquid crystal display panel. Furthermore, a liquid crystal display device of a transmission type or transflective type includes an illuminator such as a backlight. Note that part of the driving circuitry may be formed integrally with the liquid crystal display panel. Recently, liquid crystal television sets incorporating TV receivers are also rapidly gaining prevalence.
In a liquid crystal display panel, the thickness (which may also be referred to as a cell gap) of the liquid crystal layer is defined by a component called spacers. As the spacers, particulate spacers such as plastic beads and columnar structure bodies (which may also be referred to as "columnar spacers", "dot spacers", or "photospacers") which are formed on a substrate by using a photosensitive resin are employed. Although depending on the display mode, the thickness of a liquid crystal layer directly affects retardation, for example in a liquid crystal panel of the vertical alignment mode (VA mode), which is widely used in recent years. Therefore, in order to obtain a high display quality, it is important to set and maintain the thickness of the liquid crystal layer at a predetermined value. In a large-screen liquid crystal panel, it is necessary to set and maintain the thickness of the liquid crystal layer at a predetermined thickness over the entire display region, and thus optimization of the structure and location of the spacers constitutes an important technological problem.
On the other hand, as liquid crystal display panels increase in size, the "one drop filling technique" is adopted more and more frequently in the process of forming a liquid crystal layer in methods for producing a liquid crystal display panel (see, for example, Japanese Patent Publication No. 8-20627 (Patent Document 1)).
Conventionally, a method called the "(vacuum) injection technique" has widely been used. This method involves: retaining a liquid crystal cell (empty cell) within a vacuum chamber, the liquid crystal cell (empty cell) being obtained by attaching together a pair of substrates with a sealant so as to form a predetermined gap; after removing the air from within the liquid crystal cell, allowing the interior of the chamber to return to a normal atmospheric pressure while an injection inlet which is provided in a portion of a sealing section of the liquid crystal cell is in contact with a liquid crystal material; and after injecting the liquid crystal material into the liquid crystal cell by the action of atmospheric pressure, the injection inlet is sealed with resin. If such an injection technique is adopted in the manufacturing of a large-sized liquid crystal panel, injection of the liquid crystal material takes a long time, thus greatly reducing the production efficiency.
Therefore, the one drop filling technique, which can shorten the process time relative to the injection technique, is being adopted more and more.
In the one drop filling technique, as is described in Patent Document 1 above, a sealing section having a rectangular frame-like shape is formed by using a sealant on the surface of either one of a pair of substrates, and a liquid crystal material is dropped into the region surrounded by the sealing section. This is attached onto the other substrate, and the sealant is allowed to solidify (or typically "cured"), whereby a liquid crystal display panel having a liquid crystal layer is obtained. This one drop filling technique is a very important technology in the manufacturing of a large-sized liquid crystal display panel.
One of the problems of the one drop filling technique is that voids may occur in the liquid crystal layer. Various causes for voids are known. For example, Japanese Laid-Open Patent Publication No. 2002-107740 (Patent Document 2) discloses a remedy to reduce those voids which are ascribable to insufficiency in the supply of liquid crystal material. Japanese Laid-Open Patent Publication No. 11-174477 (Patent Document 3) discloses a method for reducing those voids which are ascribable to a gas which emanates from color filters and the like (including water adsorbed on the surface, e.g., color filters). Furthermore, Japanese Laid-Open Patent Publication No. 2003-84289 (Patent Document 4) discloses a remedy to reduce "low-temperature voids", which occur at a low temperature because of the spacers not being able to conform to the changing thickness of the liquid crystal layer, which in turn is ascribable to a thermal contraction of the liquid crystal material. In a liquid crystal display panel described in Patent Document 4, two types of columnar spacers of different heights are provided, and it is ensured that, within the range of elastic deformation of the taller columnar spacers, an external load will act also on the shorter columnar spacers. As a result, the taller spacers alone will absorb shrinkage of the cell gap due to a temperature change, thus reducing the occurrence of low-temperature voids.
However, through various studies of the inventors, it has been found that voids may occur due to causes which are not even described in the above Patent Documents.
In the one drop filling technique, when attaching the other substrate after dropping a liquid crystal material into the region surrounded by a sealing section on one of the substrates, the liquid crystal material will prevail over the entire liquid crystal cell as the liquid crystal material stretches (or spreads). If the liquid crystal material is difficult to stretch (or difficult to spread), there may be local insufficiencies of liquid crystal material, thus causing voids. Since these voids do not contain any gas, they may be referred specially to as "vacuum voids". Since vacuum voids are caused by the liquid crystal material's difficulty to stretch, they become more likely to occur as the spacer density (distribution density: the number of spacers per unit area) increases.
On the other hand, if the spacer density is too low, the distance between adjoining spacers becomes longer. Therefore, an external pressure to the liquid crystal cell, which is associated with the atmospheric pressure when opened to the atmosphere in the injection technique and in the one drop filling technique, will lead to an increased amount of deformation of the spacers and an increased amount of flexure of the glass substrates in between spacers. This leads to local narrowing of the cell gap, so that vacuum voids become more likely to occur. Moreover, the distance between adjoining spacers becomes longer with an increase in the size of the liquid crystal display panel (i.e., an increase in pixel size), thus making this problem more outstanding. Furthermore, in a frame region of the liquid crystal display panel (i.e., a peripheral region of the display region which lies inside the sealing section), there is a large distance between the particulate spacers mixed in the sealant and the spacers within the display region, so that the cell gap locally may become narrow due to flexure of the glass substrates, whereby vacuum voids may become more likely to occur.
Although problems of the one drop filling technique are illustrated above, when the injection technique is used, a decrease in throughput may occur due to the longer injection time of a liquid crystal material.

Color filter substrate and liquid crystal display panel equipped with same


A method and apparatus for depositing an inorganic layer onto a substrate is described. The inorganic layer may be part of an encapsulating film utilized in various display applications. The encapsulating film includes one or more inorganic layers as barrier layers to improve water-barrier performance. An oxygen containing gas, such as nitrous oxide, is introduced during the deposition of the inorganic layer. As a result, the inorganic layer is lower in stress and may obtain a water vapor transmission rate (WVTR) of less than 100 mg/m2-day.

1. Field of the Invention
Embodiments disclosed herein generally relate to the deposition of thin films using chemical vapor deposition (CVD) processing. More particularly, embodiments generally relate to methods for depositing barrier layers onto large area substrates.
2. Description of the Related Art
Organic light emitting diodes (OLED) are used in the manufacture of television screens, computer monitors, mobile phones, other hand-held devices, or other devices for displaying information. A typical OLED may include layers of organic material situated between two electrodes that are all deposited on a substrate in a manner to form a matrix display panel having individually energizable pixels. The OLED is generally placed between two glass panels, and the edges of the glass panels are sealed to encapsulate the OLED therein.
The encapsulation is achieved by sealing the active materials in inert atmosphere using a glass lid secured by a bead of UV-cured epoxy resin. The rigid encapsulation is not applicable to flexible displays, where a durable and flexible encapsulation is necessary to protect the active OLED materials from water moisture and oxygen. One approach is to use a multilayer encapsulating structure as a barrier to water moisture and oxygen permeation. Inorganic layers can be incorporated into the multilayer encapsulating structure as the main barrier layer. Organic layers can also be incorporated for the purposes of stress relaxation and water/oxygen diffusion channels decoupling layer.
Silicon nitride (SiN) is known as a good barrier material, thus it shows potential as an inorganic barrier layer in the multilayer encapsulation structure. However, SiN films deposited at low temperatures such as below 100 degrees Celsius have high stress, which can induce film peeling, also known as delamination, or mismatch issues in multi-film stack configurations. Due to the sensitivity of some of the layers of the OLED device, subsequently deposited layers over OLED materials will need to be deposited at lower temperatures, such as at temperatures less than 100° C.
Thus, there is a need for methods of depositing encapsulation/barrier films onto large area substrates with improved water-barrier performance to protect the devices underneath.

Barrier films for thin film encapsulation


A method of forming abrasion resistant nonwoven fabrics by hydroentanglement includes providing a precursor web. The precursor web is subjected to hydroentanglement on a three-dimensional image transfer device to create a patterned and imaged fabric. Treatment with an initial pre-dye finish enhances the integrity of the fabric, permitting the nonwoven to exhibit desired physical characteristics, including strength, durability, softness, and drapeability. The pre-dye finish treated nonwoven may then be dyed by means applicable to conventional wovens. A post-dye finish may then be applied to further enhance the performance of the nonwoven fabric.

The production of conventional textile fabrics is known to be a complex, multi-step process. The production of fabrics from staple fibers begins with the carding process where the fibers are opened and aligned into a feed stock known as sliver. Several strands of sliver are then drawn multiple times on drawing frames to further align the fibers, blend, improve uniformity as well as reduce the diameter of the sliver. The drawn sliver is then fed into a roving frame to produce roving by further reducing its diameter as well as imparting a slight false twist. The roving is then fed into the spinning frame where it is spun into yarn. The yarns are next placed onto a winder where they are transferred into larger packages. The yarn is then ready to be used to create a fabric.
For a woven fabric, the yarns are designated for specific use as warp or fill yarns. The fill yarn packages (which run in the cross direction and are known as picks) are taken straight to the loom for weaving. The warp yarns (which run on in the machine direction and are known as ends) must be further processed. The packages of warp yarns are used to build a warp beam. Here the packages are placed onto a warper which feeds multiple yarn ends onto the beam in a parallel array. The warp beam yarns are then run through a slasher where a water soluble sizing is applied to the yarns to stiffen them and improve abrasion resistance during the remainder of the weaving process. The yarns are wound onto a loom beam as they exit the slasher, which is then mounted onto the back of the loom. Here the warp and fill yarns are interwoven in a complex process to produce yardages of cloth.
In contrast, the production of nonwoven fabrics from staple fibers is known to be more efficient than traditional textile processes as the fabrics are produced directly from the carding process.
Nonwoven fabrics are suitable for use in a wide-variety of applications where the efficiency with which the fabrics can be manufactured provides a significant economic advantage for these fabrics versus traditional textiles. However, nonwoven fabrics have commonly been disadvantaged when fabric properties are compared, particularly in terms of surface abrasion, pilling and durability in multiple-use applications. Hydroentangled fabrics have been developed with improved properties, which are a result of the entanglement of the fibers or filaments in the fabric providing improved fabric integrity. Subsequent to entanglement, fabric durability can be further enhanced by the application of binder compositions and/or by thermal stabilization of the entangled fibrous matrix. However, the use of such means to obtain fabric durability come at the cost of a stiffer and less appealing fabric.
U.S. Pat. No. 3,485,706, to Evans, hereby incorporated by reference, discloses processes for effecting hydroentanglement of nonwoven fabrics. More recently, hydroentanglement techniques have been developed which impart images or patterns to the entangled fabric by effecting hydroentanglement on three-dimensional image transfer devices. Such three-dimensional image transfer devices are disclosed in U.S. Pat. No. 5,098,764, hereby incorporated by reference, with the use of such image transfer devices being desirable for providing a fabric with enhanced physical properties as well as an aesthetically pleasing appearance.
Heretofore, attempts have been made to develop nonwoven fabrics exhibiting the necessary aesthetic and physical properties. U.S. Pat. No. 5,393,304, discloses a washable spunlaced nonwoven cloth, with this patent contemplating use of a PAE binder composition (polyamide-amine-epichorohydrin) with inclusion of cotton fiber in the fibrous matrix.
U.S. Pat. No. 3,988,343, discloses a nylon fabric treated with a mixture of acrylic polymer and latex binder with tinting pigments. U.S. Pat. No. 5,874,159 contemplates providing a spunlaced fabric structure with durability by the provision of a bonding material in the form of a thermal plastic polymer, which may be provided in the form of a net, an apertured or punctured film, or molten drop form. The bonding material acts to join layers or laminations from which the fabric is formed.
For specific applications, a nonwoven fabric must exhibit a combination of specific physical characteristics. As an example, fabrics used in apparel should be soft and drapeable, yet withstand home laundering, and be resistant to abrasion (which can result in aesthetically displeasing fabric "pills"). Fabrics used in the fabrication of apparel must also exhibit sufficient strength, tear resistance, and colorfastness to ensure a reasonable life span for the end-use article. The physical performance of a fabric in terms of liquid handling, i.e. perspiration control, is of utmost concern when apparel fabricated from such fabric is to be worn for extended lengths of time. These are among the characteristics which have been identified as being desirable for apparel applications including outerwear, workwear, footwear, and the like.
U.S. Pat. No. 5,478,635, discloses a knitted nylon fabric, necessary for abrasion resistance, being adhesively affixed to a nylon nonwoven fabric "reservoir". The construction of this laminate structure requires the knitting of nylon yarn followed by the application of polyurethane adhesive dissolved in a highly volatile solvent such as methylene chloride. U.S. Pat. No. 4,941,884 is directed to a method of fabricating an abrasion resistant woven material having good aesthetics.
Notwithstanding various attempts in the prior art to develop a nonwoven fabric acceptable for apparel use applications, a need continues to exist for a nonwoven fabric exhibiting aesthetic appeal while obtaining requisite mechanical characteristics.

Abrasion resistant and drapeable nonwoven fabric


A hanging file folder assembly includes a file folder having a pair of upwardly extending walls joined along a lower fold line and a mounting flap folded downwardly from a top edge of one wall. The mounting flap is secured to its associated wall along a continuously extending medial joinder line to define an enclosed guide passage for insertion of a suspension bar and an open gripping channel for entry by a lower retaining plate of an index tab holder. An index tab holder for use with the file folder is provided with a lower retaining plate for insertion into the gripping channel and an upper retaining plate for engaging the file folder wall above and opposite the gripping channel.

The subject invention relates to a hanging file folder assembly comprising a pair of suspension bars, at least one of which is slidably received. It relates furthermore to a novel file folder and a novel index tab holder adapted for use in such an assembly.
Hanging file folders are commonly used for separating different categories of documents stored in cabinetry such as file cabinets, credenzas, and the like. Such cabinetry typically includes storage drawers provided with support rails mounted along both sides thereof and extending longitudinally in the direction of drawer movement. A hanging file for such an application may be fashioned from a rectangular paperboard sheet which is centrally folded to define front and rear walls for the folder. The marginal sheet portions remote from the central fold line are folded over and secured to their parent walls so as to define front and rear guide passages. Suspension bars are then inserted into these passages. The suspension bars are of sufficient length to span the distance between the support rails. When in use the suspension bars are hooked over the support rails, so that the file folder is suspended therefrom.
Hanging file folder assemblies usually include index tabs are inserted into index tab holders mounted on at least some of the file folders for displaying index tabs which identify the subject matter of the documents filed therein. However, hanging file folders come in a number of different designs, and it is desirable to provide index tab holders which are able to accommodate a range of design variations.
Hanging file folders of the above described type frequently have a plurality of spaced slits along the length of at least one guide passage. These slits afford entry points for mounting ears projecting sidewardly from opposite of such mounting is shown in Snowden, U.S. Pat. No. 4,053,057. It is apparent that this mounting technique affords mounting at only a relatively few predesignated locations. Moreover, the index tab holders must have a length equal to the distance between adjacent slits or an integral number of such distances.
It is an object of this invention to provide a hanging file folder assembly having a freely moveable index tab holder.
Another object of the invention is to provide a hanging file folder having improved means for mounting an index tab holder along a suspension bar guide passage.
It is another object of the invention to provide an index tab holder which may be mounted at any desired position along a guide passage of a hanging file folder.
It is a further object of the invention to provide an index tab holder which may be mounted along a guide passage of a hanging file folder irrespective of index tab holder length.
Other objects and advantages of the invention will be apparent from the following description, the accompanying drawings and the appended claims.


To stop, in an emergency, a revolving superstructure quickly from rotating while preventing damage of a mechanical brake. A revolving superstructure is driven swiveling using a permanent magnetic-type swiveling electric motor; in an emergency, such as a malfunction in a drive or control system for the swiveling electric motor, allowing electric power generated in the electric motor due to inertial rotation to be consumed in an external braking resistor so as to make an electric braking action; and a mechanical brake is activated to stop the rotation and hold the stopped revolving superstructure when a rotation speed of the revolving superstructure becomes equal to or lower than a preset value.

For swivel-type work machines, such as an excavator or a crane, there has been known a technique of employing an electric motor as a swivel driving source, in place of a traditional hydraulic motor, as disclosed in the following Patent Publication 1.
This conventional technique uses the electric motor also as a power generator to brake/stop a revolving superstructure by a regenerative braking torque from the power generating action.
[Patent Publication 1] Japanese Patent Laid-Open Publication No. 2001-207478
In the event of a malfunction such that power supply to the swiveling electric motor is interrupted due to a failure of a power generator, etc., or the swiveling electric motor becomes out of control due to a failure in a swivel control system, the above conventional technique will involve a situation where only inertia of the revolving superstructure acts on the electric motor as with a neutral free mode in a hydraulic motor-based system, without any braking based on the power generating action of the electric motor, and it will take time to stop the revolving superstructure.
A shovel or crane is also equipped with a mechanical brake serving as a stop-holding parking brake in a rotationally stopped state. Thus, it is contemplated to allow the mechanical brake to be activated as an emergency brake.
However, the mechanical brake originally has only a brake performance designed for a stop-holding brake. Therefore, if the mechanical brake is activated during a high-speed rotation, it is likely to be damaged due to lack of its own heat capacity. Providing the mechanical brake with a sufficient heat capacity, requires a cooling device, etc., which increase a size of the entire mechanical brake. That results in poor practicality in terms of installation space and cost.

Rotation brake method and device for working machine

Kobelco Construction Machinery Co., Ltd.

Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.)


An electronic device includes a power receiving unit and a secondary battery. The electronic device can send an instruction to an outside to stop power transmission, and operates by a discharge current of the secondary battery. In a case where the secondary battery is charged and a voltage of the secondary battery becomes higher than a first threshold and lower than a second threshold larger than the first threshold, charging of the secondary battery is stopped without sending the instruction to stop the power transmission, and after an elapse of a predetermined period of time, the charging of the secondary battery is restarted. When the voltage of the secondary battery thereafter becomes higher than the second threshold, the instruction to stop the power transmission is sent, and the charging of the secondary battery is stopped.

Among electronic devices using a secondary battery, there are electronic devices including a function of detecting the remaining battery capacity. In order to detect the remaining capacity of a secondary battery, it is necessary to detect the terminal voltage in a no-load condition (such a voltage is called "OCV (Open Circuit Voltage)"). Patent Document 1 describes a calculation method for obtaining the remaining capacity of a secondary battery. In the secondary battery remaining capacity calculation method described in Patent Document 1, when the relative remaining capacity SOC of a secondary battery is to be obtained from the open circuit voltage OCV of the secondary battery with reference to a table which shows previously obtained relationships between the open circuit voltage of the secondary battery and the relative remaining capacity [%], an open circuit voltage OCVfull in the full-charge condition of the secondary battery is detected, a relative remaining capacity SOCfull [%] is obtained with reference to the table in accordance with the open circuit voltage OCVfull, and the relative remaining capacity SOC which is obtained with reference to the table in accordance with the open circuit voltage OCV of the secondary battery that is detected when the discharge of the secondary battery is stopped is then corrected by SOCtrue=SOC×(100/SOCfull) based on the relative remaining capacity SOCfull [%] in the full-charge condition, thereby obtaining the true relative remaining capacity SOCtrue of the secondary battery.

Electronic device and electronic device charging system

Panasonic Intellectual Property Corporation of America


Multiple mobile cellular network (MCN) communication systems can be networked together to form a network of MCN communication systems (NOM). Each MCN communication system within the NOM can operate as an independent cellular network to provide communications between user equipment within a covered area. When a UE in one MCN of the NOM moves into a different MCN of the NOM, the corresponding MCN communication systems can handover the UE. The UE can also be handed over between MCN communication systems when the MCN communication systems move.

Cellular networks typically include multiple stationary base stations in different locations that communicate with a mobile telephone switching office (MTSO) that is remotely located from the different base stations. The MTSO determines how calls are routed between the base stations and enables the base stations to communicate with each other for handover purposes. If a base station cannot communicate with the MTSO, or the rest of the network, all communications at that base station are lost and user equipment (UE) in corresponding network areas cannot communicate with other UEs, even if the UEs trying to communicate with each other are in the same network area. In addition, the base stations are built to be stationary so that UEs within a particular area always have network access.
Many locations throughout the world lack a network infrastructure that would enable users to communicate via a typical telephone or cellular network. In such locations it can be difficult for users to communicate effectively. Users must often rely on technologies that are more expensive, have lower bandwidth, or have limited use distances, such as satellite phones, half-duplex radio transceivers, etc. Furthermore, these locations often lack the resources to create the network infrastructure necessary for a cellular network, such as cell towers, base stations, switching stations, etc. In some circumstances, such as war zones, etc., building the network infrastructure for such communications is not feasible due to the transient nature of military personnel and equipment. For example, for a communications command center in a battlefield area, mobility can be an important feature to allow the command center to adapt to the changing battlefield conditions. Thus, stationary network technologies can be ineffective.


This invention relates to a transition metal compound represented by the formula LMX wherein M is a Group 3 to 11 metal L is a bulky bidentate or tridentate neutral ligand that is bonded to M by two or three heteroatoms and at least one heteroatom is nitrogen; X is a substituted or unsubstituted catecholate ligand provided that the substituted catecholate ligand does not contain a 1,2-diketone functionality.

Early transition metal catalysts useful for olefin coordination polymerization include the traditional Ziegler-type catalysts based on Group-4-5 transition metals and the newer metallocene type catalysts based on Group-4-6 transition metals. But specific late transition metal catalysts suitable for olefin polymerization have not offered the same levels of activity or molecular weight capability for olefin polymerization. Further development of these catalyst systems has been attempted addressing these shortcomings.
Ancillary-ligand-stabilized metal complexes (e.g., organometallic complexes) are typically useful as catalysts, additives, stoichiometric reagents, monomers, solid state precursors, therapeutic reagents, and drugs. The ancillary ligand system generally comprises organic substituents that connect to and remain associated with the metal centers. These interactions provide an opportunity to modify the organometallic complexes' shape and their electronic and chemical properties.
Certain organometallic complexes are catalysts for reactions such as oxidation, reduction, hydrogenation, hydrosilation, hydrocyanation, hydroformylation, polymerization, carbonylation, isomerization, metathesis, carbon-hydrogen activation, cross-coupling, Friedel-Crafts acylation and alkylation, hydration, dimerization, trimerization, oligomerization, Diels-Alder reactions, and other transformations. Typical complex synthesis proceeds by combining an ancillary ligand precursor with a metal-containing precursor in a solvent at a temperature. For example, organometallic complexes can be single-site, olefin polymerization catalysts. Their active sites typically comprise an ancillary-ligand-stabilized, coordinatively unsaturated transition-metal-alkyl complex.
In Johnson, Killian, and Brookhart, J. Am. Chem. Soc., 1995, 117, 6414, the authors describe the use of Ni and Pd complexes for ethylene, propylene, and 1-hexene homopolymerization. The catalyst precursors are square-planar, M2+, d8, 16-electron complexes incorporating substituted, bidentate diimine ligands. Either methyl or bromide ligands occupy the active coordination sites. These polymerizations used H+(OEt2)2[B(3,5-(CF3)2C6H3)4]− to activate methyl ligand complexes and methylalumoxane (MAO) or diethyl aluminum chloride to activate bromide ligand complexes.
European Patent publication EP-A2-0 454 231 describes Group-8, -9, and -10 metal catalysts as being suitable for ethylene, α-olefin, diolefin, functionalized olefin, and alkyne polymerizations. The catalyst precursors are Group-8, -9, and -10 metal compounds that are activated by cocatalysts including discrete borate anions. This paper also illustrates ethylene homopolymerization in solutions of methylene chloride, toluene and diethyl ether. Few polymerizations were conducted in the presence of a support material, and broad molecular weight distribution polymers were produced.
WO 97/48736 describes supported late transition metal catalysts based on diimine nickel dihalide compounds where the transition metal complex was preactivated with an aluminate.
PACT publication WO 99/05154 relates to a variety of pnictide-based ligands and their uses for catalyst systems. In particular, it discloses metal compositions and compounds stabilized by an ancillary chelating ligand structure, that polymerize functionalized and non-functionalized monomers, either alone or with an activator.
Other references of interest include U.S. Pat. No. 6,586,358 B2, V. C. Gibson and S. K. Spitzmesser, Chem. Rev., 2003, 103, 283, and S. D. Ittel, L. K. Johnson, and M. Brookhart, Chem. Rev., 2000, 100, 1169.
With the discoveries of Brookhart and others, a new area of focus in polymerization catalysis now focuses on late transition metal chemistry. These types of catalyst precursors are typically nickel, cobalt or iron dihalide compounds complexed with bidentate or tridentate chelating ligands. These types of nickel catalyst precursors are typically only slightly soluble in commonplace polymerization solvents. The nickel complexes are also typically paramagnetic complexes that are difficult to characterize and purify. Depending on the oxidation state of the cobalt and iron complexes, they too can be paramagnetic. When complexes are paramagnetic, typically IR, elemental analysis and x-ray crystallography characterization is useful, however, these techniques can also be limiting. For example, for x-ray crystallography, growing crystals of fairly insoluble compounds can often be difficult. Elemental analysis requires a pure compound, again something often difficult to obtain with a poorly soluble compound because purification techniques are more limited. And while IR is a good characterization tool when used in combination with other characterization techniques, it also has its limitations—in particular, identifying and quantifying small amounts of impurities in a product. Thus, the need exists for more easily characterized and more soluble catalyst precursors that nonetheless retain or exceed the catalytic activity of prior art catalysts.

Late transition metal catalysts for olefin polymerization and oligomerization


A patterned metal layer is gap filled with HSQ, an oxide formed thereon by PECVD, e.g., silicon dioxide derived from silane and N.sub.2 O, and planarized. The dielectric constant of the HSQ layer is minimized by baking the deposited HSQ layer in an inert atmosphere, e.g., N.sub.2, before heat soaking in an N.sub.2 O-containing atmosphere for no more than about 10 seconds and subsequent PECVD.

The escalating requirements for high densification and performance associated with ultra large scale integration semiconductor devices require design features of 0.25 microns and under, such as 0.18 microns, increased transistor and circuit speeds, high reliability and increased manufacturing throughput. The reduction of design features to 0.25 microns and under generates numerous problems challenging the limitations of conventional interconnection technology, including conventional photolithographic, etching and deposition techniques.
Conventional methodology for forming patterned metal layers comprises a subtractive etching or etch back step as the primary metal patterning technique. Such a method involves the formation of a first dielectric interlayer on a semiconductor substrate, typically monocrystalline silicon, with conductive contacts formed therein for electrical connection with an active region on the semiconductor substrate, such as a source/drain region. A metal layer, such as aluminum or an aluminum alloy, is deposited on the first dielectric layer, and a photoresist mask is formed on the metal layer having a pattern corresponding to a desired conductive pattern. The metal layer is then etched through the photoresist mask to form the conductive pattern comprising metal features separated by gaps, such as a plurality of metal lines with interwiring spacings therebetween. A dielectric material, such as spin on glass (SOG), is typically deposited to fill in the gaps between the metal features, and baked at a temperature of about 300.degree. C. to about 450.degree. C., for a period of time up to about two hours, depending upon the particular SOG material employed. Planarization, as by CMP, is then performed.
The drive to increased density and attendant shrinkage in feature size generates numerous problems. For example, as feature sizes, e.g., metal lines and interwiring spacings, shrink to 0.25 microns and below, such as 0.18 microns, it becomes increasingly difficult to satisfactorily fill in the interwiring spacings voidlessly with a dielectric material and obtain adequate step coverage. It also becomes increasingly difficult to form a reliable interconnection structure. A through-hole is typically formed in a dielectric layer to expose an underlying metal feature, wherein the metal feature serves as a landing pad occupying the entire bottom of the through-hole. Upon filling the through-hole with conductive material, such as a metal plug to form a conductive via, the entire bottom surface of the conductive via is in direct contact with the metal feature.
Another problem generated by miniaturization relates to the RC time constant. Although semiconductor devices are being scaled in the horizontal dimension, they are not generally scaled in the vertical dimension, since scaling in both dimensions would lead to higher current density that could exceed electromigration reliability limits. Horizontal scaling, therefore, requires conductive lines having a high aspect ratio, i.e., conductor height to conductor width of greater than one, with reduced interwiring spacings. As a result, capacitive coupling between conductive lines becomes a primary limitation on circuit speed. If intrametal capacitance is high, the possibility for electrical inefficiencies and inaccuracies increase. It is recognized that a reduction in capacitance within multi-level metallization systems will reduce the RC time constant between the conductive lines.
Hydrogen silsesquioxane (HSQ) offers many advantages for use in interconnect technology. HSQ is relatively carbon free, thereby rendering it unnecessary to etch back HSQ below the upper surface of the metal lines to avoid poison via problems. In addition, HSQ exhibits excellent planarity and is capable of gap filling interwiring spacings less than 0.15 microns employing conventional spin-on equipment. HSQ undergoes a melting phase at approximately 200.degree. C., but it does not convert to the high dielectric constant glass phase until reaching temperatures of about 400.degree. C. in intermetal applications. As deposited HSQ is considered a relatively low dielectric constant material with a dielectric constant of about 2.9-3.0, vis-a-vis silicon dioxide grown by a thermal oxidation or chemical vapor deposition which has a dielectric constant of about 3.9-4.2. The mentioned dielectric constants are based on a scale wherein 1.0 represents the dielectric constant of air.
However, in attempting to apply HSQ to interconnect technology, particularly for gap filling, it was found that its dielectric constant became undesirably high as a result of subsequent processing. For example, a layer of HSQ was initially deposited on a patterned metal layer to fill in gaps between metal features. Subsequently, an oxide layer was deposited and planarized. Such an oxide layer included silicon dioxide derived from tetraethyl orthosilicate (TEOS) deposited by plasma enhanced chemical vapor deposition (PECVD) in an oxygen-containing atmosphere at about 400.degree. C. Prior to PECVD of the silicon dioxide layer, the wafer with the deposited HSQ layer thereon was acclimated by heat soaking at an elevated temperature proximate the PECVD temperature, e.g., about 400.degree. C., in an oxygen-containing atmosphere, for about 20 seconds. Another such oxide layer is silicon dioxide derived from silane deposited by PECVD in an N.sub.2 O-containing atmosphere at about 400.degree. C. Prior to PECVD of silicon dioxide derived from silane and N.sub.2 O, the wafer was heat soaked in an N.sub.2 O-containing atmosphere for about 20 seconds at about 400.degree. C. It was found that after such depositions of silicon dioxide by PECVD, the dielectric constant of the deposited HSQ layer undesirably increased from about 2.9-3.0 to about 3.6-3.7. The undesirable increase in the dielectric constant of the HSQ layer adversely impacts the interwiring capacitance and RC time constant.
In copending application Ser. No. 08/956,590, filed Oct. 23, 1997, a method is disclosed for alleviating the undesirable increase in the dielectric constant of HSQ resulting from subsequent PECVD deposition of an oxide layer and planarization. The disclosed method comprises restricting the heat soaking period to no greater than about 10 seconds. However, there exists a need for further improvements in methodology to alleviate the undesirable increase in the dielectric constant of HSQ upon subsequent processing, particularly PECVD deposition of an oxide layer, most particularly PECVD deposition of silicon dioxide derived from silane in an N.sub.2 O-containing atmosphere at a temperature of about 400.degree. C.

HSQ baking for reduced dielectric constant


A universal kit for installing a flush lever (22) on a toilet water tank wall (12A), and a toilet with the kit components installed therein, whereby the same components can be used to quickly and efficiently install the handle on the front face, side face, or angled portion of the toilet tank. The kit comprises a fixture (66) for mounting a flush rod actuation handle (20) on a tank wall, whereby the handle can be rotated about an axis (58, 60) extending perpendicularly from the wall into the tank. A flush rod (34) is angulated in three dimensions and has opposite end portions (36, 38), having the same shape, such that either end portion is selectively securable in the mounting fixture (66) for corotation with the handle.

The present invention relates to bathroom fixtures, and particularly, to the flush lever associated with toilets.
Both consumer and institutional toilets can be ordered in a wide variety of sizes, styles, and colors. Regardless of this wide variety of available options, most toilets are operated by a handle located on either the front face or the side face of the water tank that rises from behind the seat. In some toilet installations the handle is on at an angled portion of the tank at the transition from the front face to the side face. Rotation of the handle produces a levered rotation of the flush rod located in the tank, which in turn lifts a chain associated with the flapper or other flushing mechanism to release water from the tank into the bowl.
The purpose of the present is to provide a kit, and a toilet with the kit components installed therein, whereby the same components can be used to quickly and efficiently install the handle on the front face, side face, or angled portion of the toilet tank.


When an operator attempts to move a robot from a current position to a desired position, she/he operates a manipulator lever (26) corresponding to a desired direction of a manipulator (23) of a remote control device (22), for example, a number of times corresponding to a predetermined moving amount in the moving direction. At this point, the moving amount for each moving direction depending on this number of operations is set, and a leg of the robot is actuated according to a setting value of the moving amount for each moving direction to move the robot. The moving amount that can be set by the operation of the manipulator lever (26) has a relatively small moving amount that the robot may be moved by performing a lifting/landing action once for each of the legs of the robot, and a relatively large moving amount requiring multiple walking steps of the lifting/landing action for each leg of the robot.

In recent years, a bipedal mobile robot, which has been planned to be in a practical use by the present applicants and the like, moves by an action for making two legs to alternately lift and land like a human. Further, in the present specification, "movement" of the bipedal mobile robot includes a movement from one place to another place, as well as such an action as turning almost in the same place to change orientation of the robot. In this turning action, a moving direction of the robot means a turning direction such as a clockwise direction and a counterclockwise direction. Additionally, "a stopped state" of the bipedal mobile robot is a state that the movement of the robot is not performed, so that a state with the two legs stopped as well as such a state as the robot is marching in the same place without changing orientation are included.
The present applicants attempt to establish a system for moving such a bipedal mobile robot by a remote controller having a manipulator lever such as a joystick. In this situation, for example, it is possible that a moving direction and a stride of the robot is determined in real time depending on a manipulating direction and a manipulation amount of a manipulator lever of a remote controller, thereby activating the legs of the robot according to these determined moving direction and stride.
However, in such a remote control device, when an attempt is made to move the robot to a desired position, the manipulator lever has to be operated by a manipulation amount corresponding to a moving amount from a current position to the desired position, but this manipulating amount is difficult to delicately adjust. Accordingly, for example, it is difficult to operate such a manipulator lever so that the robot is moved by a relatively minute amount (such a moving amount as a movement can be made by one step) from one place to another place and stopped. Additionally, even when a place to be reached last is known, the manipulation amount of the manipulator lever is difficult to accurately adjust while moving the robot toward the place, and as a result, it is difficult to make the robot reach the desired place.
In light of such a background, it is an object of the present invention to provide a remote control device that can surely move a bipedal mobile robot to a desired position by a relatively simple operation.

Remote control device of bipedal mobile robot


A structure for mounting a magnetron for a microwave oven is disclosed. The structure includes a wave guide member engaged with a lower plate forming the bottom surface of a cooking chamber and guiding microwaves into the interior of the cooking chamber, and a magnetron mounted at one side of the wave guide member and providing microwaves into the interior of the wave guide member, whereby the microwaves are provided in the direction from the bottom surface of the cooking chamber to the interior of the cooking chamber, for thereby supplying the microwaves in the direction from the bottom surface of the cooking chamber into the interior of the cooking chamber.

1. Field of the Invention
The present invention is directed to a microwave oven, and in particular to a structure for mounting a magnetron for a microwave oven which is capable of maximizing the capacity of a cooking chamber based on the entire size of a microwave oven and supplying microwaves in the direction from the bottom surface of the cooking chamber into the interior of the cooking chamber.
2. Description of the Conventional Art
The microwave oven is directed to generating microwaves using a magnetron for thereby cooking foods therein. FIGS. 1 and 2 illustrate the structure of a conventional microwave oven.
As shown therein, in the interior of a cavity 1, a cooking chamber 2 is formed, and a machinery compartment 3 is formed beside the cooking chamber 2.
Major elements are installed in the machinery compartment 3 for an operation of the microwave oven.
In detail, a wave guide member 4 is installed on a lateral surface of the cavity forming one wall of the cooking chamber 2, and a magnetron 5 is installed at a portion of the wave guide member 4.
In addition, a high voltage transformer 6 is installed below the magnetron 5, and a suction guide member 8 is formed beside a back plate 7 of the machinery compartment 3 for guiding an externally sucked air, and a fan 9 is installed beside the suction guide 8.
The fan 9 introduces air from the outside of the machinery compartment 3 into the interior of the machinery compartment 3.
In addition, an air duct 10 is installed on a lateral surface of the cavity 1 in the direction of the machinery compartment 3 for guiding the air from the interior of the machinery compartment 3 into the cooking chamber 2 through the magnetron 5 and the high voltage transformer 6.
In the thusly constituted conventional microwave oven, the magnetron 5 is installed at one side of the wave guide 4 installed on the lateral surface of the cavity 2 in the direction of the machinery compartment 3, so that the microwaves generated by the magnetron 5 are guided by the wave guide member 4 and then are supplied into the interior of the cooking chamber 2 from the lateral surface of the cooking chamber 2.
However, recently, as various types of microwave ovens are disclosed, it is impossible to meet various microwave oven design characteristics based on the conventional magnetron mounting structure in which the microwaves are supplied from only the lateral surfaces of the cooking chamber into the interior of the cooking chamber 2.

Structure for mounting magnetron for microwave oven


A wireless temperature-measurement system comprising (a) one or more temperature probes each including one or more energy-storage capacitors which supply the electrical energy for operation of the probe(s) and (b) a probe-charging station having circuitry configured to supply electric charge to the energy-storage capacitors prior to the temperature probes being positioned to measure temperature.

There is a need for reliable and safe temperature-measurement systems, particularly for the food industry. Among the issues which exist within such applications is the safety of such systems by preventing any contamination of food being cooked from the measurement system itself. The safety of the food product itself, such as caused by failure to reach a safe temperature level, is a significant concern; the legal and financial ramifications of biologically-contaminated food product from undercooking are enormous. Further, the quality of a food product often depends on proper cooking times and temperatures, such as avoiding overcooking which can have significant and costly market implications.
Creation of a 400-600° F. high-temperature wireless temperature probe for cooking is difficult due to the limited materials that can be used to withstand high temperatures. In addition, such probes may be used in a variety of applications such as cooking in apparatus such as rotisseries, crock pots, ovens, grills, sous vide appliances, and in a variety of commercial cooking equipment. The electronics and energy source in such probes must be housed in the temperature probe tip that is inserted into the food product, thus keeping the electronics and energy source at a temperature below 212° F. However, if the probe falls out of the food product, the probe may be exposed to high temperatures that can cause materials to incinerate and expel toxic gases. For example, in a rotisserie oven, chicken meat gets very tender and may fall off the rotating spit. In this situation, if the probe contains a lithium-ion battery as its energy source, it would vent toxic gases into the oven and into the room after being exposed to such high heat.
One product on the market is called "Meater®" and was developed by Apption Labs Limited of Encino Calif. The "Meater®" uses a rechargeable lithium-ion battery that outgases when exposed to temperatures greater than 400° F., a temperature often exceeded in commercial rotisserie ovens.
At least one other battery-free temperature sensor is available, from Farsens, a company in San Sebastian, Spain. These battery-free temperature sensors are based on RFID technology and are not built to withstand the high temperatures and harsh conditions of the applications addressed by the inventive sensor disclosed herein.
The inventive temperature-measurement system disclosed herein, although presented in the context of a food-cooking application, is more broadly applicable.


A 3-dimension thermoformed bicomponent fiber nonwoven material comprising a lofty bicomponent material layer forming a plurality of peaks separated from one another by channels and having a basis weight in the range of about 0.5 to 7.0 ounces per square yard. The bicomponent material layer comprises a structural component and a heat activatable adhesive component suitable for thermoforming. Also disclosed are various configurations of this material suitable for use in absorbent personal care articles such as sanitary napkins, disposable diapers, incontinent-care pads and the like.

1. Field of the Invention
This invention relates to a bicomponent fiber nonwoven material which, due to its shape as well as the conditions for its production, exhibits ultra high resiliency. These materials are suitable for use as a body-side liner material for personal care absorbent articles including diapers, feminine pads, incontinence garments, and training pants, as inserts for personal care absorbent products, and as a shell for an absorbent core of such articles. These materials provide for feces separation and containment, air circulation, menses management and containment, and fluid distribution and containment.
2. Description of Prior Art
Absorbent personal care articles such as sanitary napkins, disposable diapers, incontinent-care pads and the like are widely used, and much effort has been made to improve the effectiveness and functionalities of these articles. Thick, flat personal care articles of the past that do not fit the shape of the human body and do not conform to the movements of the user have been largely replaced by resiliently conforming 3-dimensional, body-shaped articles.
Diaper dermatitis is a skin condition resulting from the prolonged contact of wet occlusive diapers with the skin of the wearer. This prolonged contact can lead to excessive hydration of the outermost skin layer, thereby reducing the skin's ability to function as a barrier. As a result, there is an increase in the permeation of irritants, susceptibility of the skin to physical damage, and invasion of the skin by microorganisms. Maintaining a normal skin hydration level helps the skin maintain its optimum barrier properties. Thus, it is important that personal care absorbent articles, to the extent possible, prevent excessive skin hydration while containing body exudates and providing a soft, dry and comfortable feel to the wearer.
Current occlusive absorbent garments with flat liners hold body exudates against the skin of the wearer. Heat and moisture are prevented from escaping from the product due to the close fitting nature of the product design to prevent leakage. This problem is most severe in the insult region of personal care absorbent products. The flat liner provides a high contact area with the skin which can act as a pathway to conduct back to the skin free liquid that is not locked up by the absorbent core, especially when the product is under pressure at the insult point, because the flat liner cannot provide a sufficient degree of separation of the wearer from the free liquid. In addition, flat liners do not allow the insult region of the personal care absorbent product to communicate with the ambient air to allow humidity to be reduced in the insult region as well as away from the insult region.
Numerous means for achieving communication of the interior region of a personal care absorbent product with the ambient air, including breathable backsheets, waste vents, and leg vents, are known. However, these methods suffer from a variety of difficiencies, rendering them less effective than desired to achieve normal, unoccluded skin hydration levels. For example, breathable backsheets provide a pathway for drying through the backsheet to the interior of the absorbent product. However, the wet absorbent can hinder true communication between the skin and the ambient air. In addition, waist and leg vents through the backsheet tend to either be occluded against the skin or provide leakage pathways.
Other known methods include the use of folded absorbent cores or layers under the liner to dry the liner, that is the skin contact layer. However, these methods require undesireable process options and economics and do not truly allow the ambient air to dry the skin of the wearer; rather, they merely dry the skin contact layer. As a result, there is a need for a material that can be used for, among other things, a liner material for personal care absorbent products such as diapers, training pants, incontinence garments, sanitary napkins, bandages and the like, which is capable of reducing the humidity in the insult region of the product and the skin hydration level of the wearer.

Ultra resilient three-dimensional nonwoven fiber material and process for producing the same


A rain deflector for use with a rain gauge comprises a base portion, at least one arm portion having an axis and extending upwardly from the base portion, and attachment means whereby the deflector can be secured to a rain gauge. The arm portion provides an obstruction to rain falling in a direction at an angle to the axis of the arm portion and deposits the rain obstructed into the rain gauge to thereby compensate for rain which would not otherwise be captured in the rain gauge as a result of the direction of the rainfall.

This invention relates deflectors for use with rain gauges, or rain gauges with deflectors used for enhanced and more accurate measurement of rainfall.
Rain gauges are common instruments for measuring the extent of rainfall, and come in a variety of shapes and sizes. For example, one form of rain gauge may comprise a hollow conically-shaped housing, open at its wide end which faces upwardly to collect the rain, with calibrated indications down the length of the gauge to facilitate easy reading of the amount of precipitation. One advantage of a conical shaped structure with a wide open end and a pointed lower end is that the larger surface area will be exposed to rain and therefore, based on the size of the rain gauge, capture more water as well as provide a broader indication of the amount of rain. However, cylindrical or other shaped rain gauges are equally effective and in common use.
Existing rain gauges have, of course, fixed surface areas for admitting rain, and would usually be constructed with calibration markings down the side; these calibration markings are based on rain falling about parallel to the axis of the rain gauge, usually vertically, also at about 90.degree. to the horizontal. These existing rain gauges would, therefore, be reasonably accurate for rain falling vertically, but as the direction of rain changes with respect to the vertical, the amount of water being captured by admission through an open aperture at the top of the rain gauge would decrease. As an extreme, if rain were falling at an angle approaching the horizontal, very little or no rain would pass through the aperture into the rain gauge and the rain gauge would indicate no or very little rainfall. This is, of course, inaccurate.
Under normal circumstances, rain will fall at many different angles relative to the vertical, depending on the direction of the wind, and the force of the wind, at any given time. In rainstorms, it is not unusual for the force and direction of the wind to change from one moment to the next, impacting the amount of water captured by the rain gauge over a period of time. Thus, the amount of water captured by a rain gauge would decrease as a result of wind factors, even though the amount of rain falling may have been reasonably steady.


.epsilon.-Caprolactam is continuously recovered from carpet made from nylon 6 face fibers and a backing. The carpet is fed to a separator to prepare scrap containing nylon 6 and auxiliary materials. The scrap from the separator is fed to a depolymerizing reactor to produce an .epsilon.-caprolactam containing distillate and more auxiliary materials. The .epsilon.-caprolactam in the distillate is separated from other volatiles and purified. The auxiliary materials are also recovered or re-used.

As used herein, the term "auxiliary stream" refers to a stream generated during the recovery of .epsilon.-caprolactam which does not contain primarily .epsilon.-caprolactam or poly .epsilon.-caprolactam.
As landfills continue to reach capacity, raw materials are depleted, and man recognizes that the earth's resources are limited, more and more materials are recycled. Synthetic polymers have long presented problems in recycling due to their often being commingled with other materials and to sometimes apparently irreversible polymerization from which useful raw materials cannot be easily obtained.
Certain polyamides, however, are known to be hydrolytically convertible to monomers which can be re-used. Especially in the case of nylon 6, the monomeric starting materials are reclaimed from waste polymer and used in the manufacture of man-made fibers. The literature reveals procedures for reclaiming such monomers and polymers. L. A. Dmitrieva et al., Regeneration of .epsilon.-Caprolactam from Wastes in the Manufacture of Polycaproamide Fibres and Yarns, Fibre Chemistry, March 1986, pp. 229-241, describes methods for reclaiming polycaprolactam (nylon 6) waste.
There are generally two methods for reclaiming nylon 6 waste. The first involves reprocessing the waste nylon 6, for example, via remelting and extrusion, to form useful articles. This concept is demonstrated in U.S. Pat. No. 4,143,001 to Raab et al.
The second method involves chemical regeneration through depolymerization. Processes for depolymerizing solid polyamide waste are known. For example, U.S. Pat. No. 2,343,174 to Edison et al. shows general hydrolytic depolymerization using steam. U.S. Pat. No. 3,988,406 to Nakamura et al. shows the recycling of polyamide waste by thermal depolymerization.
Among the polyamides depolymerized for re-use of the monomer is nylon 6. For example, U.S. Pat. No. 4,107,160 to Dicoi et al. describes reclamation of solid nylon 6 waste (generated during the processing of nylon 6), low molecular weight oligomers and residual monomer from the polycondensation of caprolactam.
Other polymers are also recycled. An example of a process for continuously degrading various plastics is provided in U.S. Pat. No. 4,051,212 to Grigat et al. Grigat et al. shows a process for continuously hydrolytically degrading plastics. The hydrolyzable material is introduced with water into a screw machine, where it is subjected to a temperature of 100.degree. C. to 300.degree. C. at a pressure of 5 to 100 bars for 2 to 100 minutes.
Although the motivation for reclaiming raw materials from waste polymer or spent polymeric products is well recognized, some products do not readily lend themselves to recycling. Items which are composites of several materials present problems. Along these lines, polymeric materials formed into carpets present an interesting reclamation problem. This is due, in part, to the variety of materials present in traditional carpet and the manner in which they are intimately connected. In traditional carpets, the tufts are often nylon 6, while the backing of a nylon 6 tufted carpet may include jute, polypropylene and latex, among other things. Also, the latex may contain fillers such as calcium carbonate, clay or aluminum trihydrate. The chemical and physical nature of these materials is such that reclamation of .epsilon.-caprolactam from nylon 6 carpets has traditionally been considered too complex, too expensive and too cumbersome to be practical.
Traditional thought was that polypropylene or jute and especially latex would generate impurities which would make purification so difficult or the reclaimed yield so low as to render depolymerization of carpets impractical. Moreover, the CaCO.sub.3 usually present in the latex as filler would neutralize an equivalent amount of any acid depolymerization catalyst, such as H.sub.3 PO.sub.4.
In addition, many recycling schemes focus on a single ingredient in a mixed waste stream, leaving the remaining ingredients for landfilling, incineration, etc. Yet, the more portions of mixed waste that can be regenerated to materials having another useful life, the more valuable, economically and environmentally, is the process.

Reclaiming epsilon-caprolactam from nylon 6 carpet


A process for preparing a cyclic ester by reacting an .alpha.-hydroxycarboxylic acid or an .alpha.-hydroxycarboxyliclic acid ester with an orthoester. A process for purifying a cyclic ester by containing water and acid as impurities by adding an orthoester to a cyclic ester obtained by reaction of a reaction mixture including an .alpha.-hydrocarboxylic acid or an .alpha.-hydroxycarboxyliclic acid ester. According to the present invention, a high-purity cyclic ester containing small amounts of impurities such as water and an acid component can be provided.

1. Field of the Invention
The present invention relates to a preparation process and a purification process of a cyclic ester typified by glycolide, lactide and tetramethyl glycolide. More specifically, it relates to a process for easily preparing a high-purity cyclic ester having extremely low contents of impurities such as an acid and water in a high yield by the use of an orthoester, and a process for purifying the cyclic ester.
2. Description of the Related Art
Cyclic esters typified by glycolide and lactide are cyclic dimers produced by the dehydration of two molecules of an .alpha.-hydroxycarboxyliclic acid or its ester, or by the removal of an alcohol therefrom, and they fall into the category of intramolecular cyclic esters. Thus, poly(.alpha.-hydroxycarboxyliclic acid esters) typified by poly(glycolic acid) and poly(lactic acid) obtained by the ring opening polymerization of these intramolecular cyclic esters have excellent biological degradation properties, so that they have been utilized as biologically degradable materials. In recent years, the problem of plastic wastes occurs owing to the shortage of garbage reclaiming lands and the incineration of the wastes, and so the poly(.alpha.-hydroxycarboxylic acid esters) are expected as biologically degradable plastics which can be degraded by hydrolysis, enzymes and microorganisms. In consequence, the demand and supply of these polyesters are gradually increasing.
In order to achieve a high molecular weight required for the biologically degradative materials and the biologically degradative plastics, it is necessary that the content of impurities such as an acid and water in a cyclic ester which is a starting material should be controlled to the lowest possible level, because such impurities disturb the attainment of the high molecular weight necessary to obtain sufficient physical properties. In the case of lactide, for example, it has been expected that the acid content is preferably 10 meg/kg or less, more preferably 5 meg/kg or less, and the water content is preferably 200 ppm or less, more preferably 100 ppm or less.
As a process for preparing a cyclic ester such as lactide of another .alpha.-hydroxycarboxyliclic acid or .alpha.-hydroxycarboxyliclic acid ester, there is usually a process for preparing the cyclic ester which comprises polymerizing a corresponding .alpha.-hydroxycarboxyliclic acid or .alpha.-hydroxycarboxyliclic acid ester to form a poly(hydroxycarboxylic acid) or a poly(hydroxycarboxylic acid ester) which is an oligomer, heating this oligomer up to about 200.degree. C. in vacuum in the presence of a catalyst known in this technical field which is typified by stannous octanoate to decompose the same, whereby a cyclic dimer is obtained, and then distilling off the thus obtained cyclic ester (e.g., U.S. Pat. Nos. 1,095,205, 2,668,162, 4,797,468 and 5,053,522, Japanese Patent Application Laid-open Nos. 101378/1988 and 268179/1990, and Japanese PCT Patent Application Laid-open Nos. 503490/1995 and 505150/1995).
However, in the cyclic ester obtained by such a process, volatile impurities such as water and an acidic hydroxyl compound are included (refer to Comparative Example 3). Examples of these impurities usually include water, an .alpha.-hydroxycarboxyliclic acid monomer and oligomers of the .alpha.-hydroxycarboxyliclic acid. As described above, water and the carboxylic acids function as polymerization inhibitors during the polymerization of the cyclic ester, and they also deteriorate the storage stability of the cyclic ester. Therefore, the presence of these impurities is not preferable. Furthermore, Japanese PCT Patent Application Laid-open No. 503490/1995 and 505150/1995 have disclosed methods which comprise removing the hydroxyl impurities by redistillation to obtain the high-purity cyclic ester, but these methods have many disadvantageous points with respect of industrialization. For example, the yield of the cyclic ester which can be used as a polymer material deteriorates; the cyclic ester can scarcely possess such a quality as to be usable as the polymer material, even when the redistillation is done; operation is intricate; and facilities for the redistillation are additionally required (refer to Comparative Example 4).
In Japanese PCT Patent Application Laid-open No. 504916/1995, a process for preparing the cyclic ester from hydroxy acid and its derivative has been described, in which existing water is removed by the use of water getters such as acetic anhydride, an acetal and a carbodiimide in a step. However, these compounds have not been used in examples of the above-mentioned publication, and so the effect of the compounds is indefinite. Furthermore, in view of a fact that acetic acid is produced from acetic anhydride, the employment of acetic anhydride results in a reverse effect, instead of the reduction of an acid value. According to experiments of the acetal by the present inventors, the effect of the acid value reduction has not been observed (refer to Comparative Example 6). The carbodiimide has both the effects of the water removal and the acid value reduction, but since it contains a nitrogen atom, the carbodiimide causes the coloring of the cyclic ester, and it is also very expensive. For these reasons, it is difficult to industrially use the carbodiimide. Also in Japanese PCT Patent Application Laid-open No. 504762/1994, some water getters are referred to, but it is apparent that they also have the above-mentioned drawbacks.
In Japanese Patent Application Laid-open Nos. 287056/1993 and 287278/1994, a manufacturing process of an aliphatic polyester has been described which comprises polycondensing an .alpha.-hydroxycarboxyliclic acid in the presence of a primary alcohol, a carbodiimide or a polyhydric alcohol having 3 or more hydroxyl groups (a carboxyl group concentration adjustor) to form a precursor polymer having a carboxyl group concentration of 200 meg/kg or less, heating the precursor polymer to depolymerize it, and then subjecting the resulting cyclic ester to ring opening polymerization. Furthermore, Japanese Patent Application Laid-open No. 309862/1995 has described a process for preparing lactide which comprises dehydrocondensing lactic acid, to which a polyhydric alcohol having 3 or more hydroxyl groups has been added, in the presence of a metallic compound having the electronegativity of a metallic ion in the range of 10 to 15 to synthesize a precursor polymer having a carboxyl group concentration of 200 meg/kg or less, and heating this precursor polymer to depolymerize it. However, the cyclic ester (lactide) obtained by these methods also has some drawbacks. For example, the cyclic ester (lactide) does not possess such an acid value that it withstands a use as a polymer; the purity of the cyclic ester (lactide) is low and so a purification step is necessary for the use as the polymer; and the carboxyl group concentration adjustor and a substance formed by the modification of the adjustor with a reaction always remain in a reaction solution, which fact might cause the coloring of the obtained cyclic ester (lactide).
As techniques of purifying the cyclic ester, there are known recrystallization methods in which a sufficiently dried organic solvent such as toluene, ethyl acetate or isopropanol, or a mixed solvent is used (e.g., Japanese Patent Application Laid-open No. 101378/1988, Japanese PCT Patent Application Laid-open No. 507076/1993, and Japanese Patent Application Laid-open Nos. 279435/1994, 1,182,59/1995 and 2,068,51/1995; and as methods similar to the recrystallization methods, Japanese Patent Application Laid-open No. 165430/1988, and Japanese Patent Publication Nos. 25912/1990 and 15712/1993). The cyclic ester, from which the impurities for disturbing the polymerization have been removed by the recrystallization method and which has sufficiently been purified, can be used as a monomer for the polymerization, after subjected to steps such as filtration and drying. However, such a recrystallizing operation leads to the deterioration of the yield of the cyclic ester, makes the procedure intricate, and increases costs due to facilities required for the recrystallizing operation. Hence, the recrystallization methods have many disadvantageous points which make industrialization difficult.
Japanese Patent Application Laid-open No. 256340/1994 has suggested a purification process of lactide which comprises (1) cooling a molten mixture of lactide and impurities to the solidifying point of lactide or a little lower temperature than the solidifying point of lactide, (2) partially crystallizing the molten mixture to form a solid phase having a lower impurity content than the molten mixture and a liquid phase having a higher impurity content than the molten mixture, and (3) separating the solid phase from the liquid phase to collect the solid phase. This process has succeeded in obtaining lactide having an acid value of about 2 meq/g which can be used as a polymer material. However, this process also has some drawbacks. For example, temperature control is difficult in melting a solid lactide mixture and in cooling the molten mixture to the solidifying point of lactide; productivity is poor for reasons of a low zone movement rate and the like; and a facility cost increases uneconomically. Hence, this process has many disadvantageous points which make it difficult to actually industrialize the process.
In Japanese Patent Application Laid-open No. 223248/1991, a process for preparing an unsaturated dicarboxylic acid imide compound has been disclosed which comprises dehydrating an unsaturated dicarboxylic acid amide acid compound in the presence of an acid anhydride as a dehydrating agent, a basic catalyst and a metallic salt catalyst to close its ring, and then decomposing a secondarily produced acid with an orthoester into an alcohol and an ester to remove the acid, thereby obtaining the unsaturated dicarboxylic acid imide compound. However, in this publication, the preparation method of the unsaturated dicarboxylic acid imide compound is only described, and any description regarding the process for preparing the cyclic ester is not referred to therein.

Preparation process and purification process of cyclic ester


Disclosed herein is a method for producing golf balls which comprises surface-treating a golf ball with atmospheric pressure plasma prior to finish coating. The resulting golf balls have a coating film which is in good adhesion to the golf ball and highly resistant to discoloration and deterioration by heat, moisture, and light. The surface treatment is by the atmospheric pressure plasma which does not need the treating apparatus to be evacuated. The surface treatment under atmospheric pressure requires only a simple treating apparatus and can be applied to any golf balls without evaporating volatile matters contained therein.

1. Field of the Invention
The present invention relates to a method for producing golf balls, and more particularly to a method for producing golf balls having a coating film which is in good adhesion to the golf ball.
2. Description of the Prior Art
Golf balls including thread-wound golf balls and solid golf balls such as one- or two-piece solid golf balls are always provided with a surface coating. The surface coating plays an important role not only in the protection of letters, numerals, and symbols stamped on the golf ball, and of surface gloss and good appearance, but also in the reduction of air resistance which leads to improvement in their flying performance.
The surface coating is usually formed from a polyurethane paint. However, it will peel off upon intense impact by a golf club if it is formed after molding by mere application of a polyurethane paint to the surface of a golf ball. For the improvement of adhesion between a golf ball and a surface coating, several attempts have been made to perform surface treatment on the surface of the golf ball. None of them have achieved satisfactory results and there remain many problems unsolved in the manufacturing process.
There is a known method for surface coating which consists of treating the surface of a golf ball with flame prior to coating. This method is not desirable because it is in danger of fire and burn. Moreover, it does not provide-sufficient film adhesion. There is another known method for surface coating which consists of roughening the surface of a golf ball by sandblasting or the like. This method does not improve the film adhesion as desired, but it seriously damages the dimples formed in the surface.
There is disclosed in Japanese Patent Publication No. 39266/1988 a method for improving film adhesion to golf balls by surface treatment with a low-pressure plasma. A disadvantage of this method is the necessity of a vacuum chamber for plasma treatment which has to be isolated from the atmosphere by a valve, and continuous treatment depends greatly on the life of the valve. Another disadvantage is that the plasma treatment under low-pressure is not useful for golf balls covered with balata resin which gives off volatile ingredients under reduced pressure.
There is disclosed in Japanese Patent Laid-Open Nos. 15171/1990, 48626/19901 241739/1991 and 236475/1991 a method for treating the surface of an object with a glow plasma obtained under atmospheric pressure. This method is suitable for flat objects but is not suitable for spherical objects like golf balls.