The present invention relates to a semiconductor device comprising a chip size package of the type used for a high density mounting module, a multichip module, and the like, a method of manufacturing the same, and to a semiconductor wafer used for manufacturing the semiconductor device.
Currently, in accordance with the current trend toward making electronic devices small, while retaining a high performance, semiconductor devices used therein are required to have a high integration, a high density, and to have a fast processing speed.
Corresponding to such a requirement, the methods of manufacture of semiconductor devices have been changed from the pin insertion type to a surface implementing method for increasing the implementing density; and, in order to accommodate an increasing number of pins, packages, such as a DIP (Dual Inline Package),a QFP (Quad Flat Package), a PGA (Pin Grid Array), and the like, have been developed.
However, implementation of the QFP is becoming difficult because of the increasing number of pins, since the connecting leads with the implementing substrate are concentrated at the periphery of the package, and the lead itself is thin and can be readily deformed. The PGA is disadvantageous in a high density implementation, because the increasing processing velocity is difficult to attain electrically, since terminals of the PGA for connecting with the implementing substrate are slender and are concentrated so as to be extremely close to each other, and surface implementation is impossible, since the PGA package is a pin insertion type.
Recently, in order to solve the above problems and to realize a semiconductor device having an increased processing velocity, a BGA (Ball Grid Array) package has been developed. The BGA package comprises a stress buffer layer between semiconductor chips and a substrate whereon circuits are formed, and bump electrodes, which are external terminals, on the implementing substrate side of the substrate whereon circuits are formed (U.S. Pat. No. 5,148,265). A package having a BGA structure is readily implemented on the surface, because deformation of the leads, such as occurs in a QFP does not occur, since the terminals for connection with the implementation substrate are provided in the form of ball-shaped solders, and the pitch between the terminals can be wide, since the terminals are dispersed all through the implementing plane. Furthermore, because the length of the bump electrode, i.e. the external terminal, is short in comparison with the PGA package, the inductance component is small, the signal velocity is fast, and it is possible to accommodate the requirement to increase the processing velocity.
On the other hand, JP-A-8-172,159 (1996) discloses a LOC (Lead On Chip) package, which comprises a cross sectional composition formed of sealing material/chip/protecting film/sealing material, as a chip provided with a protecting film. The protecting film increases the adhesion of the chip with the sealing material, and, at the same time, protects the chip from damage by a pick up pin.
JP-A-7-135189 (1995) discloses an invention relating to a wafer adhesion sheet for manufacturing semiconductor devices having a LOC structure. The wafer adhesion sheet is used as a protecting film until the chip is mounted in a package during the process for manufacturing the semiconductor.
Recently, in accordance with widespread use of portable information terminals, a decrease in size and a high density mounting of semiconductor devices are required. Therefore, a CSP (Chip Scale Package), the package size of which is almost the same as chip, has been developed. A CSP of various types has been disclosed in “Nikkei Micro Device” p38–p64, published by Nikkei BP Co. (February, 1998). A CSP is typically manufactured by the steps of: adhering semiconductor chips, which has been cut into respective pieces, onto a polyimide substrate or ceramic substrate, whereon a circuit layer is formed; electrically connecting the circuit layer with the semiconductor chip by a method such as wire bonding, single point bonding, gag bonding, bump bonding, and the like; sealing the connecting portion with a resin; and forming external terminals, such as solder bumps.
JP-A-9-232256 (1997) and JP-A-10-27827 (1998) disclose methods of mass production of a CSP. In accordance with these methods, the semiconductor device is manufactured by the steps of: forming bumps on the semiconductor wafer; connecting the circuit substrate electrically via the bumps; sealing the connecting portions with a resin; forming the external electrodes on the circuit substrate; and cutting the wafer into respective pieces. The “Nikkei Micro Device” p164–p167, published by Nikkei BP Co. (April, 1998), discloses another mass production method for the CSP. In accordance with the disclosed method, the semiconductor device is manufactured by the steps of: forming bumps on the semiconductor wafer by soldering; sealing portions other than the bumps with a resin; forming external electrodes at the bump portions; and cutting the wafer into respective pieces.
Among the CSP which are assembled by adhering the semiconductor chips cut in pieces to a polyimide substrate or a ceramic substrate, a CSP wherein a circuit layer is connected to the chip by wire bonding becomes larger than the chip size, naturally, because the bonding area of the circuit layer is located outside of the chip. In the case of a CSP connected by bump bonding, the substrate becomes larger than the chip in order to prevent resin from flowing down at the time of potting, because the interval between the chip and the substrate is sealed with resin after bonding. Accordingly, a problem occurred in that the package size of such a CSP became larger than the chip.
A CSP using chips cut in pieces experienced a problem in that it took a long time to manufacture the semiconductor device, because, after dicing the chips, each respective chip must be located correctly on the substrate, adhered thereon, connected electrically, and sealed.
A CSP using a resin substrate, such as a substrate made of polyimide and the like, as the circuit layer had a problem in that water, absorbed in the package at re-flowing when the package was provided onto the mounting substrate, was expanded and failures, such as bubble formation and peeling off, were generated, because the chip was adhered with an adhering agent.
A CSP, which was manufactured by the steps of: forming bumps on the semiconductor wafer; connecting the semiconductor wafer with the substrate; sealing the interval between the substrate and the semiconductor wafer with a resin; forming the external electrodes; and cutting the semiconductor wafer into respective pieces; had a problem of warping of the semiconductor wafer and the semiconductor device due to curing shrinkage, because the resin layer was formed on only one side of the wafer.
Additionally, except for the wire bonding type CSP, many of the CSP have an exposed plane, which is opposite to the plane whereon the circuits are formed on the chip. Therefore, there was a problem in that failures, such as cracks, were generated at the edge of the chip, and damage to the rear plane occurred due to the package falling down during transportation and handling thereof, such as when the package is picked up during a mounting operation.


At the present time several magazines run a dating column where a person may leave a message for an unknown person whom they have seen or encountered, in the hope that said person will see the message and respond to them. This system is unsatisfactory because of the low probability that the person to whom they wish to send the message would see the message, the low probability that they would be able to recognise that it was themselves for whom it was intended and the fact that because they would not see it until some time after the chance meeting, they are less likely to want to respond.
The aim of the present invention is to allow a person to send a message to a stranger whom they encounter. Typically, they will send an e-mail or short text message from their own mobile telephone.
The invention aims to enable that message to reach the intended person and preferably to allow them to respond in a fun, safe and convenient fashion.


1. Field of the Invention
The present invention relates generally to traveling lights, and more particularly to lights for use with in-line roller skates.
2. Description of the Prior Art
Roller skating at night or near dusk is an exciting but potentially dangerous activity. Recognizing this fact, inventors have tried to provide lights for roller skates, but have failed to provide lights that are genuinely easy to apply to, and remove from, a variety of skates.
U.S. Pat. No. 4,367,515, issued on Jan. 4, 1983, to Steven F. Beard, describes a roller skate light attachment that mounts on a stop portion of a roller skate. There is no provision for mounting the attachment on a skate not having a stop portion.
U.S. Pat. No. 4,463,412, issued on Jul. 31, 1984, to Ronald W. Broach, describes an illuminated shoe skate attachment. The attachment mounts to bolts or ridges on a skate by use of a complicated set of brackets. The attachment is detachable for use on other skates, but only if the brackets fit the other skates.
U.S. Pat. No. 4,991,066, issued on Feb. 5, 1991, to Gregory L. McCowan, describes an adaptor kit for providing lighting for a skateboard. The lighting replaces a part ordinarily present on a skateboard and is thus unsuitable for use with roller skates.
U.S. Pat. No. 4,997,196, issued on Mar. 5, 1991, to John L. Wood, describes a system in which lights are mounted in grooves in a skateboard or in skid bars in a skateboard. There is no provision for mounting lights on roller skates.
U.S. Pat. No. 5,033,212, issued on Jul. 23, 1991, to Walter R. Evanyk, describes a lighting system which is mounted to objects such as shoes by use of hook-and-loop fasteners. There is no use of stretchable cord to ensure an easy and lasting engagement of the lighting system with an object to which it is attached.
U.S. Pat. No. 5,327,329, issued on Jul. 5, 1994, to David L. Stiles, describes lighting attachments for in-line skates that are frictionally and adhesively mounted. There is no use of stretchable cord to ensure an easy and lasting engagement of the lighting system with an object to which it is attached.
Canadian Patent Document No. 1 253 832, issued on May 9, 1989, to Nicholas A. Rodgers, describes lights for footwear. There is an internally disposed switch that responds to movement of a wearer. There is no provision for mounting lights on roller skates.
French Patent Document No. 2 643 794, issued on Sep. 7, 1990, to Jean Leonard Darfeuille, describes head-lights for footwear. There is an internally disposed switch that senses presence of a wearer. There is no provision for mounting lights on roller skates.
None of the above inventions and patents, taken either singly or in combination, is seen to describe the instant invention as claimed.


The invention relates to a trampoline with a base, which includes a frame, and with a jumping sheet, which preferably includes hook elements on its underside, the jumping sheet being connected to the frame by means of a plurality of annular strap sections, which each extend at least partially around the frame and are secured to the hook elements. The invention is also directed to a hook element for trampolines.
Trampolines are widely used in physiotherapy and in the leisure area.
In the case of so-called mini-trampolines, a distinction is made between trampolines with a spring suspension and a rubber strap ring suspension. In the case of a spring suspension, the jumping sheet is secured to the frame by means of spiral springs. Such a suspension makes considerable acceleration forces available and is thus suitable, in particular, for sports training with high demands on the cardiovascular system.
In the case of a rubber strap ring suspension, one or more elastic straps or strap sections are used, which connect the jumping sheet to the frame. The larger elasticity of such a fastening produces “softer” deceleration of the body and is thus primarily suitable in the case of joint and back problems, in rehabilitation, for relaxation and combating stress and for children.
Only a single elastic strap was originally provided in strap suspensions, see for example DE 299 19912 U1. The strap is wound alternately about the frame of the trampoline and pulled through loops arranged on the underside of the jumping sheet. It has, however, transpired in practice that the known trampoline has disadvantages in operation. Thus the fastening of the jumping sheet to the frame is perceived to be complex. Furthermore, tilting of the jumping sheet with respect to the frame can occur in use. In particular, however, the entire strap must be replaced if only one point on the strap is abraded or worn.
There has therefore been a move to suspending the jumping sheet on a plurality of annular strap sections, which are preferably fastened to the underside of the jumping sheet and are looped around the frame. Such a trampoline is disclosed in, for instance, DE 102 26707 B4 emanating from the applicant. By contrast with the suspension of the jumping sheet with only a single strap, the individual strap suspension combines a number of advantages. Above all, the durability is significantly increased. Furthermore, replaceability is also better (and cheaper). If a strap section is worn, it is simply replaced individually. The other strap sections remain untouched. Finally, the individual strap suspension always ensures correct centering of the jumping sheet.
The individual strap suspension has basically proved to be satisfactory. There is, however, the endeavour to improve the known trampoline. This applies, in particular, with regard to the wear resistance of the suspension.


1. Technical Field
The present invention is directed to elevator dispatching. More particularly, the present invention is directed to assigning an elevator car to a floor in response to a hall call registered at the floor, based on a series of bonuses and penalties and remaining response time.
As used herein, remaining response time means an estimation of the amount of time required for an elevator car to reach the floor at which the hall call is registered, given the car calls and hall calls to which the elevator car is committed.
2. Background Information
In a building having a plurality of floors, each floor typically has a set of buttons located in the hallway at or near the elevators. These buttons, commonly referred to as hall call buttons, enable users to request elevator car service in a predetermined direction, i.e., up and/or down. Additionally, the interior of an elevator car is generally equipped with a plurality of buttons, commonly referred to as car call buttons, which enable users to request service to specific floors.
In simplified terms, an elevator control system, also referred to in the art as an elevator dispatching system, monitors the status of the hall call buttons at the floors and car call buttons in the elevator cars, assigning elevator cars to the floors in response to hall call and/or car call registration.
As used herein, relative system response, commonly abbreviated RSR, means an elevator dispatching system which employs a series of bonuses and/or penalties to determine which elevator car to assign to a registered hall call. RSR dispatching systems are well known in the art. For example, U.S. Pat. No. 4,363,381 issued to Bittar, entitled Relative System Response Elevator Call Assignments, U.S. Pat. No. 4,815,568 to Bittar, entitled Weighted Relative System Response Elevator Car Assignment System With Variable Bonuses And Penalties, U.S. Pat. No. 4,782,921 to MacDonald et al., entitled Coincident Call Optimization In An Elevator Dispatching System, U.S. Pat. No. 4,790,412 to MacDonald et al., entitled Anti-Bunching Method For Dispatching Elevator Cars, and U.S. Pat. No. 4,793,443 to MacDonald et al., entitled Dynamic Assignment Switching In The Dispatching Of Elevator Cars, herein incorporated by reference.
In RSR dispatching systems, each elevator car has associated therewith a value for each one of the bonuses and penalties, the values being dependent upon the elevator status, relative to the registered hall call. An RSR value for each elevator car is determined by cumulating the bonuses and penalties for each elevator car, and the elevator car having the most favorable RSR value is assigned to respond to the registered hall call.
Certain penalties of the Bittar systems combine to yield an estimate of the response time of each elevator car to respond to the registered hall call. Some of the various penalties used in the Bittar systems include a run time penalty (RTP) based on the time required for an elevator car to travel between hall and car stops assigned thereto; a travel-through express zone penalty (TRE) based on the time required to travel through the express zone; and a hall stop penalty (HSP) and a car stop penalty (CSP) based on the time delay incurred for each hall stop and car stop, respectively, assigned to the elevator car.
The bonuses of the Bittar systems offset the penalties, thereby favoring an elevator car based on certain conditions. Examples of various bonuses used in the Bittar systems include a coincident car call bonus (CCB) which favors an elevator car having a car call coincident with the floor registering the hall call; a contiguous stop bonus (CSB) which favors an elevator car having a commitment at a floor contiguous with the floor registering the hall call; and a previously-assigned bonus (PAB) which favors the elevator car previously assigned to the hall call.
In the Bittar systems, the RSR value is determined by subtracting the bonuses and adding the penalties, and the elevator car having the lowest RSR value is the most favorable. Similarly, in the MacDonald systems, the RSR value is determined by substracting bonuses from an estimated arrival time, based on items substantially similar to RTP, TRE, HSP and CSP, with the elevator car having the lowest RSR value being the most favorable. The bonuses employed by the MacDonald systems are similar to the CCB (see U.S. Pat. No. 4,782,921), the CSB (see U.S. Pat. No. 4,790,412), and the PAB (see U.S. Pat. No. 4,793,443) of the Bittar systems.
Although these systems are defined such that the lowest RSR value is most favorable, additions and subtractions can be reversed such that the highest RSR value is most favorable.
The RSR determination typically occurs either every cycle, e.g., every 250 milliseconds, or on an "as needed" basis, e.g., whenever an elevator car changes positions, responds to a hall or car call, or whenever a new hall or car call is registered. It is conceivable that the system can reassign the unanswered hall calls to a different elevator car quite often. In order to dampen what might otherwise be an erratic dispatching system, the previously assigned bonus (PAB) is included in the Bittar and MacDonald RSR systems to favor the elevator car which was previously assigned to the unanswered hall call.
The habits and customs of the elevator user dictate the value typically assigned to the previously assigned bonus (PAB). The user predominantly in Europe and the Americas wants to be informed which elevator car will be arriving in response to the hall call shortly before it arrives. Thus, the hall lantern located at or near the arriving elevator car illuminates and/or sounds shortly before the elevator car arrives. In these types of RSR systems, the Bittar systems typically assign a relatively low value to the PAB. Thus, if another elevator car can service an unanswered hall call by at least the PAB value before the assigned car, the unanswered hall call is reassigned to that other car.
The user predominantly in Japan, on the other hand, wants to be informed which elevator car will be responding to the hall call at the time of hall call registration. In this way, the user can wait at the door of the assigned elevator. In these RSR systems, commonly referred to as instantaneous car assignment systems, the elevator car having the most favorable RSR value is almost immediately assigned to the hall call, and the hall lantern located at or near the assigned elevator car illuminates and/or sounds upon assignment. In these types of RSR systems, the Bittar systems typically assign a relatively high value to the PAB, so as to maintain the integrity of the initial car assignment.
There are situations where the initial elevator car assignment, although the best when made, subsequently turns out to be less than satisfactory. For example, in response to an intervening car and/or hall call, the boarding passengers register a plurality of car calls. Additionally, the elevator car, while traveling through the lobby or while responding to an intervening car and/or hall call, gets delayed by boarding passengers who hold the door open, e.g., to wait for others or to finish a conversation with a non-boarding person. Further, an empty elevator car may be assigned a hall call moments before a boarding passenger registers a car call in the direction opposite the assigned hall call.
Due to the large value of PAB, in immediate car assignment systems any one of these situations can drastically extend the system's registration time, defined as the time between when the hall call is registered and when the elevator car is about to arrive in response thereto, as indicated by the hall lantern at or near the arriving elevator car. The maximum registration time is a conventional indicium of overall system responsiveness. In RSR systems employing instantaneous car assignment, some buildings have rather large maximum registration times.
Such large registration times are considered highly unacceptable for at least two reasons. First, a user's irritation level is a function of the amount of time spent waiting for an elevator car. Thus, the longer the wait, the more severe his or her irritation. Second, and more importantly, before the assigned elevator car can get to the floor to service the unanswered hall call, the floor may be bypassed, up-going hall call, by at least one of the other elevator cars; e.g., a car traveling in the up direction travels past a floor having an unanswered up-going hall call.
However, due to the relatively large PAB value, the initially-assigned elevator car remains assigned to the unanswered hall call, despite the fact that at least one other elevator car is bypassing the floor having the unanswered hall call. The other elevator cars do not stop because they do not get the assignment.


The present invention relates to polymer solutions containing a sulfur-containing or oxygen-containing aromatic polymer, methods of forming such solutions, methods of using such solutions to form conducting polymer articles including films and methods of using such solutions as electrically conducting liquids.
Conductive poly(p-phenylene sulfide) and other chalcogenide polymers rendered conductive by doping with a Lewis Acid halide and other dopants are disclosed in European published patent application No. 31,444 (July 8, 1981) the subject matter of which is included in U.S. Pat. No. 4,375,427, issued Mar. 1, 1983. Such materials are prepared, in some forms, by introducing a gaseous dopant into the solid polymer pellet.
It is indicated in U.S. Pat. No. 4,375,427 that arsenic trifluoride gas, when introduced with arsenic pentafluoride gas as dopant, increases the doping efficiency.
In the general field of conducting polymers, such as polyphenylene, polyphenylene sulfide, polypyrrole and polyacetylene, it has been heretofore believed impossible to dope one of these polymers to the extent that it becomes a semiconductor or conductor and thereafter dissolve the polymer. In the absence of such solutions, the ability to form certain articles out of conducting polymers, and especially conducting or semiconducting polymer films, is restricted. In particular, doping with a gas after forming a polymer article is known to expand or distort the polymer article. Thus a need exists for techniques to facilitate the production of conductive polymers, to facilitate the doping process and, especially, to form shaped articles such as films and fibers of conducting polymers.


Sweet syrups are widely used in the baking, confectionery and beverage industries, for example. These syrups generally consist of sucrose (cane sugar) or dextrose-containing products obtained from starch hydrolysis as the principal sweetening agent. When a syrup is needed that is sweeter than that obtained from sucrose, an invert sugar syrup is employed. This is produced by acid hydrolysis of sucrose to produce a mixture of about 50 percent glucose (dextrose) and about 50 percent fructose (levulose). While glucose is somewhat less sweet than sucrose, the fructose is considerably sweeter than sucrose so that the overall sweetness is increased as compared to sucrose.
It is well known that dextrose can be converted under alkaline conditions to fructose. This conversion has great potential value in the production of sweet syrups. However, the alkaline conversion has not been commercially successful because the alkaline reaction produces an undesirably high ash level in the product syrup which is uneconomical to remove. The syrup is not acceptable unless this ash is removed. Alkaline isomerization and its attendent problems are discussed in U.S. Pat. No. 3,383,245.
The prior art then turned to an enzyme conversion of glucose to fructose. It was found that species of Pseudomonas hydrophila, Streptomyces flavovirens, Streptomyces achromogenus, Streptomyces echinatur, Streptomyces albus, Streptomyces olivaceus, and Bacillus coagulans, for example, could be grown in appropriate nutrient media to form enzymes having glucose isomerase properties. This is described in U.S. Pat. Nos. 2,950,228; 3,616,221; 3,625,828; and 3,979,261, for example. None of the known prior art suggests the use of a Bacillus licheniformis species to produce a glucose isomerase having the desirable characteristics of being stable under a wide range of pH and temperature conditions.


This invention relates to a process for producing a single crystal of garnet ferrites, and more specifically to a process for producing a single crystal of garnet ferrite suitable for use as a Faraday rotation material in an optical isolator adapted to prevent light from returning to a semiconductor laser employed for optical communication or in an optical magnetic field sensor adapted to control or protect electric power system in transformer substations.
As techniques for producing a single crystal of garnet ferrite useful as magnetooptical materials, the flux technique and LPE technique have been usually employed to date.
Of these techniques, the flux technique comprises melting raw materials for such respective components that form a ferrite having the garnet structure together with a flux component such as PbO, PbF.sub.2 and/or B.sub.2 O.sub.3 in a crucible, for example, made of platinum into a homogeneous melt and cooling the melt gradually to cause a single crystal of the garnet ferrite to grow.
Further, the LPE technique also comprises similarly to the flux technique, melting raw materials for such respective components that form a ferrite having the garnet structure into a homogeneous melt as described above and dipping a substrate having the garnet structure in the resulting melt while maintaining it at a temperature slightly lower than the saturation temperature to cause a single crystal of the garnet ferrite to grow on the substrate as a thin film.
However, the flux technique is accompanied by such problems that it requires long time, i.e., from a week to a month, for the growth of a single crystal and it cannot avoid the inclusion of impurities from the flux and crucible used.
On the other hand, the LPE technique requires shorter time for the growth of each crystal. However, in this technique, a larger single crystal having a three-dimensional structure cannot be obtained and mixing of impurities is also unavoidable because a flux and a crusible have to be used similarly to in the former technique.
Among these impurities, mixing of impurity ions other than trivalent ions, especially, Pb.sup.2+, Pt.sup.4+ and the like in a single crystal of garnet ferrite leads to a modification to the ionic valence of ferric ions (trivalent ions), thereby adversely affecting primarily the light absorption characteristic of the single crystal.
In addition, the above-employed crucible is usually made of a noble metal such as platinum. In order to cause a large single crystal to grow, it is indispensable to enlarge the crucible, resulting in a problem that the production cost jumps up.
Moreover, although it has been known that the degree of Faraday rotation .theta..sub.F (deg/cm) of the garnet ferrite can be remarkably increased by substituting the c-site component in the garnet structure partially with Bi.sup.3+, and increase in Faraday rotation is useful for miniaturing an element, it has been difficult to prepare single crystals of the garnet ferrite having such a large Faraday rotation.


Membrane processes have been applied to a wide variety of industrial separation processes for process schemes requiring either concentration or purification of aqueous streams ranging from clarification of juices, removal of products from fermentation broths and desalination of brackish waters, etc. Some of the processes described above have been demonstrated on an industrial scale. This technology has been possible due to the development of new membranes which exhibit a high degree of hydraulic permeability coupled with ability to retain small molecules.
The membrane filtration process is, however, adversely affected by two phenomena, namely, concentration polarization and fouling. Concentration polarization is caused by the accumulation of solute molecules at the upstream surface of the membrane. This phenomena causes a reduction in the efficiency and of rate of the membrane filtration process. Concentration polarization is generally a hydrodynamic and diffusion phenomena.
Fouling also occurs with a variety of feeds including proteins and colloids. Fouling can be the result of an insoluble precipitate/ particle or gel layer within the pores (plugging) or the result from build-up on the surface of the membrane itself. It has been reported in the literature that up to 100 micron thick gel layers can be formed over a period of 24 hours as a result of the denaturation of proteins. The presence of fat globules can also be responsible for formation of gel layers.
Such gel layers and plugging are responsible for decreases in membrane flux and, hence, affect product throughput and economics. Various methods of treating fouling and concentration polarization have been reported in the literature but have only had limited success in minimizing the problem. Some of these methods are heat treatment with pH adjustment, immobilized protease treatment and membrane scouring.
Some typical industrial applications of membrane separation in the food and beverage industry are removal of casein, fats and lactose from whey; clarification of liqueur and vodkas; sterilization of liquids, e.g. beer, wine; continuous microfiltration of vinegar; and concentration and demineralization of cheese, whey, soy whey and vegetable extracts. Other applications in the wastewater treatment industry include removal of cyanides from electroplating wastewaters; reuse of wastewater from ammunition manufacture; recovery and recycling of sewage effluent; and recovery of starch and proteins from starch factory waste, wood pulp and paper processing. Further applications are listed in an article by Minh S. Le et al, The Chemical Engineer, pp. 48-53, July/August 1985.
Previous work in this area includes the following U.S. Pat. Nos.: 2,571,247; 3,980,541; 4,032,454; 4,057479; 4,100,068; 4,224,135; 4,269,681; 4,276,146; 4,343,690; 4,421,579; and 4,617,128.
Membrane separation techniques typical of the prior art include those that employ classical crossflow electrofiltration. Several good review articles that give an excellent background discussion include: Electrokinetic Membrane Processes, Milan Bier, Membrane Processes in Industry and Biomedicine, Milan Bier--Editor. Plenum Press, N.Y.-London, (1971) pp. 233-266; A Solid/Liquid Separation Process Based on Cross Flow and Electrofiltration, J. D. Henry, Jr., et al, AlChE Journal, Vol. 23, No. 6. November 1977, pp. 851-859; Membrane Fouling Prevention in Crossflow Microfiltration by the Use of Electric Fields, R. J. Wakeman et al, Chemical Engineering Science, Vol. 42, No. 4, pp. 829-842, 1987. In classical crossflow electrofiltration the material to be filtered passes between a first electrode and a membrane or filter with a second electrode positioned on the other side of the filter. The electrodes are energized to pull suspended particles from the material to be filtered toward the first electrode and away from the filter. Thus the suspended particles cannot deposit on the filter or membrane.
U.S. Pat. No. 4,604,174 to Bollinger et al teaches an improvement of the prior art crossflow: however, the general design follows FIGS. 1 and 2 herein that illustrate typical prior art crossflow arrangements. In Bollinger, one electrode assembly forms a wall of the crossflow chamber and the second electrode is located in the filtrate chamber. This arrangement causes the slurry material passing through the crossflow chamber to flow between the two electrodes see FIG. 1 of Bollinger and the discussion in the Summary of the Invention, Column 2, line 57 to Column 3, line 32.
Objects of the present invention include the enhancement of crossflow and dead-end electrofiltration by reducing energy requirements, improving filtration efficiency, reducing filtration time, reducing costly filter cleaning steps, and reducing filter fouling.


1. Field of the Invention
The present invention relates to the field of vacuum cleaners in general, and in particular to an adjustable handle construction for a vacuum cleaner.
2. Description of Related Art
As can be seen by reference to the following U.S. Pat. Nos. 4,662,026; 5,016,315; 5,109,568; and 5,564,160, the prior art is replete with myriad and diverse handle constructions for vacuum cleaners.
While all of the aforementioned prior art constructions are more than adequate for the basic purpose and function for which they have been specifically designed, they are uniformly deficient with respect to their failure to provide a simple, efficient, and practical handle construction for vacuum cleaners that can be angularly adjustable, not only to suit the personal preferences of the individual user, but also to reduce the occurrence of carpel tunnel syndrome among individuals who use a vacuum cleaner on a daily basis.
As most individuals in the building maintenance field are all too well aware, even the most ergonomically designed rigid vacuum handle construction can lead to a repetitive motion injury with continued usage.
As a consequence of the foregoing situation, there has existed a longstanding need for a new and improved type of adjustable vacuum handle construction that cannot only be adjusted to a preferred position, but whose position can be varied to reduce the occurrence of repetitive motion injuries, and the provision of such a construction is a stated objective of the present invention.


A polymer electrolyte fuel cell (PEFC) can operate in a low-temperature region and has high energy conversion efficiency, and a time period required for its startup is short. In addition, the system of the PEFC can be made small and lightweight. Accordingly, the PEFC has been expected to find applications in power sources for electric vehicles, portable power sources, and household co-generation systems.
However, large amounts of platinum catalysts are used in the PEFC. The use of the platinum catalysts causes an increase in cost, which is one factor that may inhibit the widespread use of the PEFC. In addition, a concern has been raised in that restriction is imposed on the PEFC in terms of platinum reserves.
In view of the foregoing, the development of a novel catalyst that can replace the platinum catalyst has been advanced. That is, for example, a carbon catalyst obtained by imparting a catalytic activity to a carbon material itself has been proposed (see, for example, JP 2007-026746 A, JP 2007-207662 A and JP 2008-282725 A).


Polyolefin polymers are very well known in the art. Methods of manufacturing and/or processing polyolefins are likewise well known in the art. These methods of processing include but are not limited to blow molding, injection molding, pultrusion and pulforming, and extrusion. The problems associated with each of these processes are known, and seeking solutions to these problems, and/or improvements in processing conditions and equipment remains of interest to the art and industry.
For example, it is known that olefinic homopolymers such as high-density polyethylenes (HDPE) and polypropylenes generally have poor processability and poor impact properties. Because of the wide commercial uses of these polymers in various applications such as automotives, households, and. packaging, it is always desirable to discover new methods, additives, and/or equipment which enable these polymers to be better and more economically processed, and to improve the mechanical and other properties of these polymers and/or products made from the polymers.


At present, 3GPP (3rd Generation Partnership Project) has been examining LTE Advanced (hereinafter referred to as “LTE-A”) for a further increase in communication speed. SC-FDMA (Single Carrier Frequency Division Multiple Access) system with excellent PAPR (Peak to Average Power Ratio) characteristics is adopted in uplink in LTE. In LTE uplink, spatial multiplexing using MIMO (Multiple Input Multiple Output) can be used. In particular, MU-MIMO (Multi-User MIMO) that performs spatial multiplexing in which multiple mobile station apparatuses use the same frequency and time resource can be used.
To reduce degradation of characteristics in MIMO communication caused by noise, interference, or the like, it is desirable to highly accurately calculate the channel (may also be referred to as “propagation path”) of each antenna port (defined for every physical antenna or combination of two or more physical antennas) in transmission and reception. In LTE, orthogonality in frequency domain is realized by code multiplexing implemented by allocating, to each antenna port, a sequence generated by applying a cyclic shift in time domain to an uplink demodulation reference signal (UL DMRS: Uplink Demodulation Reference Signal) generated on the basis of a Zadoff-Chu sequence. Further, since there are two sequences of UL DMRS (that is, two SC-FDMA symbols) in one subframe, LTE-A applies a Walsh sequence in units of SC-FDMA symbols, thereby realizing orthogonality in time domain (Non Patent Literature 1). This spread sequence applied in time domain is referred to as an orthogonal cover code or an OCC (Orthogonal Cover Code).
A condition in which orthogonality is established by a cyclic shift in UL DMRS is limited to the case in which the allocated frequency regions are completely the same. Therefore, when MU-MIMO is applied to mobile station apparatuses to which different frequency regions are allocated, orthogonality between the mobile station apparatuses can be realized by allocating orthogonal OCCs, such as [+1 +1] and [−1 −1], to the mobile station apparatuses, respectively. Further, as in Non Patent Literature 2, it has been proposed to use IFDM (Interleaved Frequency Domain Multiplexing) that arranges DMRS in a comb-shape on the frequency axis. Orthogonality of multiplexed UL DMRS can be realized by changing the offset of a subcarrier to be allocated.


Bone morphogenetic proteins (BMPs) are members of the TGF-β superfamily that can induce endochondral bone formation in adult animals. This superfamily includes a large group of structurally related signaling proteins that are secreted as dimers and then cleaved to result in biologically active carboxy terminal domains of the proteins. These bioactive proteins are characterized by 7 highly conserved cysteine residues. Interestingly, these proteins have different roles at various stages of embryogenesis and in adult animals. Recombinant BMPs are now available and have been shown to induce endochondral bone formation when assayed in vivo.
Indeed, the initial discovery of the BMPs was facilitated by such in vivo assays for cartilage and bone development. These assays were based on the observation that bone development could be initiated by subcutaneous or intramuscular implantation of compositions comprising an extract of demineralized bone and residual bone powder. The novel proteins identified in the extracts were termed “bone morphogenetic proteins.” These proteins were subsequently classified as members of the TGF-β superfamily by virtue of amino acid sequence relatedness. Screening of genomic and cDNA libraries led to the isolation of polynucleotides encoding BMP-2, -3, -4, -5, -6 and -7.
One deficiency of the bone induction assay regards its inability to distinguish the physiological roles of different BMP family members. The cartilage and bone inducing activity of the BMPs is remarkable because the normal stages of endochondral bone formation that occur during ontogeny are recapitulated in the adult animal. These stages include mesenchymal condensation, cartilage and bone and bone marrow formation and eventual mineralization to produce mature bone.
Several observations suggest that BMPs have wide-ranging extraskeletal roles in development. First, localization studies in both human and mouse tissues have demonstrated high levels of mRNA expression and protein synthesis for various BMPs in kidney (BMPs-3, -4, -7), lung (BMPs-3, -4, -5, -6), small intestine (BMPs-3, -4, -7), heart (BMPs-2, -4, -6, (BMPs-2, -4, -5, -7) and teeth (BMPs-3, -4, -7). Second, several members of the family, including BMP-4 and -7, are key molecules in epithelial-mesenchymal interactions, for instance during odontogenesis. Third, BMP-2 and BMP-4 are involved in the signaling pathway that controls patterning in the developing chick limb and BMP-4 is a ventralizing factor in early Xenopus development. Fourth. Drosophila homologs of the BMPs, the decapentaplegic (dpp) and 60 A gene products, have the capacity to induce bone in mammals whereas human BMP-4 confers normal embryonic dorso-ventral patterning in Drosophila transformants defective in dpp expression. Thus, the BMPs are now appreciated as pleiotropic cytokines.
Interestingly, none of the known BMPs are strongly expressed in the chondroblasts and chondrocytes of the cartilage core of developing long bones. The hypertrophic chondrocytes, where both Vgr-1 (BMP-6, (Lyons et al., Development 109:833 (1990)) and OP-1 (BMP-7)(Vukicevic et al., Biochem. Biophys. Res. Commun. 198:693 (1994)) have been found are exceptions in this regard.


The present invention is related to transportable service carts, of the type commonly used for the convenient storage and transportation of items.
Service carts of the described type come in a variety of shapes and sizes that are typically tailored to a specific application or for use with particular items. They usually comprise a storage compartment and a plurality of wheels. The storage compartment may also comprise surfaces and/or shelves that provide a support surface for the stored items and may comprise drawers, cabinets, or other components that may completely enclose the stored items. The plurality of wheels is provided for convenient transport of the service cart.
One application for a service cart is in automotive repair facilities, wherein the service cart stores a technician's tools. The service cart may be transported to the approximate area that the technician is working, typically near a vehicle, to provide convenient access to the stored tools. Occasionally, a service cart will strike a vehicle while the vehicle is in the automotive repair facility, which is undesirable because such impacts between the service cart and vehicle may damage the exterior of the vehicle or the service cart and may damage the internal components of the vehicle or the stored items in the service cart. Repair facility equipment may also come into contact with the service cart on occasion. Such equipment may comprise shelving, vehicle lift systems, or other machinery that may also be damaged if impacted by a service cart.
The damage to the struck object or the service cart is typically caused by the extremities of the cart, such as the corners of the cart, protruding shelves, protruding handles, or the like. The extremities of the cart are most likely to come into contact with other objects, and the extremities often define relatively sharp features, such as a non-radiused corner or a corner with minimal curvature. Such sharp features concentrate the impact on the struck object during the impact, which increases the amount of damage to the object rather than dispersing the impact over a larger area and reducing the damage.
Therefore a need exists for a transportable service cart that reduces or prevents damage to struck objects and the service cart when the service cart impacts other objects. A further need exists for a transportable service cart that reduces the likelihood of impacts between a service cart and other objects.


1. Field of the Invention
This invention relates to ion implantation and more particularly to a non-mass-analyzed ion implantation process wherein ions of non-selected species are accelerated and implanted into a target.
2. Description of Prior Art
Today, ion implantation is evaluated as one of important techniques, especially, in the semiconductor industry. Conventionally, most ion implantation apparatus for processing semiconductors have been based on mass-analyzed ion implantation wherein mass analysis is effected by utilizing a static magnetic field generated by a magnet and an ion of one selected species is used as an ion source. The mass-analyzed ion implantation has an advantage of high purity of implanted impurities but it requires a mass analyzer and suffers from a disadvantage that the apparatus is costly and running cost is high.
On the other hand, non-mass-analyzed ion implantation has been proposed especially for formation of a pn junction of solar batteries and it eliminates the above disadvantage (Japanese Patent Application Kokai (Laid-Open) No. 130975/78). In the non-mass-analyzed ion implantation, ions are accelerated and without being subjected to mass analysis, implanted into a target. This ion implantation process dispenses with the mass analyzer so that not only apparatus cost and running cost can be reduced but also travel path of ion beams can be reduced to reduce loss of ions due to collision and scattering of the ion beams at the inner wall of the apparatus. The reduction in loss leads to an increase in implantation current which in turn increases implantation processing speeds.
The conventional non-mass-analyzed ion implantation, however, simply implants all the ions of nonselected species into the target and has difficulties with the use of compound source materials. Further, even with an elemental source material such as for example red phosphorus, a phosphorus vaporizer is required and it is necessary to prevent solidification of vaporized phosphorus by heating an atmosphere between the phosphorus vaporizer and the ion source up to about 400.degree. C.


There are numerous reasons to limit or otherwise block the origination of outgoing calls. Parents may want to limit their children's ability to call certain people, or make certain types of calls. Further, parents may want to limit the times at which calls can be made. Office administrators or business owners often desire to impose similar limitations on employees.
Unfortunately, there are very few ways to limit outgoing calls. Typically, a telephony switch servicing a telephony terminal must be provisioned to block certain types of calls from that telephony terminal. Such provisioning is generally limited to blocking broad categories of calls, such as 900, long distance, or international calls. In addition to being limited to blocking certain categories of calls, such provisioning requires subscribers or their representatives to request that the service providers provision the telephony switch in the desired fashion. Accordingly, current techniques for blocking certain types of outgoing calls are not only inflexible, but also cumbersome. There is a need for an efficient and flexible way for subscribers or their representatives to block outgoing calls as they desire, as well as a telephony system in which such blocking of calls can be efficiently implemented.


a. Field of the Invention
The present invention is in the field of semiconductor die packaging.
b. Description of the Related Art
Electronic equipment that includes packaged semiconductor dies, such as portable telephones, personal computers, and digital cameras, are being developed with increased functionality. To meet this trend, companies that assemble semiconductor dies into packages are developing semiconductor packages that include a plurality of stacked semiconductor dies in a single package.
A conventional technique for stacking plural semiconductor dies in a single package is to couple an inactive (i.e., backside) surface of a first semiconductor die to a substrate, so that the active surface of the first semiconductor die faces away from the substrate, and then to attach the inactive surface of a second semiconductor die onto the active surface of the first semiconductor die using an electrically insulating adhesive layer. The first and second semiconductor dies are each electrically coupled to the substrate by bond wires that extend from bond pads on the active surface of the respective semiconductor dies to the substrate. In order that the upper second semiconductor die not interfere with the bond wires coupled to the lower first semiconductor die, the second semiconductor die is typically smaller than the first semiconductor die so that the second semiconductor die fits fully within the opposed parallel rows of bond pads on the active surface of the first semiconductor die. In a case where a die attach paste is used to couple the first and second semiconductor dies, the size of the second semiconductor die also is limited to account for the die-attach fillet that is formed during the die-attach process for the second semiconductor die. Unfortunately, this approach of stacking a smaller second semiconductor die on a larger first semiconductor die is not feasible where it is desired to stack two same-size semiconductor dies, or to stack a larger semiconductor die on top of a smaller semiconductor die.
An alternative approach for die stacking is to attach a first side of a rectangular prism of silicon or of a dielectric film, called a “spacer,” to the active surface of the first semiconductor die, and to attach the inactive surface of the second semiconductor die to an opposite second side of the spacer. The spacer has an upper and lower surface area that is smaller than the area of the active surface of the lower die, and is placed so as to be entirely within the bond pads and active surface edges of the lower semiconductor die. The spacer has a thickness sufficient to space the inactive surface of the second die above the bond wires that are coupled from the bond pads of the first semiconductor die to the substrate. Unfortunately, the spacer adds additional vertical height to the package, and thus is not optimal for certain applications.
Accordingly, a new approach to stacking a plurality of semiconductor dies is desirable.


The invention relates to a method of manufacturing a lithium battery comprising a stack of a negative electrode, a separator, and a positive electrode, which method comprises the steps of applying negative electrode material on a negative current collector so as to form the negative electrode, applying positive electrode material on a positive current collector so as to form the positive electrode, and arranging a separator between the negative electrode and the positive electrode, and which method comprises the following steps:
a) producing a pattern of holes in the negative electrode;
b) producing a pattern of holes in the positive electrode;
c) applying a polymeric material on at least one side of the stack and subjecting the stack and the polymeric material to heat and pressure, so that the polymeric material penetrates the hole, whereby which the negative electrode, the positive electrode, and the separator are stuck and pressed together.
The growing market for lightweight, portable cordless consumer products, such as CD-players, mobile telephones, laptop computers and video cameras, has increased the need for high-density batteries. Specifically, very thin and flexible batteries are required. If an acceptable portability is to be achieved, the batteries contained in said consumer products should provide the necessary amount of energy at the smallest possible weight and volume. Lithium is a very advantageous material for use in batteries in which a high energy density at a minimum weight is required. However, the thinner the battery, the more difficult the application of a pressure needed to maintain a sufficient contact between the respective components of the battery.
A method of manufacturing a lithium battery according to the preamble is known from the International patent application with publication number 00/04601.
The battery obtained by said method has thin and flexible shape and at the same time provides a very high energy density. Moreover, the contact between the electrodes and the separator is obtained and maintained in a very efficient way. The battery can be packed in a thinwalled canister, as the wall of such canister is not needed for maintaining a sufficient pressure on the respective components of the battery. In one of the methods according to the International application 00/04601, a film of a polymeric material is applied to both sides of the stack, and said polymeric film is subjected to heat and pressure. As a result thereof, the polymeric material melts and penetrates into the holes. A battery is obtained by said method with a polymeric film at both sides of the stack as well as polymeric material in each of the holes acting as a plug or rivet and sticking to the respective layers, causing these layers to be bonded together.
It is an object of the invention to provide a method of manufacturing a lithium battery according to the preamble by which an even thinner battery can be created.
To this end, the method of manufacturing a lithium battery according to the preamble is characterized in that the polymeric material comprises bulges which are partially located in the holes of the electrode(s).
By providing such bulges of polymeric material at the ends of the holes in the electrode(s), enough polymeric material is provided to fill the holes and stick together the electrodes and the separator, whereas on the outer sides of the stack, in between the holes, the polymeric material may be very thin or even be absent. The battery thus obtained can provide the same amount of energy as the battery obtained according to the prior art method, but at a smaller volume. Thus, the battery obtained according to the method of the present invention has a higher capacity.
In a particular embodiment, the polymeric material comprises a polymer foil which is provided with bulges.
As was mentioned above, the polymer foil itself may be very thin, while the bulges have to comprise enough polymeric material to fill the holes in the electrodes, thereby sticking together the electrodes and the separator.
In a preferred embodiment, the polymeric material is placed on a carrier foil.
Placement of the polymeric material on a carrier foil facilitates the handling thereof. After stacking of the battery, the carrier foil may either be removed or be left in place.
Advantageously, the carrier foil comprises a polymeric material with a high melting point.
If such carrier foil is provided, the carrier foil itself will not melt during the application of heat, whereas the polymeric material will melt, thereby penetrating the holes of the electrodes.
In a further preferred embodiment, the polymeric material is placed in a patterned arrangement of bulges on the carrier foil.
During the application of heat the bulges will melt and penetrate into the holes in the electrodes. Afterwards the carrier foil can be removed. In the battery thus obtained, the polymeric material which has penetrated the holes in the electrodes is substantially not present at the outer sides of the electrodes.
In another advantageous embodiment, the polymeric material is placed in a patterned arrangement of bulges between portions of a carrier.
Also in this case, after the melting of the polymeric material and penetration thereof into the holes, the carrier foil can be removed from inbetween the openings of the holes in the electrodes. A battery is thereby obtained in which the polymeric material which has penetrated the holes in the electrodes is substantially not present at the outer sides of the electrodes.
In the above methods, use is preferably made of a porous polymeric material for the polymeric material which has to enter the holes in the electrodes, e.g. porous polyethylene. Preferably, the polymeric material is elastic. The carrier foil which may be used preferably comprises a strong foil, such as Mylar(trademark) or Kapton(trademark).
The electrode materials can be made by mixing negative or positive active material, conductive material, and binder material, which are all in the form of powder, in a dry process, or in a wet process in which water or an organic solvent is further added.
The paste-like mixture obtained is then provided over the current collector, dried and compressed. For this purpose, one of the following coating methods can be generally employed: screen printing, roller coating, doctor blade coating, knife coating, extrusion coating, bar coating, dip coating and squeeze coating. The thickness of the coated layer, which is compressed after drying, generally is in the range of 1 to 1000 xcexcm.
Pressing of the stack in the above methods is accomplished by simply pressing it for a short period of time between heated metal plates at a pressure of about 5.104 Pa at about 110 to 150xc2x0 C. The operation may also be carried out using calender rollers. After heating, the stack is cooled down to room temperature. Heating and cooling down may also be carried out in a mold with a particular shape, e.g. the shape of the appliance into which the battery is to be fitted.
In the same way as described above, a multilayer stack of layers can be bonded together in one step, thereby obtaining a battery of increased capacity or voltage.
The lithium battery of the invention can be used in various (cordless) appliances, for example notebook personal computers, portable CD-players, portable telephones, paging equipment, video cameras, electric shavers, electric tools, electric vehicles, and hearing aids. The lithium battery may be used as a primary or as a secondary battery.


The present invention relates to aqueous solutions and dispersions of binders for preparing aqueous coating materials, and to processes for their preparation.
The condensation of alcohols with carboxylic acids produces per crosslinked hydroxyl or carbonylxe2x80x94group one molecule of water, H2O:
R1xe2x80x94OH+HOOCxe2x80x94R2xe2x86x92R1xe2x80x94Oxe2x80x94COxe2x80x94R2+H2O
alcohol+carboxylic acidxe2x86x92ester+water
Since the ester is the reaction product which is of interest, in the prior-art preparation processes the water produced is removed from the reaction mixture as so-called xe2x80x9cwater of reactionxe2x80x9d. This water of reaction is generally contaminated with other components of the reaction and must therefore be disposed of. A procedure of this kind is necessary, for example, in the coatings industry in connection with the preparation of coating binders.
In the coatings industry, the preparation of polyesters and alkyd resins from polycarboxylic acids and/or polycarboxylic anhydrides and polyalcohols and, if desired, monocarboxylic acids by condensation reactions gives rise to a quantity of about 5 to 11%, based on the polymer produced, of water of reaction. The water of reaction is normally removed effectively from the reaction mixture with the assistance of entrainers (for example xylene).
The vapor mixture comprising water of reaction and entrainer isxe2x80x94especially where saturated polyesters are being preparedxe2x80x94passed through a column whose function is to separate volatile polymer building blocks (especially lower polyalcohols) from the vapor mixture by liquid/vapor exchange and thereby to avoid losses of these building blocks from the reaction mixture. For polyesters and alkyd resins, which contain no constituents which are volatilexe2x80x94under the reaction conditions in the reactor or with steamxe2x80x94an overflow pipe is employed.
In each case, however, the vapor mixture is subsequently liquefied in a condenser and is collected in a separation receiver. In the separation receiver, an aqueous phase of relatively high specific gravity separates from the organic phase of lower specific gravity. The organic phase consists almost entirely of the entrainer employed; it is separated from the aqueous phase by means of an overflow and is passed into the reactor at the head of the column (circulation technique) possibly under control and by means of the use of a pump (possibly a metering pump).
Another possibility is to operate without entrainer. In this case there is no need for a separation receiver but only for a single receiver into which aqueous phase is collected.
Although the aqueous phase contains high proportions of water, it is always contaminated with relatively small amounts of volatile or steam-volatile building blocks (mostly lower polyols) and/or with water-soluble degradation products from the building blocks of the polyester as well. Degradation products which may be produced and may be present in the aqueous phase of the water of reaction are monoalcohols, partial aldehydes of polyols, acetals, and in special cases cyclic, oxygen-containing compounds as well.
Separation of the secondary constituents from the aqueous phase during the preparation of polyesters and alkyd resins, by distillation or extraction, is complex and does not lead to reusable materials. Simple disposal of the distillate, for example by way of settling basins, is a risk. Usually, therefore, despite its small content of organic constituents the water of reaction is incinerated, usually together with other residues which are richer in organic substances. This requires separation and storage of the waters of reaction and special control as they are fed to the incinerator.
Because of their ecological advantages, water-dilutable coating materials have increasingly been used in the coatings industry in recent years. With these coating materials it is possible largely or completely to dispense with organic solvents whose evaporation as the coating material dries leads to emissions and to the known, associated environmental problems. In the course of preparing such aqueous coating systems, the binders of the coating material must be brought into the form of an aqueous solution or dispersion. Dispersions of this kind are highly unstable. Even small quantities of impurities may destroy or severely hinder the dispersibility of the binders. For example, a solution of this kind cannot be prepared using tap water (drinking water, mains water), which contains inorganic constituents. It is therefore necessary to employ deionized or distilled water. This implies more complex preparation and therefore increased preparation costs as well.
The object which the present invention has set itself is to avoid the disadvantages of the prior art, described above, which occur in particular during the disposal of water of reaction and during the preparation of binder dispersions.
This object is achieved in accordance with the invention by an aqueous solution or dispersion of a binder for preparing aqueous coating materials, which solution or dispersion includes as at least one aqueous component the water which can be prepared by condensation of alcohols with carboxylic acids and can be separated off from the condensation mixture.
It has surprisingly been found that during the preparation of polyesters or alkyd resins (which are then preferably employed for water-dilutable coating PAT 95445 systems, the water of reaction is able to replace a portion of the distilled or deionized water which is otherwise used to prepare the aqueous colloidal solution or dispersion of the polyester or alkyd resin. Unlike tap water (drinking water, mains water), which contains certain proportions of inorganic constituents which impair the usefulness for preparing aqueous colloidal solutions or dispersions of coating binders, it is possible with fractions of the waters of reaction to prepare stable aqueous colloidal solutions. The use of these aqueous polyester-resin or alkyd-resin solutions or dispersions in aqueous coating systems has only an insignificant influence on their properties. This effect was completely surprising in view of the sensitivity of the binder dispersions to impurities. On the basis of conventional experience, the opposite was to be expected. However, it is found that in most cases the secondary constituents act as cosolvents. If aqueous coating systems are employed on application lines with stoving furnacesxe2x80x94which is generally the case with the industrial use of aqueous coating systemsxe2x80x94the abovementioned substances accompanying the water of reaction do not become volatile until they are in the stoving furnace, although some of them also participate in film forming (for example reaction with amine resins). Environmental pollution as a result of the constituents, therefore, is largely ruled out, and in any case the waste air from stoving furnaces includes organic cleavage products and is therefore cleaned by means of catalytically processes or filters.
In the text below, the term water of reaction is intended always to denote the water which is eliminated during the condensation of alcohols with carboxylic acids and which is or can be separated off from the condensation mixture.
In accordance with the invention, the water of reaction is preferably taken from reactions in which the alcohols are present as polyalcohols, the term polyol referring to an organic compound which bears at least 2 hydroxyl groups. Examples of suitable polyols are ethylene glycol, propanediols, butanediols, pentanediols, neopentylglycol, hexanediols, diethylene glycol, glycerol, trimethylolethane, trimethylol-propane, pentaerythritol, dipentaerythritol, neopentylglycol hydroxypivalate, 2-methyl-2-propyl-1,3-propanediol, 2,2,4-trimethyl-l,3-pentanediol and 2,2,5-trimethyl-1,6-hexanediol It is preferred to employ neopentylglycol, 1,6-hexanediol and neopentylglycol hydroxypivalate. The polyols can of course be employed in pure form or as mixtures.
In the case of the novel preparation of the water of reaction, polycarboxylic acids are preferably employed. These may comprise a polycarboxylic acid containing at least three carboxyl groups, or derivatives of such an acid (e.g. anhydride, ester or halide). It is likewise possible to employ a mixture of such acids and/or acid derivatives. As examples there are, trimellitic acid, trimesic acid (1,3,5-benzenetricarboxylic acid), pyromellitic acid and trimeric fatty acids. Trimellitic acid is preferably employed.
As carboxylic acid it is also possible to employ a polyol which has at least one carboxyl group. Dimethylolprophonic acid is preferably employed. It is likewise possible to employ any polycarboxylic acid which contains two carboxyl groups and is suitable for preparing polyesters, or to employ a reactive derivative (e.g. anhydride, ester or halide) or a mixture of such acids and/or acid derivatives. Examples of suitable acids which may be mentioned are: phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, endomethylenetetrahydrophthalic acid, succinic acid, adipic acid, suberic acid, acelaic acid, sebacic acid and dimeric fatty acids. It is preferred to employ phthalic acid, isophthalic acid, adipic acid and dimeric fatty acids.
As its aqueous component the novel aqueous solution or dispersion of a binder may include a mixture of the water of reaction according to the invention and deionized water. This is sensible, for example, if owing to the production process there is not sufficient water of reaction available to prepare the desired quantity of dispersion. The aqueous component preferably includes from 0.1 to 80% by weight, and with very particular preference from 1 to 20 by weight, of the water of reaction in the sense of the invention.
Suitable binders from which it is intended to prepare an aqueous solution or dispersion are in principle all binders known for this purpose. Particularly suitable binders are: polyester, alkyd, acrylate, epoxy, polyurethane and/or epoxide-modified polyester resins, and also modifications of these binders. The preparation of epoxide-modified polyester resins, for example, takes place in accordance with techniques which are known per se.
The novel water-dilutable coating compositions may in principle contain all binders suitable for water-dilutable coating compositions.
Binders which can be used are, accordingly, both refined natural products, for example from rosins or oils or cellulose nitrates, and resins built up entirely by synthetic means The latter include phenolic resins, amine resins (e.g. urea resins, melamine resins), alkyd resins, polyvinyl acetates, epoxy resins, polyurethane resins, polyester resins, rosin-modified phenolic resins, chlorinated rubbers, chlorinated polypropylene, cyclized rubbers, ketone resins and acrylate resins.
Amino resins, polyester resins, polyacrylate resins and polyurethane resins which can be prepared in organic solution and which are water-dispersible or water-dilutable, and mixtures thereof, are employed in particular as binders.
The polyurethane resins employed as binders are known in principle. Examples of suitable polyurethane resins are those described in the literature for use in waterborne coating materials, provided these polyurethane resinsxe2x80x94in a modification of the preparation described in the respective literature can be prepared in the form of organic solutions.
Examples of suitable polyurethane resins are the resins described in the following documents: EP-A-355433, DE-A 3545618, DE-A 3813866 and the as yet unpublished German Patent Application DE 4005961.8. For further details of the preparation of the polyurethane resins and examples of suitable compounds, therefore, reference may be made to these documents.
The polyacrylate resins employed as binders are likewise known and are described, for example, in DE-A 3832826. Suitable polyacrylate resins are General water-dilutable and/or water-dispersible polyacrylate resins which can be prepared in the form of organic solutions.
Also suitable as binders are polyester resins which are water-dilutable or water-dispersible and can be prepared in the form of organic solutions. Use is made, for example, of corresponding commercially available water-dilutable or water-dispersible polyester resins, and of the polyester resins which are customarily employed in waterborne coating materials.
Water-dilutable and water-dispersible amino resins are also suitable as binders. It is preferred to employ water-dilutable melamine resins. Generally, these are etherified melamine-formaldehyde condensation products.
The water-solubility of the amino resins dependsxe2x80x94apart from the degree of condensation, which should be as low as possiblexe2x80x94on the etherification component, with only the lowest members of the alcohol or ethylene glycol monoether series giving rise to water-soluble condensation products. The methanol-etherified melamine resins are of greatest importance. If solubilizers are used, butanol-etherified melamine resins can also be dispersed in aqueous phase. Another possibility is to incorporate carboxyl groups into the condensation product. Transetherification products of highly etherified formaldehyde condensation products with hydroxycarboxylic acids are water-soluble via their carboxyl groups, after neutralization, and may be present in the base paints.
As binders it is of course also possible to employ mixtures of the binders mentioned and, in addition or alone, other water-dilutable or water-dispersible binders.
The novel coating compositions may include customary additions, such as solvents, fillers, plasticizers, stabilizers, wetting agents, dispersion auxiliaries, leveling agents, antifoams and catalysts, and also additives, individually or in a mixture in the customary quantities. These substances may be added to the individual components and/or to the overall mixture.
Examples of suitable fillers are talc, mica, kaolin, chalk, quartz flour, absestos flour, slate flour, barium sulfate, various silicic acids, silicates, glass fibers, organic fibers or the like.
In addition to water, the novel coating compositions may include the customary solvents, for example aliphatic or aromatic hydrocarbons, mono- or polyhydric alcohols, ethers, esters, glycol ethers and their esters, ketones, such as, for example, toluene, xylene, butanol, ethyl- or butylglycol (=ethylene glycol monoethyl or -butyl ether) and their acetates, butyl diglycol (ethylene glycol dibutyl ether), ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, cyclohexanone, methyl ethyl ketone, acetone, isophorone or mixtures thereof.
It is additionally possible to add crosslinked polymeric microparticles, as are disclosed, for example, in EP-A-38 127, and/or customary inorganic or organic additives to the novel basecoats. Thus examples of effective thickeners are water-soluble cellulose ethers, such as hydroxyethyl cellulose, methylcellulose or carboxymethylcellulose, and also synthetic polymers having ionic and/or associative groups, such as polyvinyl alcohol, poly(meth)acrylic acid, polyvinylpyrrolidone, styrene-maleic anhydride or ethylene-maleic anhydride copolymers and their derivatives, or else hydrophobically modified ethoxylated piperidine and triethanolamine used [sic]. With particular preference, tertiary amines are employed as neutralizing agents, especially dimethylethanolamine, triethylamine, tripropylamine and tributylamine.
The novel basecoat compositions may include all dyes or pigmets which are known and are customary in the coatings industry.
Examples of dyes and pigments, which may be inorganic or organic in nature, are titanium dioxide, graphite, carbon black, zinc chromate, strontium chromate, barium chromate, lead chromate, lead cyanamide, lead silicochromate, zinc oxide, cadmium sulfide, chromium oxide, zinc sulfide, nickel-titanium yellow, chromium-titanium yellow, iron oxide red, iron oxide black, ultramarine blue, phthalocyanine complexes, naphthol red, quinacridones, halogenated thioindigo pigments or the like.
As particularly preferred pigments use is made of metal powders, individually or in a mixture, such as copper, copper alloys, aluminium and steel, preferably aluminium powders, in at least the predominant proportion, namely in a quantity of from 0.5 to 25% by weight based on the overall binder solids content of the coating compositions. Preferred metallic pigments are those commercially available metal powders which have been specially pretreated for aqueous systems. The metal powders may also be employed together with one or more of the abovementioned nonmetallic pigments and/or dyes. In this case their proportion is chosen such that the desired metallic effect is not suppressed.
The novel binder solution or binder dispersion is preferably used for producing aqueous coating materials. For this purpose it is processed further, together with crosslinkers (e.g. amino resins, especially those of the type hexamethoxymethylmelamine, urea resin, water-dilutable epoxy resin and the like) optionally further binders, pigments, fillers and other customary additives, to form an aqueous coating material. In addition to water, the latter may also, to a minor extent, comprise organic solvents as diluents.
The scope of the present invention also includes the aqueous coating material obtained by using the described binder solution or binder dispersion. The present invention started out, inter alia, from the object of avoiding the problems associated with the water of reaction which occurs in the case of condensation reactions. In the prior art, this water of reaction is separated off from the reaction mixture and then disposed of expensively. The invention, by contrast, proposes employing the water of reaction as an aqueous component in the preparation of aqueous dispersions or solutions of organic substances. Examples of such substances and/or of such a use is the above-described preparation of aqueous binder dispersions and binder solutions. However, it is obvious that the use of the water of reaction is not restricted to these specific groups of substances. Rather, the water of reaction can be employed as solvent whenever the contaminants which it may still contain are harmless for the dispersion or solution to be prepared. The advantage of such a water of reaction is that its composition and the possible accompanying substances which are present in it are known with great precision, provided one knows the precursors of the underlying condensation reaction. In particular, the water of reaction has none of the inorganic impurities of customary tap water.
The invention also relates to a process for preparing binder solutions or binder dispersions for aqueous coating materials, which is characterized by the following steps:
a) water of reaction eliminated during the condensation of alcohols and carboxylic acids is separated off from the condensation mixture,
b) if desired, the water of reaction separated off is mixed with deionized water, and
c) the binder is dissolved or dispersed in the aqueous component obtained in accordance with a) and b).
The water of reaction in process step a) may in principle come from a condensation reaction which has nothing to do with the binder concerned. Preferably, however, at least part of the binder is prepared by the condensation reaction of step a). This is because a particularly rational process is one in which the water of reaction of a polyester or alkyd resin which is employed in aqueous coating systems is employed directly by decantation from the separating receiver in the course of preparing the aqueous colloidal solution of the polyester concerned in a dilution vessel which in most cases is connected to the reactor.
In a further, independent process for preparing binder solutions or binder dispersions for aqueous coating materials, the following steps are carried out:
a) binder is prepared by condensation of polyol and poly- or monocarboxylic acids, with the water of reaction eliminated during the condensation remaining in the condensation mixture,
b) if desired, deionized water is added, and
c) if desired, further binders are added.
This process can be employed whenever at least some of the binder is prepared in a condensation reaction of polyols and carboxylic acids and when the water of reaction which occurs in this condensation reaction, including the impurities which may still be present, does not impair the dispersion which is to be prepared. In this case the process described is particularly advantageous, since it avoids the step of separating off the water of reaction from the condensation mixture. Since the water of reaction in some cases is not present in sufficient quantities for the dispersion to be prepared, it is possible if required to add further deionized water.


1. Technical Field
The present invention is generally related to media storage boxes and, more particularly, to lockable media storage boxes.
2. Background Information
Renting items of recorded media such as video cassettes and video games has become immensely popular in recent times given the ever increasing number of items available for home viewing and use as well as the decrease in price of the machines that play the media. Typical rental stores display the items available for rental in storage boxes that protect the items from dust, ultraviolet light, and damage from impact if accidentally dropped. Stores protect themselves against theft by placing one or more EAS tags on or inside the item of recorded media. An EAS tag is adapted to activate an alarm when passed through a sensing device that may be disposed around the exit of the store. It is generally desirable to place the EAS tags in places where they cannot be easily removed by a shoplifter.
A rental establishment typically places older rental stock out for sale when it no longer needs the item for rental. When items are put out for sale, the EAS tags are removed from the items and reused on items that are being rented. The EAS tags are removed from the items of recorded media prior to sale so that the purchaser will not activate the alarm systems in other stores with the EAS tags. Without the EAS tags in the items themselves, a rental store must protect itself against shoplifting by placing an EAS tag on the storage container holding the item for sale. It is desirable that the EAS tag be placed on the storage container in a way that allows a sales clerk to quickly and easily remove the tag after the sale is made but also in a manner that prevents a shoplifter from easily removing the tag. Placement of the EAS tag in such a position is, however, difficult because a storage container provides few, if any, areas where the EAS tag may be hidden. If the EAS tag is placed on the storage container in a fashion such that it can be easily removed, a shoplifter may simply remove the tag and steal the item without activating the alarm. It is thus desired in the art to provide a storage container suitable for holding and displaying an item of recorded media during display for rental that has locking holes that can later accept a lock containing an EAS tag when the container is used to sell an item.
Such a storage box and lock combination must be configured to prevent the thief from simply breaking the lock off the storage box with a small pry bar. Although the storage box and lock must be relatively strong, the cost of manufacturing the lock and storage box must not be prohibitive. It is thus also desired in the art to provide a relatively inexpensive storage box and lock and key combination that securely locks the storage box while preventing a pry bar from being inserted between the lock and the storage box.