An oscillator and a method for producing an improved oscillator that will generate an accurate frequency when encountering a vibration. The oscillator and method uses a crystal with minimal cross-axis coupling. Further, a first accelerometer produced using MEMS technology is used. The first accelerometer is positioned inside of the oscillator so that the accelerometer accurately measures any vibration encountered by the oscillator. The first accelerometer and the crystal are maintained at constant temperature to minimize phase shifts and gain variations.

Stress compensated ("SC") cut quartz crystals have been extensively used as the resonating element in oscillator circuits as a reliable element to generate accurate frequencies. Under static conditions, i.e., an acceleration-free (vibration-free) environment, a well-designed SC-cut quartz crystal oscillator when powered will produce an output signal at a particular carrier frequency with relatively low sideband frequencies with respect to the carrier frequency. However, when the same oscillator is subjected to acceleration or to changes in spatial orientation, undesirable spurious sidebands occur in the output signal. Depending on the particular application of the oscillator, these spurious sidebands, as well as unwanted signal noise, can translate into overall system errors when motion and vibration are encountered. The effects on a quartz crystal resonating element of both periodic and random acceleration (vibration) have been well documented. However, known methods for compensating for the acceleration effects have not resulted in a sufficiently compensated crystal that can be produced with good commercial yields with economies of manufacturing.
In addition, oscillators may be subject to changes in spatial orientation, i.e., the oscillator may be mounted in a vertical position inside an instrument that is positioned on a non-vibrating platform such as a laboratory worktable. The instrument may be moved and turned 90 degrees on its side resulting in the oscillator changing its spatial orientation or positioning by 90 degrees and, thus, resulting in degradation to the oscillator's output signal. Better techniques and methods to adequately compensate for changes in spatial orientation are needed. Specifically, an apparatus and methodology is needed that seamlessly compensates from 0 Hz (no vibration but changes in spatial orientation) to 2000 Hz (with sinusoidal and/or random vibration and high g-levels). It is believed that no previously known method has ever economically compensated for both the effects of changes in oscillator spatial orientation, i.e., 0 Hz, and for higher vibration frequencies.
What has been needed and heretofore unavailable is a quartz crystal resonating element that both can effectively compensate for a broad range of conditions, such as changes in oscillator spatial orientation and periodic and random vibration effects, and a method for fabricating the oscillator that is highly reproducible and permits high yields at an optimum manufacturing cost. The present invention satisfies these needs.

Method for achieving highly reproducible acceleration insensitive quartz crystal oscillators


The present invention provides an easily employed and economical process for removing substantially all of the metals from vinylphenol polymers by dissolving the vinylphenol polymer in a solvent and contacting the solution with a strong acidic cation exchange resin. In this way, vinylphenol polymers of high purity are attained, with a metal content which is virtually eliminated or substantially reduced.

1. Field of the Invention
The present invention relates to a process for removing metals such as, for example, sodium, potassium, calcium, iron, nickel, etc., from vinylphenol polymers, i.e., vinylphenol homopolymers, vinylphenol copolymers, modified polymers thereof, derivatives thereof, etc., by contacting a solution thereof with a strongly acidic cation exchange resin.
2. Description of the Prior Art
It is known that vinylphenol can be manufactured by dehydration of acetoxyphenylmethyl carbinol, decomposition of hydroxycinnamic acid by decarboxylation reaction, dehydrogenation of ethylphenol, or the like. It is also known that vinylphenol monomers manufactured by these processes can be polymerized or copolymerized in the presence of a cation or a radical polymerization initiator to produce vinylphenol-containing polymers (hereinafter referred to simply as vinylphenol polymers).
A number of products, processes for manufacturing thereof, and processes relating to the use of vinylphenol polymers are known in the art, including a process for producing a modified vinylphenol polymer product having a superior light transmittance by hydrotreating a vinylphenol polymer (Japanese patent Laid-open No. Hei 1 (1989)-103604, a process for producing a modified vinylphenol polymer product having excellent flexibility by a heat fusing reaction of a vinylphenol polymer or a mixture of a vinylphenol polymer and a novolak-type phenol resin (Japanese Patent Laid-open No. Sho 60 (1985)-58407, No. Sho 60 (1985)-81228), processes for manufacturing various ester or ether derivatives by the reaction of the hydroxy group of vinylphenol polymers, processes for the manufacture of various nuclear substituted derivatives of vinylphenol polymers, and the like.
These vinylphenol polymers generally contain metals such as sodium, iron, and the like originating from raw materials and auxiliary materials used in the manufacturing processes. Furthermore, it is very difficult to avoid contamination of vinylphenol polymers with metals during the manufacturing processes from materials from which the manufacturing apparatus is constructed, or from foul in the manufacturing apparatus as well as contaminants coming from the environment. Thus, contamination of vinylphenol polymers with metal impurities such as sodium and iron has been unavoidable according to conventional manufacturing processes of vinylphenol polymers. No process for removing these metal impurities has been known in the art heretofore.

Process for removing metals from vinylphenol polymers


A steering tool for use in drilling a borehole, including a tubular housing, a tool actuating device movably supported within the housing, a plurality of hydraulically actuated steering devices circumferentially spaced about the housing, and a hydraulic control system interposed between the tool actuating device and the steering devices for converting an actuating movement of the tool actuating device to independent actuation of the steering devices.

In vertical drilling, a typical objective is to drill a consistently vertical borehole in a manner which minimizes the number and magnitude of unintended deviations of the borehole from vertical. In directional drilling, a typical objective is to drill a borehole along a predetermined path or paths to reach a subsurface target in a manner which minimizes the number and magnitude of unintended deviations and other unintended directional changes of the borehole.
In either case it is desirable to have the ability to control the drilling direction while drilling, since the existence of unintended directional changes complicates both drilling and completion and can increase the amount of time required to drill and complete the borehole.
Unintended directional changes in a borehole may be due to such causes as the characteristics of the formation being drilled, the characteristics of the drilling string, or to phenomena such as bit walk and reactive torque. The resulting borehole may exhibit crookedness or spiralling, may include doglegs and/or keyseats and may cause increased drag and torque on the drilling string, drilling string failures and production problems. The borehole may also miss an intended subsurface target.
Various options are available for providing steering capability to a drilling tool during drilling in an effort to ensure straightness and/or a desired direction of the borehole.
In directional drilling applications, a first option is to attach a bent-housing or a bent-sub downhole drilling motor to the end of the drilling string as a steering tool. When steering is required (such as, for example, to correct the effects of an unintended directional change) the drilling string can be restrained against rotation and the drilling motor can be pointed in a desired direction and operated for both drilling and steering in a "sliding drilling" mode. When steering is not required, the drilling string and the drilling motor can be rotated together in a "rotary drilling" mode. One advantage to this first option is its relative simplicity. One disadvantage to this first option is that steering is only possible in the sliding drilling mode. A second disadvantage to this first option is that the straightness of the borehole in rotary drilling mode may be compromised by the presence of the bent drilling motor.
A second option for steering in directional drilling applications is the use of a "rotary steerable" drilling system as a steering tool. In a rotary steerable drilling system, the drilling string may be rotated while the drilling tool is being steered either by being pointed or by being pushed in a desired direction either directly or indirectly by a steering device or steering devices. A rotary steerable drilling system may include a component which is non-rotating relative to the drilling string in order to provide a reference point for the desired direction and a mounting location for the steering device or devices. Alternatively, a rotary steerable drilling system may be "fully rotating".
One advantage to rotary steerable drilling systems is that they can provide relatively high steering accuracy. One disadvantage to rotary steerable drilling systems is that they tend to be relatively expensive and relatively complex apparatus, due in part to the necessity of determining orientations and directions in three dimensions for directional drilling applications.
U.S. Pat. No. 5,168,941 (Krueger et al) describes a drilling system which includes an array of extendable and retractable force transmitting members and pressure members which are actuated in response to positional data from sensors. The force transmitting members and pressure members are hydraulically actuated by electrically operated control valves using drilling fluid as the hydraulic fluid. The actuating pressure is generated by the creation of high pressure and low pressure drilling fluid regimes through the use of throttles either within the tool or in the borehole.
U.S. Pat. No. 5,603,386 (Webster) describes a drilling system which includes an array of extendable and retractable stabilizer blades. The system may be used for vertical well control. When used in vertical well control applications the stabilizer blades are hydraulically actuated in response to movement of ball bearing sensors which form a link in a "hydraulic solenoid" when the tool deviates from vertical. A system of pilot valves is actuated by the hydraulic solenoid in order to extend or retract the stabilizer blades. The actuating pressure is generated using a pump.
For vertical drilling applications, several options for steering tools are disclosed in the prior art for providing steering capability to a drilling tool during vertical drilling of a borehole.
U.S. Pat. No. 2,075,064 (Schumacher et al) describes a steering tool for use in rotary drilling which includes a free swinging pendulum mounted in a barrel, a closure plate positioned at the lower end of the pendulum, and a plurality of discharge ports associated with the closure plate. In operation, deviation of the drilling string from vertical results in blocking of the discharge port adjacent to the low side of the borehole, with the result that drilling fluid flowing through the barrel is preferentially directed against the high side of the borehole to exert a force to direct the drilling string back to a vertical orientation.
U.S. Pat. No. 2,153,680 (Schumacher et al) describes a steering tool for use in rotary drilling in which a plurality of discharge passages are associated with sealing rings located on an exterior surface of a pendulum mounted in a barrel. In operation, deviation of the drilling string from vertical results in the sealing rings sealing the discharge passages adjacent to the low side of the borehole, with the result that drilling fluid passing through the barrel is directed against the high side of the borehole to exert a force to direct the drilling string back to a vertical orientation.
U.S. Pat. No. 3,141,512 (Gaskell et al) describes a steering tool for use in sliding drilling in which a pendulum in a casing is associated with a plurality of potentiometers. In operation, deviation of the drilling string from vertical causes control signals to be generated by the potentiometers, which in turn actuates an electro-hydraulic control valve, which results in energization of one or more pistons located inside the casing and pivoting of a lower casing section relative to an upper casing section to bring the lower casing section in line with the pendulum. The pistons are hydraulically actuated using oil as the hydraulic fluid, which oil is pressurized by a pump.
U.S. Pat. No. 3,243,001 (Vincent) describes a steering tool for use in rotary drilling which includes a pendulum in a housing with a ring at its lower end which functions to selectively expose or block a plurality of ports which are located adjacent to the lower end of the pendulum during the passing of drilling fluid through the housing. The ports communicate with a plurality of conduits and pistons and each conduit is provided with an orifice for providing a pressure drop in the conduit. In operation, deviation of the drilling string from vertical causes the ring to block the port or ports adjacent to the high side of the borehole and expose the port or ports adjacent to the low side of the borehole. Exposure of the port or ports at the low side of the borehole results in actuation by drilling fluid of the piston associated with the port, which in turn causes the piston to exert a force on the inside of he housing to pivot the drilling string relative to the housing in a direction away from the low side of the borehole.
U.S. Pat. No. 3,637,032 (Jeter) and related U.S. Pat. No. Re. 29,526 (Jeter) describe a steering tool for use in rotary drilling which includes a pendulum inclinometer and a compass as direction sensing means which are mounted in a housing and which together rotate relative to the drilling string at the speed of the drilling string and in the opposite direction in order to hold the direction sensing means substantially non-rotative relative to the earth. In operation, deviation of the drilling string either azimuthally or vertically results in actuation of one or more mechanical valves, resulting in selective inflation of bladders by drilling fluid and extension of ribs to impose a lateral force on the drill bit to urge the drilling string back on course.
U.S. Pat. No. 5,314,030 (Peterson et al) describes a steering tool for use in sliding drilling which includes an oscillating pendulum which is mounted on a rotatable drilling shaft. The pendulum is constrained so that it can oscillate only in a single plane. In operation, deviation of the drilling string from vertical results in similar deviation of the oscillating pendulum. The amplitude and phase relationship of the oscillations of the pendulum relative to the angular position of the drilling shaft are sensed with a transducer to produce control signals. The control signals are used to regulate fluid jets from the drill bit, providing preferential flushing to guide the drill bit back to a vertical course.
The AutoTrak™ drilling system, developed by Baker Hughes INTEQ, is an automated steering system for use in sliding drilling to drill vertical wells. The AutoTrak™ system is therefore intended to be used in conjunction with a drilling motor. The AutoTrak™ system includes three extendable and retractable stabilizer pads, inclinometers, microprocessors and internal hydraulic pumps. In operation, deviation of the drilling string from a desired orientation is sensed by the inclinometers and results in activation of the hydraulic pumps. Signals from the inclinometers are provided to the microprocessors which calculate the force required to overcome the deviation. The hydraulic pumps then deliver an extending force to one or more of the stabilizer pads in order to direct the drilling string back to the desired orientation. The VertiTrak™ drilling system, also developed by Baker Hughes INTEQ, is a version of the AutoTrak™ system which has been adapted for use in vertical drilling applications.
The PowerDrive™ drilling system, developed by Schlumberger, is an automated steering system for use in rotary drilling to drill vertical wells. The PowerDrive™ system is a fully rotating rotary steerable system. The PowerDrive™ system includes a bias unit with extendable and retractable pads. The bias unit rotates with the drill string. The extension and retraction of the pads is synchronized with the rotation of the drill string so that the pads are extended and retracted at a consistent rotational orientation. The extension and retraction of the pads is controlled by a control unit which contains self-powered electronics and sensors. The control unit is a "roll-stabilized platform" which maintains a constant orientation by rotating relative to the drill string. The PowerV™ drilling system, also developed by Schlumberger, is a version of the PowerDrive™ system which has been adapted for use in vertical drilling applications.
There remains a need for a steering tool which is relatively easy to construct and maintain and which is relatively simple to operate. There remains a need for a steering tool which does not require electrical sensors or electrically operated valves in order to perform the steering function. There remains a need for a steering tool which can be adapted for use in either rotary drilling or sliding drilling.


Provided is a hair dyeing composition, containing a first part containing (a) a nitrogen-containing compound expressed by the general formula (1) or a salt thereof and a second part containing a component (b) of an oxidizing agent, wherein a pH upon use is 7.5 to 12,

An oxidative hair dye having a first part containing an alkali agent, a precursor, and a coupler and a second part containing hydrogen peroxide is preferable in that gray hair can be more evenly dyed and in that a hair color is greatly changed, as compared to other hair dyes, and thus has been widely used in general. This is derived from characteristics that in an oxidative hair dye, alkaline hydrogen peroxide decomposes melanin inside hair and the color of the hair can be thus bleached to be brightened. Particularly, in recent years, it has become preferred that black and white hair is dyed without unevenness with more bright colors and with bright and vivid color tone, and there has been a tendency that higher bleaching ability is required.
In order to obtain higher bleaching ability, it is considered that an alkali agent or an oxidizing agent is contained in a large amount, but there is a possibility of causing problems such that, depending on its amount, strong pungent odor is accompanied, hair is damaged, and the scalp is irritated.
Accordingly, a method of containing a specific triazacyclononane compound in a hair dye (Patent Document 1) and a method of containing a specific cyclic amine compound in a hair dye (Patent Document 2) have been proposed. However, these methods are insufficient for obtaining high bleaching ability with less pungent odor and less hair damage.
[Patent Document 1] JP-A-2002-255763
[Patent Document 2] WO Publication No. 2003/051322

Abstract: wherein R1 and R3 to R5 represent H, a hydroxy group, and an alkyl group with C12 or less optionally having a substituent, R2 represents a hydroxy group, —R or —OR, in which R means the same as R3 to R5, and two or more of R1 to R5 may be taken together to form a 3 to 8 membered-ring optionally having a substituent.


The disclosure discloses an antenna module and an electronic system. The antenna module includes a waterproof protective cover, a transparent cap, a printed circuit board, a wireless communication unit and an antenna unit. The waterproof protective cover is removably assembled onto an opening on a metal shielding case of the electronic system. The water-proof protective cover has a housing slot. The transparent cap is mounted on the waterproof protective cover. A first part of the printed circuit board is inserted into the housing slot. A second part of the printed circuit is located within the metal shielding case. The wireless communication unit is disposed on the second part of the printed circuit board. The antenna unit is disposed on the first part of the printed circuit board and electrically connected with the wireless communication unit.

1. Technical Field
The present disclosure relates to an antenna. More particularly, the present disclosure relates to a modularized antenna suitable for a power system.
2. Description of Related Art
Power systems (e.g., power plants, power generators, solar panels, etc) require controlling circuits for maintaining their functions or monitoring their conditions. There are many ways to implement the controlling circuits, such as implementing programmable logic controllers (PLC) on each individual device, setting up a central controller to control multiple devices, or implementing a wireless controller for controlling all devices remotely. Among these solutions, the wireless controller provides the best flexibility and controllability.
The wireless controller requires an antenna for transferring or receiving the telecommunication signals or information between two devices. Some traditional antennas are sealed within the metal casing of the device. Some other antennas are formed as individual pieces extending from a printed circuit board of the device to an external space outside the device. The traditional antenna design is suitable for an indoor device. However, the same design of antenna encounters some problem while being utilized in an outdoor device, such as a micro-inverter or an electronic device with requirements of ingress protection (IP).
For example, the micro-inverter is one of common electrical device with requirements of ingress protection (IP) and is widely used in a distributed power network. Many devices in the distributed power network are implemented outdoors. Therefore, the micro-inverter usually has a metal shielding case for providing an ingress protection. For example, some micro-inverters are required to have a high ingress protection rating, e.g. rating at IP65. If the antenna is sealed inside the metal shielding case, the telecommunication signal will be blocked by the metal shielding case. On the other hand, if the antenna is extended through a through hole on the metal shielding case, it is hard to achieve the waterproof requirement for the ingress protection rating.
In addition, some electronic devices with requirements of ingress protection (IP) may require extra holes opened on the metal shielding case in order to display indicative light signals representing the working state of the electronic devices. However, extra holes on the case may increase the difficulty of waterproof feature.


A variety of methods and arrangements for determining whether a high pressure exhaust spring is present in a cylinder of an internal combustion engine are described. For spark ignition engines, the electrical properties of the spark plug spark gap may be used to determine whether a high pressure exhaust spring is present.

Fuel efficiency of internal combustion engines can be substantially improved by varying the displacement of the engine. This allows for the full torque to be available when required, yet can significantly reduce pumping losses and improve thermal efficiency by using a smaller displacement when full torque is not required. The most common method today of implementing a variable displacement engine is to deactivate a group of cylinders substantially simultaneously. In this approach the intake and exhaust valves associated with the deactivated cylinders are kept closed and no fuel is injected when it is desired to skip a combustion event. For example, an 8 cylinder variable displacement engine may deactivate half of the cylinders (i.e. 4 cylinders) so that it is operating using only the remaining 4 cylinders. Commercially available variable displacement engines available today typically support only two or at most three displacements.
Another engine control approach that varies the effective displacement of an engine is referred to as "skip fire" engine control. In general, skip fire engine control contemplates selectively skipping the firing of certain cylinders during selected firing opportunities. Thus, a particular cylinder may be fired during one engine cycle and then may be skipped during the next engine cycle and then selectively skipped or fired during the next. In this manner, even finer control of the effective engine displacement is possible. For example, firing every third cylinder in a 4 cylinder engine would provide an effective displacement of ⅓rd of the full engine displacement, which is a fractional displacement that is not obtainable by simply deactivating a set of cylinders.
U.S. Pat. No. 8,131,445 (which is incorporated herein by reference) teaches a continuously variable displacement engine using a skip-fire operational approach, which allows any fraction of the cylinders to be fired on average using individual cylinder deactivation. In a continuously variable displacement mode operated in skip-fire, the amount of torque delivered generally depends heavily on the firing fraction, or fraction of combustion events that are not skipped. In other skip fire approaches a particular firing pattern or firing fraction may be selected from a set of available firing patterns or fractions.
In order to operate with skip fire control it is desirable to control the intake and exhaust valves in a more complex manner than if the cylinders are always activated. Specifically the intake and/or exhaust valves need to remain closed during a skipped working cycle to minimize pumping losses. This contrasts with an engine operating on all cylinders, where the intake and exhaust valves open and close on every working cycle. For cam operated valves a method to deactivate a valve is to incorporate a solenoid controlling a collapsible valve lifter into the valve train. To activate the valve the lifter remains at its full extension and to deactivate the valve the lifter is collapsed. Other mechanisms exist to deactivate valves in engines with cam operated valves. Engines with electronic valve actuation generally have more flexibility in the valve opening and closing because the valve motion is not constrained by rotation of a camshaft.
If cylinder deactivation occurs after a combustion event but prior to an exhaust event, all of the exhaust remains in the cylinder during the duration of deactivation. This condition may be referred to as the cylinder having a high pressure exhaust spring (HPES) in the cylinder. If instead, the cylinder deactivation occurs after the exhaust valve has opened but before the intake valve is opened, only a small residual charge remains in the cylinder. This condition may be referred to as the cylinder having a low pressure exhaust spring (LPES).
A potential problem with skip fire control is that if for some reason the exhaust gases associated with a cylinder firing have not been vented from the cylinder attempting to open the intake valve may damage the valve, push rod, lifter or any component in the valve train because of the high pressure contained in the cylinder. It is desirable if a determination of whether a cylinder has vented can be made prior to activation of the intake valve.

Determination of a high pressure exhaust spring in a cylinder of an internal combustion engine


A system includes a lead-sleeve coupled to a platform. The platform attaches to a sheet metal having alternating peaks and valleys, and the platform includes a block-out component that conforms to a valley of the sheet metal. The system also includes an indicator system coupled to a cap of the lead-sleeve, where the indicator system protrudes through the concrete after the concrete is poured and solidified around the lead-sleeve.

The present disclosure relates generally to the field of firestop protection, and more particularly to systems and methods for indicator systems within a firestop protection system.
In contemporary building constructions, formworks formed of corrugated sheet metal having alternating valley and peak regions are widely used. Formworks may be used in substantially horizontal ceilings, in floors, or in walls. In certain situations, formworks utilized in horizontal ceiling applications may be cast in concrete on-site, such that the corrugated sheet metal remains on the lower side of the ceiling. Furthermore, in certain construction applications, tubular leads, conduits, cables, or various other items are routed through the formwork and the concrete. Various techniques may be utilized to form through-penetrations through the corrugated sheet metal so that these and other materials may be routed through the ceiling. For example, in certain situations, through-penetrations may be formed with pre-installation systems that are fixed to the formwork before the concrete is poured. After the concrete has been formed and solidified, the through-penetrations may be formed by drilling holes (e.g., coring) through the corrugated sheet metal in the concrete-free region underneath the pre-installation system.
However, in certain situations, it may be difficult for an operator to locate and identify the drilling site, at least in part because the pre-installation system may be partially or entirely concealed by the poured concrete. Accordingly, it may be beneficial to provide systems and methods for locating and/or identifying the drilling site (e.g., the pre-installation system) after the concrete has been poured and solidified on the formwork.

Systems and methods for an indicator system in firestop protection systems


A cold trap includes two individually controllable cooling units. The cold trap is provided in an evacuation path for connecting a vacuum chamber to a turbomolecular pump, The first cooling unit includes a first panel unit provided in the evacuation path such that the panel is exposed, and a first refrigerator thermally coupled to the first panel unit so as to cool the first panel unit. The second cooling unit includes a second panel unit provided in the evacuation path such that the panel is exposed, and a second refrigerator thermally coupled to the second panel unit so as to cool the second panel unit. The first panel unit is spaced apart from the second panel unit.

1. Technical Field
The present invention relates to a cold trap and a method of controlling the cold trap.
2. Description of the Related Art
Cryopanels and cold traps are known as apparatus for evacuating by condensing and adsorbing gas molecules on a cryopanel cooled to an extremely low temperature. Normally, a cold trap is provided in a stage preceding a vacuum pump in a turbomolecular pump and is used in combination with a vacuum pump for evacuation. Normally, a cooling apparatus such as a system for supplying a cooling fluid or a cryogenic refrigerator is provided in association with the cold trap so that the surface of the cryopanel is cooled to a cryogenic temperature.

Cold trap and method of controlling cold trap


A tethering device (10) comprising a support member (12) and a rotatable member (14) rotatably mounted on the support member (12) and about which a flexible tether line (16) can be wound for tethering an animal or object to the support member (12).

The use of animal tethering devices is known in the prior art. Animal tethering devices are used to restrain animals so that their ranges of movement are restricted. These devices typically comprise a flexible member such as a chain or rope which is attached to the animal usually by means of a collar around the neck of the animal.
However, difficulties have been encountered with known tethering devices as a result of the twisting and tangling of the leash. If an animal becomes entangled in the leash the animal's movement is restricted which could result in injury to the animal.
Furthermore, problems have been experienced with known devices in attempting to restrict the precise radius of movement of the animal. This is desirable where it is required to restrict the particular area of grazing of an animal for example to concentrate grazing in one area of a field or garden.
A further disadvantage of previously known tethering devices is that they are large and unwieldy and difficult to set up and take down. Furthermore, many of these devices require another implement such as a hammer to drive them into the ground. Thus, a device which may be easily driven into and taken out of the ground without the need for another implement is desirable.
It is an object of the present invention to overcome at least one of the above difficulties.


Described is a permanently and continuously fragrance-emitting dry or wet wipe laminar fabric article comprising a non-woven fabric lamina having woven therethrough and substantially throughout at least a major portion of the lamina surface at least one continuous fragrance-containing thermoplastic, substantially water-insoluble fiber, which controllably and continuously releases fragrance at least for the time period during which the fabric article is in use. Such fragrance may also have antimicrobial properties. Optionally, one or more antimicrobial substances may also be releasably contained in the fiber containing the fragrance or in a fiber apart therefrom. The fabric article optionally contains additional fragrance and/or antimicrobial agent absorbed in or adsorbed on the non-woven fabric lamina. Also described is a process for preparing the permanently fragrance-emitting dry or wet wipe laminar fabric article by means of (a) creation of a non-woven fabric lamina optionally containing fragrance which may also have antimicrobial properties and/or at least one antimicrobial agent; (b) creation of a fragrance-containing polymeric fiber which, optionally, also contains at least one antimicrobial agent; and (c) weaving the fragrance-containing fiber through the non-woven fabric lamina substantially across at least a major portion of the surface area of the non-woven fabric lamina.

Our invention is directed to a controllably releasable or permanently fragrance-emitting dry or wet wipe laminar fabric article which optionally has efficacious antimicrobial properties comprising a non-woven fabric lamina having woven therethrough and substantially throughout at least a finite portion of the laminar surface, at least one continuous fragrance-imparting component-emitting fiber, which controllably and continuously releases fragrance and, optionally, antimicrobial agent at least for the time period of use of said dry or wet wipe laminar fabric article. Our invention is also directed to a process for the production of such dry or wet wipe laminar fabric article.
Dry and wet wipes are well known commercial consumer products which have been available in many forms. Perhaps the most common form of wet wipes has been a stack of moistened sheets which have been packaged in a plastic container. The wet wipes have been made from a variety of materials which have been moistened with a variety of suitable wiping solutions. Such wet wipes have been used for baby wipes, hand wipes, household cleaning wipes, industrial wipes and the like. By the same token, dry wipes have been made from a variety of materials containing various substances such as antibacterial substances.
With respect to the wet wipes, typically, such conventional wet wipes have included a single layer of a substantially homogeneous material. For example, conventional wet wipes have included an air laid web of fibers which are uniformly mixed or distributed throughout the web. The wipes have included polymeric fibers such as polyester, polyethylene and polypropylene and natural or synthetic fibers such as cellulosic fibers. Other conventional wet wipes have included a co-formed web of polypropylene and cellulosic fibers wherein the fibers are uniformly mixed throughout the web.
European Published Patent Application No. 914,509 published on May 12, 1999 (corresponding to PCT Application No. 98/03713) discloses improved wet wipe articles including a multiple layer base sheet to provide a unique combination of properties to the wipe which are not capable in a single layer base sheet. The layered base sheet includes, in said European Published Patent Application No. 914,509, at least two layers which include different fibers and have different physical properties. One of the layers may include polyethylene fibers to provide a soft, gentle feel for contacting the skin of the user during use while the other layer may include polypropylene fibers to provide strength and resiliency to the wipe to withstand the forces exerted by the user and maintain its shape and integrity in use. The specification of Published European Patent Application No. 914,509 published on May 12, 1999 as well as the corresponding PCT Application No. 98/03713 and the corresponding United States Application No. 97-U.S.-0723 filed on Jun. 19, 1997 are incorporated herein by reference.
The wet wipes and dry wipes referred to in Published European Patent Application No. 914,509 as well as the corresponding PCT Application No. 98/03713 are not disclosed to be fragranced or fragrancable.
However, fragranced fiber materials are well known in the prior art. Thus, U.S. Pat. No. 3,567,118 issued on Mar. 2, 1971 discloses composite fiber materials which are adapted for odorizing, deodorizing, sanitizing and cleansing purposes by treating the fibrous material with a coating of a hydrophilic acrylate or methacrylate containing an appropriate essence, bactericide, cleansing agent or the like. It is indicated in said U.S. Pat. No. 3,567,118 that both natural and synthetic fibers can be treated with a solution of the hydrophilic polymer, and that entrapment of the chemical agent can be prolonged by using a copolymer of the hydrophilic monomer with a minor amount of a hydrophobic monomer. U.S. Pat. No. 3,567,118 does not set forth the creation of a permanently, continuously fragrancing wet wipe or dry wipe. By the same token, U.S. Pat. No. 3,567,119 issued on Mar. 2, 1971 discloses methods for the incorporating of fragrance compounds or oil bouquets and/or topical antifungal or antibacterial agents, insect repellent compounds and certain odoriferous medicaments into polymeric or natural materials so that the fabricated product possesses the properties imparted by the additive or additives for a long period of time. Further, in U.S. Pat. No. 3,567,119, it is indicated that the efficiency of incorporating additives such as fragrance materials into the articles of the invention is improved by the use of surfactants and the effectiveness and duration of the additive or additives in the fabricated product is enhanced by employing antioxidants and/or ultraviolet radiation absorbers.
However, neither U.S. Pat. No. 3,567,118 nor U.S. Pat. No. 3,567,119 discloses the efficacious continuous and permanent fragrance-emitting dry or wet wipe article of our invention which has woven therethrough fragrance-emitting fiber which is thermoplastic and substantially water-insoluble.
Non-woven fabrics having fibers woven therethrough substantially throughout at least a major portion of the laminar surface thereof are known in the prior art. Thus, U.S. Pat. No. 5,902,757 issued on May 11, 1999 (the specification for which is incorporated herein by reference) discloses a stitch bonded fabric sheet having a felt web with a hydrophobic layer and a hydrophilic layer stitch bonded with yarns to create yarn faces over the respective outer surfaces of the felt web. The sheet may be used as a fluid retention fabric such as to replace the facing fabric and felt layer in an incontinent pad. Nothing is set forth in U.S. Pat. No. 5,902,757 indicating or inferring the utility of such a yarn containing fragrance and/or antimicrobial substance.
However, fragrant fibers per se are well known in the prior art. Thus U.S. Pat. No. 4,713,291 issued on Dec. 15, 1987 discloses fragrant fiber wherein a fragrant sheath-core composite fiber xe2x80x9csuitable for beddingxe2x80x9d and having a cross section including a sheath and a core including a hollow portion wherein an aromatic perfume having a boiling point higher than 150xc2x0 C. under normal pressure is incorporated and dispersed in an amount 0.1 to 10.0% by weight in a thermoplastic polymer constituting the core. The core component in U.S. Pat. No. 4,713,291 is preferably a polyethylene-type polymer, and the sheath component is preferably a polyethylene terephthalate polymer. One of the typical compositions of the aromatic perfume of U.S. Pat. No. 4,713,291 is an essential oil mixture including (i) 10 to 20% of lemon oil; (ii) 5 to 15% of bergamot oil; (iii) 2 to 8% of lavender oil; (iv) 2 to 8% of lemongrass oil; (v) 2 to 8% of cedarwood oil and (vi) 0.5 to 1.5% of jasmine absolute. The disclosure of U.S. Pat. No. 4,713,291 is incorporated by reference herein. However, U.S. Pat. No. 4,713,291 does not disclose the use of such fragranced fibers as an essential component of a dry wipe or a wet wipe. Antimicrobial component-containing fibers which can be sewn into textile prostheses for insertion into the body, and epidermal pads and bandages are disclosed in PCT Published Application No. 99/21507 published on May 6, 1999. However, PCT Published Application No. 99/21507 does not disclose the use of such fibers in conjunction with wet wipes or dry wipes and, furthermore, does not disclose the incorporation into such fibers of fragrance materials.
The entire specifications of PCT Published Application No. 99/21507 as well as U.S. Pat. Nos. 3,567,118 and 3,567,119 are incorporated herein by reference.
In summary, although the prior art shows (a) dry wipes and wet wipes made of non-woven fabric; (b) shows fragranced fibers; and (c) shows fragranced non-woven fabrics, nothing in the prior art sets forth wet wipes or dry wipes of our invention which are permanently and continuously fragrance-emitting and, optionally, antimicrobial substance-emitting of our invention.
Our invention is directed to a controllably releasable or permanently fragrance-emitting dry or wet wipe laminar fabric article which optionally has efficacious antimicrobial properties comprising a non-woven fabric lamina having woven therethrough and substantially throughout at least a finite portion of the laminar surface at least one continuous fragrance-imparting component-emitting fiber which controllably and continuously releases fragrance and, optionally, antimicrobial agent at least for the time period of use of the dry or wet wipe laminar fabric article.
More specifically, our invention is directed to a permanently and continuously fragrance-emitting dry or wet wipe laminar fabric article comprising a non-woven fabric lamina having woven therethrough and substantially throughout at least a major portion of the lamina surface at least one continuous fragrance-containing thermoplastic substantially water-insoluble fiber which controllably and continuously releases fragrance (which may also have antimicrobial properties) at least for the time period during which the fabric article is in use. Optionally, one or more antimicrobial substances may also be releasably contained in the fiber containing the fragrance or in a fiber apart therefrom. The fabric article optionally contains additional fragrance and/or antimicrobial agent absorbed or adsorbed on the non-woven fabric lamina.
Our invention is also directed to a process for preparing the permanently fragrance-emitting dry or wet wipe laminar fabric article by means of (a) creation of a non-woven fabric lamina optionally containing fragrance which may also have antimicrobial properties and/or at least one antimicrobial agent; (b) creation of the fragrance-containing polymeric fiber which optionally also contains at least antimicrobial agent; and (c) weaving the fragrance-containing fiber through the non-woven fabric lamina substantially across at least a major portion of the surface area of the non-woven fabric lamina.
More specifically, the process of our invention for producing a fragrance-emitting laminar fabric article comprises the sequential steps of:
(a) providing polymer matrix particles having releasably entrapped therein at least one aroma-imparting component which optionally has efficacious antimicrobial properties in a concentration of from about 1% up to about 45% by weight of the polymer particles and, optionally, one or more antimicrobial substances (with the polymer matrix being composed of a thermoplastic substantially water-insoluble polymer);
(b) optionally admixing the matrix particles with a compatible thermoplastic substantially water-insoluble polymer whereby a matrix polymer mixture is formed;
(c) forming the polymer particles or matrix polymer mixture into one or more continuous fragrance-imparting component-emitting fibers of from about 3 denier up to about 60 denier;
(d) providing a non-woven fabric laminar substrate (which may be a monolayer laminar substrate, a bilayer laminar substrate, a trilayer laminar substrate or another multilayer laminar substrate having as much as six layers);
(e) weaving the fragrance-imparting component-emitting fiber or fibers through the non-woven fabric laminar substrate across at least a major portion of the surface area of the non-woven fabric laminar substrate (with the xe2x80x9cweavingxe2x80x9d operation being, for example, a xe2x80x9cneedlexe2x80x9d punching operation); and
(f) optionally adding additional fragrance and/or antimicrobial agent to the resulting laminar fabric article.
The non-woven fabric lamina may be any non-woven fabric lamina known to those skilled in the art, which lamina is substantially water-insoluble, but which has the property of absorbing therein additional water on use of the wet wipe or dry wipe article. Thus, for example, the non-woven fabric may be a filament non-woven fabric comprising thermoplastic conjugated filaments comprising at least one low melting point resin or low softening point resin selected from the group consisting of olefin binary copolymer or olefin terpolymer as the first component and crystalline thermoplastic resin as the second component as set forth in European Published Patent No. 908,549 published on Apr. 14, 1999.
Preferably, the non-woven fabric lamina useful in the practice of our invention contains from about 5 up to about 20% cellulose acetate fiber; from about 10 up to about =30% polypropylene; and from about 50 up to about 80% by weight of viscose.
Furthermore, the non-woven fabric lamina may comprise a non-woven layered base sheet which includes at least two layers positioned in facing relation with each other, 20 at least one of the layers including fibers not included in the other layers as disclosed in Published European Patent Application No. 914,509 published on May 12, 1999, the specification for which is incorporated by reference herein. Thus, European Published Application No. 914,509 claims:
(1) a multilayer of wet wipe comprising:
(a) a liquid;
(b) a first non-woven outer layer;
(c) a second non-woven outer layer positioned in facing position to the first outerlayer; and
(d) a non-woven inner layer positioned in facing relation between the first outer layer and the second outer layer, with the outer layers including fibers different from those of the inner layer; and
(2) a method of providing wet wipes comprising:
(a) providing a first continuously moving non-woven layer of material;
(b) providing a second continuously moving non-woven layer of material in facing relation with the first non-woven base sheet, the second layer comprising fibers not included in the first layer;
(c) a least partially securing the first and second layers together;
(d) adding a liquid to the layered base sheet; and
(e) cutting the continuously moving layered base sheet into individual sheets to provide the wet wipes.
Omission of step (d) and consequent omission of the addition of the liquid to the layered base sheet yields a dry wipe sheet as opposed to a wet wipe sheet.
Additional non-woven laminae useful in the practice of our invention are produced according to the processes of U.S. Pat. No. 5,906,890 issued on May 25, 1999, the specification for which is incorporated by reference herein. U.S. Pat. No. 5,906,890 discloses a polypropylene fiber which is suitable for hot rolling and which is used for producing a non-woven fabric having high tenacity and good feel by heat rolling within a wide range of processing temperatures. The polypropylene fiber contains boiling in heptane extract in the amount of 1.5-5% by weight after extraction with boiling in hexane, and the extract has a melting point peak of 140xc2x0 C. or higher.
The non-woven laminae useful in the practice of our invention can also be produced from olefin polymer fiber containing polypropylene and heterophasic polymer as disclosed in granted European Patent No. 632,148 granted on May 12, 1999, the specification of which is incorporated herein by reference. In said Published European Patent No. 632,148, it is disclosed that an olefin polymer fiber for non-woven fabrics comprises:
(1) 50-80 parts by weight of propylene homopolymer with an isotactic index greater than 90 or a random copolymer of propylene with ethylene and/or C4-C8 xcex1-olefin; and
(2) 20-50 parts by weight of heterophasic polymer comprising:
(a) 20-70 parts by weight of propylene homopolymer and/or a random copolymer of propylene with 0.5-10 weight percent ethylene and/or C4-C8 xcex1-olefin; and
(b) 30-80 parts by weight of copolymer of ethylene with propylene and/or C4-C8 xcex1-olefin containing 40-47 weight percent ethylene and having a xylene solubility of 45-98% at 25xc2x0 C. and intrinsic viscosity of no more than 1.5 dl/g or containing less than 40 weight percent ethylene and having an intrinsic viscosity of no more than 2.3 dl/g; the fiber being obtained by spinning via an orifice with an actual or equivalent diameter of less than 0.5 mm and then drawing at a ratio of 1.1 up to 1.8.
The polymer matrix particles having releasably entrapped therein at least one aroma-imparting component which optionally has efficacious antimicrobial properties may be prepared according to processes well known in the prior art, for example, the processes as set forth in U.S. Pat. No. 4,542,162 issued on Sep. 17, 1985, the specification for which is incorporated herein by reference. Furthermore, such polymer matrix particles having releasably entrapped therein at least one aroma-imparting component may also be prepared according to United Kingdom Patent Specification No. 1,589,201 assigned to Hercules, Inc., which discloses a thermoplastic resin body consisting of a thermoplastic polymer of ethylene and 6-60 weight percent of a polar vinyl monomer selected from the group consisting of vinyl acetate, methyl acrylate, ethyl acrylate, buytl acrylate and acrylic acid wherein the perfumed resin body is suitable for the preparation of shaped objects from which the perfume odor emanates over a prolonged period at a stable level. Another process for preparing the polymer matrix particles having releasably entrapped therein at least one aroma-imparting component is U.S. Pat. No. 3,505,432, the specification for which is incorporated by reference herein. U.S. Pat. No. 3,505,432 discloses a method of scenting a polyolefin and forming polyolefin-scented particles which comprises:
(a) mixing a first amount of liquid polyolefin, e.g., polyethylene or polypropylene, with a relatively large amount of scent-imparting material to form a flowable mass;
(b) forming drops from said mass and causing substantially instantaneous solidification of said drops into polyolefin pellets having a relatively large amount of scent-imparting material imprisoned therein;
(c) if desired, melting said pellets with a second amount of said polyolefin, said second amount being larger than said first amount; and
(d) solidifying the melt of (c).
Other references which disclose microporous polymers useful in the practice of our invention are set forth as follows:
(a) U.S. Pat. No. 4,247,498 issued on Jan. 27, 1981, the specification for which is incorporated by reference herein;
(b) U.S. Pat. No. 4,156,067 issued on May 22, 1979, the specification for which is incorporated by reference herein; and
(c) U.S. Pat. No. 4,521,541 issued on Jun. 4, 1985, the specification for which is incorporated by reference herein.
The resulting polymer matrix particles having releasably entrapped therein at least one aroma-imparting component, may then be further admixed with additional compatible polymer. Thus, for example, additional polypropylene may be admixed with polypropylene particles which contain between about 1 and about 45% by weight of the polymer of fragrance.
The resulting mixture or the resulting polymer matrix particles having releasably entrapped therein at least one aroma-imparting component is then formulated into one or more continuous fragrance-imparting component-emitting fibers of from about 3 denier up to about 60 denier (1 denier means that 9,000 meters of fiber weigh 1 gram). The resulting mixtures can be formulated into such fibers by means of specific extruders for fiber manufacturing produced, for example, by the Davis-Standard Corporation of #1 Extrusion Drive, Pawcatuck, Conn. 06379. Such extrusion apparatus is preferably equipped with xe2x80x9chot runnerxe2x80x9d systems which enable the fibers to be produced at a uniformly constant diameter and to be produced in large quantity in an efficient manner.
In producing the fiber for purposes of weaving same into the lamina surface, it is preferred that the weight ratio of the polymer matrix particles having releasably entrapped therein at least one aroma-imparting component: additional compatible polymer being from about 2:1 down to about 1:1 with a preferred weight ratio of matrix particle:additional polymer being about 1.5:1.
The fibers of our invention which are used for weaving through the lamina surface need not necessarily be produced from matrix particles as set forth, supra. Instead, fragrance-emitting fibers for use in weaving same through the lamina surface of non-woven fabric may be produced according to processes as set forth in:
(a) PCT Application No. 99/21507 published on May 6, 1999;
(b) U.S. Pat. No. 4,713,291 issued on Dec. 15, 1987; and
(c) U.S. Pat. No. 3,567,118 issued on Mar. 2, 1971.
Each of the foregoing documents are incorporated herein by reference.
In PCT Application No. 99/21507, there is disclosed a synthetic fiber having cavities for holding large quantities of active material exemplified by medicaments. The Fragrance materials can be introduced into such fibers in place of the disclosed medicaments. Thus, alternative processes for producing such fibers are as follows:
(i) manufacturing fibers by extruding a plural-component fiber from a spinneret, dissolving a soluble component to form cavities and securing a fragrance into the cavities;
(ii) manufacturing fibers by extruding a single component fiber from a spinneret forming cavities and introducing therein fragrance components; and
(iii) manufacturing fibers by mixing a fragrance with a polymer and extruding the resulting mixture from a spinneret and forming island-in-the-sea plural-component fibers.
In U.S. Pat. No. 4,713,291, a fragrant sheath core composite fiber having a cross section including a sheath and a core including a hollow portion is produced wherein an aromatic perfume having a boiling point higher than 150xc2x0 C. under normal pressure is incorporated and dispersed in an amount of from about 0.1 up to about 10.0% by weight in a thermoplastic polymer constituting the core. The core component is preferably a polyethylene-type polymer and the sheath component is preferably a polyethylene terephthalate polymer.
In U.S. Pat. No. 3,567,118, composite fiber materials are adapted for odorizing purposes by treating the fibrous material with a coating of a hydrophilic acrylate or methacrylate containing an appropriate essence. Entrapment of the essence can be prolonged by using a copolymer of the hydrophilic monomer with a minor amount of a hydrophobic monomer.
Fragrance materials which are preferably incorporated in the polymer matrix particles or which are, in general, incorporated into the fiber, which is to be woven through the lamina surface, are preferably those fragrances which also have antimicrobial properties; for example, those set forth in Published Japanese Application No. JP101/94905 assigned to the Lion Corporation and published on Jul. 28, 1998, to wit:
(a) one or more aldehydes selected from cinnamic aldehyde, benzaldehyde, phenyl acetaldehyde, heptylaldehyde, octylaldehyde, decylaldehyde, undecylaldehyde, undecylenic aldehyde, dodecylaldehyde, tridecylaldehyde, methylnonyl aldehyde, didecylaldehyde, anisaldehyde, citronellal, citronellyloxyaldehyde, cyclamen aldehyde, xcex1-hexyl cinnamic aldehyde, hydroxycitronellal, xcex1-methyl cinnamic aldehyde, methylnonyl acetaldehyde, propylphenyl aldehyde, citral, perilla aldehyde, tolylaldehyde, tolylacetaldehyde, cuminaldehyde, LILIAL(copyright), salicyl aldehyde, xcex1-amylcinnamic aldehyde and heliotropin; and
(b) from about 0.01 up to about 10 weight percent of one or more crystallization controlling agents selected from dibutyl hydroxytoluene, butyl hdroxyl amisole, propyl gallate, xcex1-tocopherol, isopropyl citrate, erysorbic acid, sodium erysorbate, guaiac resin, calcium disodium ethylenediamine tetra acetate and disodium ethylenediamine tetra acetate.
Other preferable fragrance compositions are those set forth in U.S. Pat. No. 5,420,104 issued on May 30, 1995, the specification for which is incorporated by reference herein. Such perfume compositions as described in U.S. Pat. No. 5,420,104 contain a cationic phospholipid having the structure:
wherein R is linoleamidopropyl or cocamidopropyl; and X+y=3; a perfume base having antimicrobial activity and a fatty alcohol having from 10 up to 22 carbon atoms. Such a perfume base having antimicrobial activity contains:
benzyl acetate;
cyclohexyl acetate
styrallyl acetate;
n-octanol;
n-decanol;
amylcinnamic aldehyde
rosewood oil;
geraniol;
clove oil;
methyl jasmonate;
hydroxycitronellal;
methyl dihydrojasmonate;
ylang oil; and
mixture of methylionone isomers.
Furthermore, perfume compositions such as those set forth in:
U.S. Pat. No. 5,300,489 issued on Apr. 5, 1994 (the specification for which is incorporated by reference herein);
U.S. Pat. No. 5,932,771 issued on Aug. 3, 1999 (the specification for which is incorporated by reference herein); or
U.S. Pat. No. 5,942,272 issued on Aug. 24, 1999 (the specification for which is incorporated by reference herein),
may also be utilized in the fragrance-containing fiber which controllably and continually releases fragrance and which is woven through the major portion of the laminasurface of the non-woven fabric.
Thus, for example, the fragrance formulation contained in the fragrance-containing fiber which controllably and continuously releases fragrance, may include:
dihydromethyl jasmonic acid;
geraniol;
citronellol; and
oil of chamomile.
Along with the fragrances contained in the fragrance-containing fiber which controllably and continuously releases fragrances, the fiber may optionally have incorporated therein antimicrobial agents such as those set forth in the following list:
triclosan having the structure:
(an example is IRGASAN(copyright) DP 300, a trademark of Ciba Specialty Chemicals Holding Incorporated of Basel, Switzerland);
triclocarban having the structure:
the compound having the structure:
marketed as AMICAL(copyright) by Angus Chemie GmbH of Zeppelinstrasse, Ibbenbuhren, Germany;
the compound having the structure:
where X is halogen; R1 is hydrogen, halogen or alkyl; R2 is hydrogen or alkyl; and R3 and R4 are the same or different hydrogen, halogen or alkyl;
the compound having the structure:
a 2,3-dithiolane wherein R3 and R4 are the same or different hydrogen, alogen or alkyl, for example, the compound having the structure:
the compound having the structure:
the compound having the structure:
a compound having the structure:
wherein n is 0, 1 or 2;
the compound having the structure:
the compound having the structure:
the compound having the structure:
the compound having the structure:
the compound having the structure:
wherein the average values of x, y and z are, respectively, 75, 30 and 75;
compounds defined according to the structure:
wherein n is 1 or 2 and M is alkali metal when n is 1 or alkaline earth metal when n is 2; wherein R4 is hydrogen or methyl and R2 and R3 are hydrogen or C1-C18 alkyl as exemplified in Japanese Published Application JP111/16822, incorporated herein by reference; and
compounds defined according to the structure:
wherein R2 and R3 represent hydrogen, or C1-C18 alkyl and R4 is hydrogen or methyl (as exemplified in Japanese Published Application No. JP111/16822, incorporated herein by reference).
In addition to the fragrance ingredients together with the optional antimicrobial agents being present in the fiber used to be woven through the lamina of the non-woven fabric article of our invention, fragrance and/or antimicrobial agent as described, supra, may also be incorporated into the non-woven fabric itself, in addition to such fragrance being incorporated into the fiber. The presence of fragrance in the non-woven fabric article permits an initial xe2x80x9cburstxe2x80x9d of fragrance on use of the dry wipe or wet wipe and, in addition, the continuous controlled release of fragrance on continued use of the dry wipe or wet wipe article. In addition, the antimicrobial agent when incorporated directly into the non-woven lamina article provides an initial xe2x80x9cburstxe2x80x9d of antimicrobial agent in addition to continuous release of antimicrobial agent when such agent is incorporated into the continuous fragrance-containing fiber which controllably and continuously releases fragrance at least for the period of time during which the fabric article is in use.
The step of weaving the fragrance-imparting component-emitting fiber or fibers (once they are produced) through the non-woven fabric laminar substrate across at least a major portion of the surface area of the non-woven fabric laminar substrate is carried out by means of xe2x80x9cstitch bondingxe2x80x9d as more specifically described in such references as U.S. Pat. No. 5,902,757 issued on May 11, 1999, the specification for which is incorporated herein by reference. Thus, referring to U.S. Pat. No. 5,902,757, a stitch bonded fabric sheet has a felt web with a hydrophobic layer and a hydrophilic layer stitch bonded with yarns to create yarn faces over the respective outer surfaces of the felt web. The bonded fabric sheet may be used as a fluid retention fabric such as to replace facing fabric and a felt layer in a wet wipe or dry wipe article. Thus, the xe2x80x9cyarnxe2x80x9d of U.S. Pat. No. 5,902,757 is replaced in accordance with our invention with a continuous fragrance-containing fiber which controllably and continuously releases fragrance at least for the time period during which the fabric article is in use. As stated, supra, such continuous fragrance-containing fiber also may contain antimicrobial agent.
The quantity of fragrance material in the fragrance-containing fiber may vary from about 1% up to about 45% by weight of fragrance when no antimicrobial agent is present; or the sum total of antimicrobial agent and fragrance may vary from about 1% up to about 45% by weight of the fiber when antimicrobial agent is present. Preferably, the amount of fragrance or sum total of fragrance and antimicrobial agent varies between about 1% and about 20% by weight of the fiber.
Optionally, the additional fragrance and/or antimicrobial agent can be added to the laminar fabric article prior to weaving the fragrance-imparting component-emitting fiber or fibers through the non-woven fabric laminar substrate or subsequent to weaving the fragrance-imparting component-emitting fiber or fibers through the non-woven fabric laminar substrate or both prior to and subsequent to weaving the fragrance-imparting component-emitting fiber or fibers through the non-woven fabric laminar substrate.
Thus, in summary, the process for producing a fragrance-emitting laminar fabric article of our invention comprises more broadly the sequential steps of:
(a) forming one or more continuous fragrance-imparting component-emitting fibers optionally containing antimicrobial agent, of from about 3 denier up to about 60 denier;
(b) providing a non-woven fabric laminar substrate;
(c) weaving said fragrance-imparting component-emitting fiber or fibers through said non-woven fabric laminar substrate across at least a major portion of the surface area of the non-woven fabric laminar substrate; and
(d) optionally adding additional fragrance and/or antimicrobial agent to the resulting laminar fabric article.
Alternatively, the process of our invention comprises the sequential steps of:
(a) providing a non-woven fabric laminar substrate;
(b) optionally adding fragrance and/or antimicrobial agent to the fabric laminar substrate;
(c) forming one or more continuous fragrance-imparting component-emitting fibers optionally containing antimicrobial agent of about 3 denier up to about 60 denier; and
(d) weaving said fragrance-imparting component-emitting fiber or fibers through said non-woven fabric laminar substrate across at least a major portion of the surface area of the non-woven fabric laminar substrate.
Alternatively, the process of our invention comprises the sequential steps, broadly, of:
(a) providing a non-woven fabric laminar substrate;
(b) optionally adding fragrance and/or antimicrobial agent to the non-woven fabric laminar substrate;
(c) forming one or more continuous fragrance-imparting component-emitting fibers optionally containing antimicrobial agent of about 3 denier up to about 50 denier;
(d) weaving said fragrance-imparting component-emitting fiber or fibers through said non-woven fabric laminar substrate across at least a major portion of the surface area of the non-woven fabric laminar substrate; and
(e) optionally adding additional fragrance and/or additional antimicrobial agent to the resulting laminar fabric article.
Additional non-woven fabrics which may be used in the practice of our invention are referred to in the following references:
PCT Application No. 99/19452 published on Apr. 22, 1999 (xe2x80x9claundry treatment products for SPANDEX(copyright)-containing fabrics), incorporated by reference herein (PCT Application 99/19452 discloses a fabric treatment product containing a perfume which includes a mixture of fragrance materials for the treatment of garments containing SPANDEX(copyright) and other fibers, preferably after wearing thereof, to deposit fragrance materials to a greater extent on the SPANDEX(copyright) fibers other than on the other fibers);
U.S. Pat. No. 5,454,142 issued on Oct. 3, 1995 (xe2x80x9cNONWOVEN FABRIC HAVING ELASTOMETRIC AND FOAM-LIKE COMPRESSIBILITY AND RESILIENCE AND PROCESS THEREFORxe2x80x9d). In U.S. Pat. No. 5,454,142, a needlepunch fabric of staple polyester fibers is disclosed that is elastomeric and has foam-like compressibility and resilience. The polyester staple is formed of fibers having a differential berefringence. Mechanically crimped fibers are carded, crosslapped and needlepunched to from about 150 to 1,500 ppsi, and the resultant fabric is heated to from about 120xc2x0 C. up to about 240xc2x0 C. to induce a latent crimp in the fabric and to develop the elastomeric and foam-like properties of the fabric. U.S. Pat. No. 5,454,142 issued on Oct. 3, 1995 is incorporated herein by reference;
U.S. Pat. No. 5,906,890 issued on May 25, 1999, the specification for which is incorporated by reference herein;
U.S. Pat. No. 5,881,440 issued on Mar. 16, 1999, the specification for which is incorporated by reference herein;
U.S. Pat. No. 5,824,610 issued on Oct. 20, 1998, the specification for which is incorporated by reference herein. U.S. Pat. No. 5,824,610 discloses a non-woven fabric of chemically bonded non-cellulose fibers having improved wet tensile properties. The fabric includes a random arrangement of non-cellulose fibers and an essentially formaldehyde-free latex binder. The latex binder contains at least 6.7 weight percent vinyl cyanide monomer to bond the non-cellulose fibers and form a non-woven fabric having at least 10% improvement in wet tensile strength over a comparable non-woven fabric having latex binder essentially of formaldehyde and free of vinyl cyanide monomer in the monomeric mixture;
PCT Application No. 99/22619 published on May 14, 1999, the specification for which is incorporated by reference herein;
PCT Application No. 99/22059 published on May 6, 1999, the specification for which is incorporated by reference herein;
U.S. Pat. No. 5,783,503 issued on Jul. 21, 1998, the specification for which is incorporated by reference herein. In U.S. Pat. No. 5,783,503, it is disclosed that multicomponent thermoplastic continuous filaments are provided, including hollow core multicomponent filaments. The filaments are at least partially splitable into smaller filaments in the absence of mechanical treatment or application of high pressure water jets. The surface energy of the components can be controlled to control separation of the multicomponents"" filaments. Subdenier and microdenier filaments of low orientation can be produced in U.S. Pat. No. 5,783,503 from relatively high molecular weight polymers to produce non-woven fabrics of relatively high strength, barrier and cover;
U.S. Pat. No. 5,631,083 issued on May 20, 1997, the specification for which is incorporated by reference herein. U.S. Pat. No. 5,631,083 discloses a drawn, polyolefin fiber useful for non-woven fabrics with a thermobonding index being from about 4.5 up to about 9 Newtons and a flexibility being from 1,020 up to 1,500. The fiber of U.S. Pat. No. 5,631,083 is composed of a blend of specific polymers. Also disclosed in U.S. Pat. No. 5,631,083 is a process for making the fiber by spinning the blend from a die hole having at the output end a diameter less than 0.5 mm and drawing the resulting fiber at a draw ratio of 1:1 to 1:8; and
U.S. Pat. No. 5,925,581 issued on Jul. 20, 1999, the specification for which is incorporated by reference herein. U.S. Pat. No. 5,925,581 discloses a textile laminate comprising a fiber fill web substrate and a face layer. The fiber fill web substrate has a plurality of first fibers at the surface of the substrate. The face layer comprises a plurality of extruded second fibers which are mechanically intertangled with the plurality of first fibers at the surface of the substrate to thereby form the textile laminate. The first fibers of the fiber fill web of U.S. Pat. No. 5,925,581 are polyester fiber fill fibers and the second fibers of the extruded face layer are polypropylene fibers. The non-woven fabrics of U.S. Pat. No. 5,925,581 incorporated by reference herein are particularly suitable for use in conjunction with our invention.
Also useful in the practice of our invention are the antimicrobial mixtures claimed in the following patents and published patent applications:
Japan Published Application No. 28/91622 granted on May 17, 1999 discloses and claims antibacterial agents which are mixtures of the compounds having the structures:
wherein X is halogen; R1 is hydrogen, halogen or alkyl; R2 is hydrogen or alkyl; and R3 and R4 are the same or different hydrogen, halogen or alkyl;
Japan Published Application No. 28/91623 granted on May 17, 1999 discloses and claims a mixture of compounds having the structures:
wherein X is halogen; Y is hydrogen or halogen; R1 is hydrogen or lower alkyl; R2 is hydrogen or hydrocarbyl; and R3 and R4 are the same or different hydrogen or halogen;
Japan Published Application No. 28/91629 granted on May 17, 1999 discloses the use as an antimicrobial mixture of the compounds having the structures:
Japan Published Application No. 28/91635 granted on May 17, 1999 discloses the use as an antimicrobial mixture of the mixture of compounds having the structures:
(wherein X is halogen; R1 is hydrogen, halogen or alkyl; R2 is hydrogen or alkyl; and R3 and R4 are the same or different hydrogen, halogen or alkyl); and the compound having the structure:
European Published Application No. 917880 published on May 26, 1999 discloses an inclusion complex of the compound having the structure:
with cyclodextrin derivatives.
Other polymers that can be used for creation of the continuous fragrance-containing fiber which controllably and continually releases fragrance at least for the time period during which the fabric article is in use are disclosed in PCT Application No. US 99-05657 (PCT Serial No. 97 93 86 14.1, the disclosure of which is incorporated by reference herein). PCT Application No. US 99-05657 discloses the fragrance-emitting specially designed hydrophilic polyurethanes with certain hydrophobic components that retain aroma chemicals in the dry state and provide sustained fragrance release upon moisture exposure. The polymers are soluble in solvent mixtures ranging from 95:5 up to 20:80 weight:weight propylene glycol:water. In addition, they are also soluble in solvent mixtures of lower alcohols:water with similar ranges. Accordingly, the wet wipes and dry wipes which are composed of the polymers of PCT Application No. US 99-05657 are not to be used within the scope of this invention with alcohol or propylene glycol.
Additional perfumed fibers and antimicrobial product-containing fibers which can be employed in the practice of our invention are set forth in the following references (incorporated by reference herein):
Japan Published Application No. 63/135573 published on Jun. 7, 1988 (perfumed fiber production by applying perfume emulsifier including spinning oil to fiber and heating in steam), assigned to Takasago Perfumery Company, Ltd.; and
Japan Published Application No. 111/17174 published on May 27, 1999 discloses an antimicrobial fiber made up of polyester resin having a surface layer containing an antimicrobial agent. The antimicrobial agent consists of a quaternary phosphonium salt group which bonds ionically with an acid component of a hydrophilic resin (assigned to Toyobo KK).
In formulating polymer matrix particles having releasably entrapped fragrances or fragrance components therein and optionally one or more antimicrobial substances entrapped therein, the procedure of U.S. Pat. No. 4,542,162 granted on Sep. 17, 1985 may be utilized thusly:
foamed fragrance-containing polymeric pellets are produced by means of introduction into a single screw or twin screw extruder of, in series, thermoplastic polymer followed by fragrance followed by the introduction of a gaseous blowing agent or blowing agent which will produce a gas which is inert to the polymer and to the fragrance fluid or solid previously introduced into the extruder. Antimicrobial agent optionally may be introduced simultaneously with the introduction of fragrance or upstream from the point of introduction of fragrance into the extruder or downstream from the point of introduction of the fragrance into the extruder.
The advantages of using the foamed polymeric particles are multiple, to wit: improved handling; greater retention of fragrance; and, if desired, antimicrobial agent; greater length of time during which release of fragrance and, optionally, antimicrobial agent from polymer is at xe2x80x9csteady statexe2x80x9d or xe2x80x9czero order.xe2x80x9d
The nature of the extruder utilized in the process of our invention to form the foamed polymeric fragrance-containing polymer particles of our invention may be either single screw or double screw. Thus, the types of extruders that can be used are disclosed at pages 246-267 and 332-349 of the Modern Plastics Encyclopedia, 1982-1983, published by the McGraw-Hill Publishing Company, the disclosure of which is incorporated by reference herein. Similarly, such extruders are disclosed in the Modern Plastics Mid-November 1996 Encylcopedia, published by the McGraw-Hill Publishing Company, the disclosure of which is incorporated by reference herein. More specifically, examples of extruders which are usable in carrying out this aspect of the process of our invention are as follows:
1. The Welex xe2x80x9cSuper Twinchxe2x80x9d 3.5 inch extruder manufactured by Welex Incorporated, 850 Jolly Road, Blue Bell Pa. 19422;
2. Krauss-Maffei twin screw extruder manufactured by the Krauss-Maffei Corporation/Extruder Division, 3629 West 30th Street South, Wichita, Kan. 67277;
3. Modified Sterling model 4000 and 5000 series extruder manufactured by Sterling Extruder Corporation of 901 Durham Avenue, South Plainfield, N.J.;
4. CRT (xe2x80x9cCounter-Rotating Tangentialxe2x80x9d) Twin Screw Extruder manufactured by Welding Engineers, Inc. of King of Prussia, Pa. 19406;
5. The Leistritz Twin Screw Dispersion Compounder manufactured by the American Leistritz Extruder Corporation of 198 U.S. Route 206 South, Somerville, N.J. 08876;
6. The ZSK Twin Screw Co-Rotating Extruder maufactured by the Werner and Pfleiderer Corporation of 663 East Crescent Avenue, Ramsey, N.J. 07746;
7. The Farrel Extruder manufactured by Farrel Connecticut Division, Emhart Machinery Group, Ansonia, Conn. 06401;
8. The MPCNV Baker Perkins Twin Screw Extruder manufactured by the Baker Perkins Inc. Chemical Machinery Division of Saginaw, Mich. 48601; and
9. The Berstorff single screw, twin screw or foam extrusion equipment manufactured by the Berstorff Corporation, P.O. Box 240357, 8200-A Arrowridge Boulevard, Charlotte, N.C. 28224.
In producing the foamed fragrance-containing polymer particles of our invention (which optionally contain antimicrobial agent), various polymers may be utilized, for example, low density polyethylene, high density polyethylene, polypropylene, the copolymer of ethylene and vinyl acetate, and polyvinyl chloride. More specifically, the polymers used in the practice of our invention may be copolymers of ethylene and a polar vinyl monomer selected from:
(a) vinyl acetate;
(b) ethyl acrylate;
(c) methyl acrylate;
(d) butyl acrylate; and
(e) acrylic acid,
including the hydrolyzed copolymer of ethylene and vinyl acetate. Preferred co polymers are ethylene vinyl acetate with about 9 to 60% vinyl acetate and ethylene/ethyl acrylate with about 6 to 18% ethyl acrylate. As set forth, supra, other polymers which may be admixed with such materials include the polyurethane polymers of PCT Application No. PCT-US99-05657, incorporated herein by reference.
Resins of the type disclosed for use as copolymers are commercially available in the molding powder form. For example, ethylene vinyl acetate copolymers are marketed by the E.I. duPont de Nemours Company under the tradename xe2x80x9cELVAXxe2x80x9d and by the Arco Polymer Division under the trademark xe2x80x9cDYLAND(copyright)xe2x80x9d and by the Exxon Corporation of Linden, N.J. under the trademark xe2x80x9cDEXXON(copyright).xe2x80x9d Ethylene/ethyl acrylate copolymers are marketed by the Union Carbide Corporation under the tradename xe2x80x9cEEA RESIN(copyright).xe2x80x9d
The polymer is added to the single screw or twin screw extruder at a feed rate in the range of from about 80 up to about 300 lbs per hour, while maintaining the temperature in the screw extruder between about 160 and about 240xc2x0 C. If the polymer or copolymer powder is added to the extruder at a reference xe2x80x9cbarrel segment,xe2x80x9d then the fragrance and, optionally, the antimicrobial agent is added to the extruder in solid or liquid form under pressure downstream from the addition point of the polymer at one or more xe2x80x9cbarrel segmentsxe2x80x9d 2-9.
Thus, this aspect of our invention provides a process for forming fragrance and, optionally, antimicrobial liquid or solid-containing foamed polymeric particles such as foamed polymeric pellets, which include a relatively high concentration of a material having at least the function of fragrancing and, optionally, the function of imparting antimicrobial properties to the ultimately-produced fiber. The fragrance and, optionally, the antimicrobial agent in a fluid or solid form are added at xe2x80x9cbarrel segmentsxe2x80x9d 2-9 of the single screw or twin screw extruder. Furthermore, the fragrance and optionally antimicrobial agent added at xe2x80x9cbarrel segmentsxe2x80x9d 2-9 must be previously made to be compatible with the polymer added at xe2x80x9cbarrel segmentxe2x80x9d 1 of the single screw or twin screw extruder.
The use as to type and proportion of fragrance and optionally antimicrobial agent is limited only by either (a) their solubility in the resin or mixture of resins used and/or (b) the volume ratio of microvoids in the polymer to the said polymer and/or (c) the solubility of the fragrance and optionally antimicrobial agent in the polymer on solidification. The proportion of fragrance and optionally antimicrobial agent can in many instances go up to 45% by weight based on the total weight of fiber which is to ultimately be used in being woven across at least a major portion of the surface area of the non-woven fabric laminar substrate.
Thus, the proportion of fragrance and optionally antimicrobial agent to the weight of resin body for formation of the fiber to be woven across the non-woven fabric lamina can vary from small but effective amounts on the order of about 1% of the weight of the resin body (that makes up the fiber) up to about 45% by weight of the resin body (that makes up the weight of the fiber). In general, it is preferred to use between about 1% up to about 30% based on the weight of the resin body of the fragrance taken alone or taken together with optional antimicrobial agent. This is an optimum amount balancing the proportion of fragrance and optionally antimicrobial agent in the product against the time period over which the article emits the fragrance and optionally the antimicrobial agent, and against the tendency of the fragrance and optionally antimicrobial agent fluid or solid to oil out.xe2x80x9d This xe2x80x9coiling outxe2x80x9d is avoided as a result of the use of foaming agent.

Continuously fragrance-emitting dry or wet wipe fabric article and method for preparing same

International Flavors and Fragrances Inc.


An oxygen storage material based on cerium oxide with at least one other oxide of the metals silicon and zirconium, wherein the cerium oxide and the other oxides are present in the form of a mixed oxide. The material is obtainable in that hydroxidic precursors of the mixed oxide are first prepared in a manner known per se using a wet-chemical route, these precursors are optionally dried at temperatures between 80 and 300° C. and the dried precursors are then treated under a hydrogen-containing atmosphere at a temperature between 600 and 900° C. for a period of 1 to 10 hours. The reductive thermal treatment endows the material with a greatly improved dynamic behavior as compared with conventional calcination in air.

The present invention provides an oxygen storage material containing cerium oxide as well as a process for its preparation and its use for the catalytic conversion of substances, in particular for the treatment of exhaust gases from internal combustion engines.
Internal combustion engines emit as primary pollutants, with the exhaust gases, carbon monoxide CO, unburnt hydrocarbons HC and nitrogen oxides NOx, a high percentage of which are converted by modem exhaust gas treatment catalysts into the harmless components water, carbon dioxide and nitrogen. Conversion takes place substantially under stoichiometric conditions, that is to say the oxygen present in the exhaust gas is controlled with the aid of a so-called lambda probe in such a way that the oxidation of carbon monoxide and hydrocarbons and the reduction of nitrogen oxides to nitrogen can take place almost quantitatively. The catalysts developed for this purpose are called three-way catalysts. They usually contain, as catalytically active components, one or more metals from the platinum group in the Periodic Table of Elements on high surface area support materials such as γ-aluminum oxide with specific surface areas of more than 50 m2/g.
Stoichiometric conditions are present when the air/fuel ratio λ is 1. The air/fuel ratio λ is the air/fuel ratio normalized to stoichiometric conditions. The air/fuel ratio states how many kilograms of air are required for complete combustion of one kilogram of fuel. In the case of conventional gasoline engine fuels, the stoichiometric air/fuel ratio has a value of 14.6. Substoichiometric exhaust gas compositions with λ<1 are called rich and superstoichiometric compositions with λ>1 are called lean.
The engine exhaust gas, depending on the load and the speed of revolution of the engine, experiences relatively large periodic variations in air/fuel ratio around the value 1. For better conversion of oxidizable pollutant components under these dynamic conditions, oxygen storage components such as, for example, cerium oxide, are used which bind oxygen by changing the oxidation state from Ce3+ to Ce4+ when it is present in excess and release it again for the oxidative reaction by changing from Ce4+ to Ce3+ when there is a insufficiency of oxygen in the exhaust gas.
Car exhaust gas catalysts are subjected to exhaust gas temperatures of up to 1100° C. These high temperatures require the use of appropriate materials for the catalysts which are thermally resistant and have long-term stability.
EP 0 207 857 B1 describes a material based on cerium oxide which contains as essential components cerium oxide and an additive consisting of at least one of the oxides of the metals A from the group aluminum, silicon, zirconium and thorium. The material, with a specific surface area of more than 10 m2/g, is stable up to a firing temperature of 900° C.
EP 0 444 470 A1 describes a high surface area cerium oxide which consists of an intimate mixture of cerium oxide with 5 to 25 mol %, with respect to moles of cerium oxide, of a cerium oxide stabilizer. Lanthanum, neodymium and yttrium are mentioned as stabilizers. The material is obtained by co-precipitation from a common solution of a cerium oxide precursor and a precursor of the cerium oxide stabilizer and subsequent calcination in air at temperatures above 500° C. The BET surface area of this material after calcination at 980° C. for a period of 4 hours is still more than 20 m2/g.
EP 0 337 809 A2 describes a catalyst composition which contains, inter alia, zirconium oxide particles stabilized with cerium oxide. The zirconium oxide particles are stabilized with cerium oxide by impregnating zirconium oxide with a cerium salt solution. The impregnated particles obtained therefrom are dried and calcined until the graphical representation of the X-ray diffraction spectrum no longer shows a peak for the crystalline form of cerium oxide. Cerium oxide is present in the cerium oxide/zirconium oxide mixture in an amount of 10 to 50 wt. %, with respect to the zirconium oxide. In addition to the cerium salt, an yttrium and/or calcium salt may also be used. The X-ray diffraction spectrum, after the material has been calcined for 10 hours in air at a temperature of 900° C., shows only a peak for tetragonal zirconium oxide and no peak for cerium oxide. Cerium oxide is thus present in this material substantially in the form of a solid solution with the zirconium oxide.
EP 0 827 775 A1 describes an oxygen storage mixed oxide. The mixed oxide consists of cerium oxide or a cerium/zirconium mixed oxide which is loaded with praseodymium oxide. The molar ratio of praseodymium to cerium in the mixed oxide is between 1:4 and 4:1.
WO 98/42437 describes a catalyst composition which contains a mixed oxide of cerium and praseodymium and optionally one or more other rare earth oxides. The atomic ratio Pr:Ce is in the range between 2:100 and 100:100. The mixed oxide may be obtained by co-precipitation or by impregnating cerium oxide particles with a praseodymium precursor compound and then calcining in air and has, compared with pure cerium oxide, an improved oxygen storage capacity.
WO 98/45027 describes another catalyst composition which contains an oxygen storage material with improved oxygen storage capacity. The oxygen storage material is a mixed oxide which contains oxides of cerium, neodymium and zirconium. The material can be obtained by co-precipitation of compounds of zirconium and the rare earth metals followed by calcination in air.
The known oxygen storage materials are used in three-way catalysts for the treatment of exhaust gases from stoichiometrically operated internal combustion engines. An essential criterion for assessing these materials is thus their ability to improve the conversion of carbon monoxide and nitrogen oxides under the dynamic conditions prevailing in the exhaust gas. One measure of the dynamic conversion is the point of intersection of the conversion curves for carbon monoxide and nitrogen oxides, the so called "cross-over" point for exhaust gas compositions varying periodically between rich and lean. The conversion measured at the cross-over point is the highest conversion which can simultaneously be obtained for carbon monoxide and nitrogen oxides and is a measure of the rate at which it is possible to change the oxygen storage material being used from one oxidation state to the other. This property of the storage material is called the dynamics in the following. The higher the conversion at the cross-over point, the better also is the dynamic behaviour of the catalyst under consideration.
An object of the present invention is to provide an oxygen storage material which has better dynamic behaviour than the materials described hitherto. Further objects of this invention are a process for preparing this material and the use of this material in exhaust gas treatment catalysts for internal combustion engines.

Oxygen storage material based on cerium oxide, a process for its preparation and its use


A reduced iron production method includes: a reduction-step of producing reduced iron by heating an agglomerate containing iron oxide and carbonaceous reducing agent to reduce the iron oxide and solidifying a product produced by melting the reduced iron; a first-magnetic-separation-step of separating, among granular metallic iron, first slag, and second slag containing more fine-granular metallic iron than the first slag that are contained in the product, at least the granular metallic iron from the first slag by use of a first magnetic separator to separate first slag containing substance and a granular metallic iron containing substance from each other; a second-magnetic-separation-step of separating the second slag from the first slag containing substance or the granular metallic iron containing substance by use of a second magnetic separator having attraction force different from attraction force of the first magnetic separator; and a crushing-step of crushing the second slag.

There has conventionally been known a method for producing reduced iron by reducing iron oxide in the process of heat-melting an agglomerate containing an iron oxide containing substance and a carbonaceous reducing agent in a heating furnace. In such a method, various techniques have been proposed in order to efficiently recover reduced iron (that is, metallic iron to be a product) from a discharged material discharged from the heating furnace.
For example, Patent Literature1 proposes a technique that separates granular metallic iron contained in a discharged material discharged from a heating furnace from slag by a magnetic separator in order to extract the granular metallic iron to be a product from the discharged material.
Further, Patent Literature 2 proposes, as another conventional technique for separating and recovering metallic iron, a technique including passing a discharged material discharged from a heating furnace through a sieve, crushing the whole discharged material on the sieve by use of a crusher, and sorting a crushed material obtained by the crushing by use of a separator such as a magnetic separator to recover metallic iron to be a product.
However, in the production method described in Patent Literature 1, when a large amount of granular metallic iron with slag adhered or slag containing fine-granular metallic iron is produced due to unfavorable production conditions of reduced iron, the ratio of slag mixed into a group of metallic iron extracted by the magnetic separator increases. This makes it difficult to separate and recover high-purity granular metallic iron. The existence of slag containing fine-granular metallic iron in this manner (that is, the fine-granular iron containing slag) is not taken into consideration in a conventional reduced iron production field.
In the production method described in Patent Literature 2, the whole discharged material discharged from the heating furnace is crushed by use of the crusher. Thus, granular metallic iron that contains no impurity and can originally be shipped as a product in the discharged material is also wastefully crushed. Further, granular metallic iron is harder than the other substance (e.g., slag) in the discharged material. Thus, the granular metallic iron is difficult to crush, and crushing the granular metallic iron imposes a large load on equipment such as the crusher.

Reduced iron production method and production apparatus