A method for moving permanent virtual circuits in an ATM network with minimal downtime includes creating a list of the permanent virtual circuits to be moved; building a set of shadow permanent virtual circuits using the new ATM port and a temporary set of virtual path identifier and virtual circuit identifier pairs; moving a physical connection from the original ATM port to the new ATM port; deleting the permanent virtual circuits on the original ATM port; and changing the shadow permanent virtual circuits to use the original virtual path identifier and virtual circuit identifier pairs.

1. Field of the Invention
The present invention relates generally to broadband network management, and more particularly to management of asynchronous transfer mode networks.
2. Background of the Invention
Traditionally, telecommunications service providers have offered basic services such as local and long distance exchange services for voice communications. More recently, with the explosive growth of the Internet and other data services, telecommunications service providers have expanded beyond basic telephone services to the provision of very high bandwidth network services. Examples of such newer network services include, for example, digital subscriber line (DSL), asymmetric digital subscriber line (ADSL), integrated services digital network (ISDN) digital subscriber line (IDSL), and the like. The underlying transmission facility supporting such high bandwidth networks may comprise an asynchronous transfer mode (ATM) network as shown in FIG. 1A.
ATM network or "cloud" 10 in FIG. 1A comprises one or more ATM switches 11-15. The switches may be interconnected in any suitable manner to provide redundancy in the network and to ensure high speed transmission of network packets. ATM switches are well-known in the art and are available from numerous switch vendors, including, for example, Lucent, Seimens and Northern Telecommunications. ATM switches typically comprise a processor, a memory and a backplane for supporting multiple network cards in a plurality of slots 16 as shown in FIG. 1B. A network card, for example, network card 17, typically comprises multiple ports 18 for supporting multiple communications paths. A distinct physical transmission cable, for example, a coaxial cable or fiber optic cable, may be connected to any given port on the network card. Each physical transmission cable carries thousands of logical circuits providing voice and data service.
Network service providers (NSP) 20-22 are provided connectivity to their end-users, subscribers 30, via ATM cloud 10 and central office DSLAM 40 via a permanent virtual circuit (PVC). The network traffic for each NSP is carried via a plurality of PVCs. A PVC is a connection that is established from a source end point to a destination end point without the ability of either end point to dynamically establish or release the connection. PVCs are manually implemented and must be manually released. A PVC is a "permanent" circuit because each PVC defines an end-to-end path for routing packets. However, the PVC is a "virtual" circuit because bandwidth from the cloud is utilized only when it is required. Each PVC is assigned a virtual path identifier (VPI) and a virtual connection identifier (VCI), which together identify the virtual circuit's end points, in accordance with well-known ATM standard specifications. Each ATM packet transmitted in ATM network 10 includes a VPI field and a VCI field in a packet's header. Within ATM network 10, the combination of VPI/VCI must be unique for each PVC at the network interface point (the source end and destination end of the PVC) to the ATM network, i.e., the physical network interface.
As described above, each ATM switch 11-15 supports multiple network cards, and each network card supports multiple physical connections. However, in conventional ATM networks, the lack of tools for adequately planning capacity changes in the network has proven to be a problem. For example, if every slot 16 on ATM switch 11 is configured with a network card supporting a eight ports (i.e., physical connections), and each port was configured with over one thousand PVCs, an unacceptable performance may result. One method for reducing such problems in conventional ATM networks has been to initially under-build the ATM network. That is, for example, an ATM switch having twelve slots may only be filled with ten cards, and each card may only have connections going into six of the eight available ports.
While an ATM network capacity manager may have anticipated such limitations when the network was designed, an accurate capacity plan may not be achievable without real-world network traffic being observed. This may be particularly true in situations where the demand for such high-bandwidth network services could not be adequately predicted. After an ATM network has been established, any changes to the physical card and port configuration require re-provisioning of every PVC affected. Accordingly, even moving one ATM physical connection from one switch to another may require re-provisioning of thousands of PVCs, which means hours and hours of service interruption.
Because each PVC must have a unique VPI/VCI at each network interface (it takes two network interfaces to create a destination and end point), the conventional method for re-provisioning a PVC required the following general steps:
1. select the new interface port;
2. unplug physical connection from old port and terminate to the new port; and
3. reassign, or relocate, the logical or virtual circuits to the new port.
This methodology is necessary due to the fact that the stationary end of the virtual circuit (the side not being relocated) cannot be manipulated due to the restriction of the unique VPI/VCI for the interface port.
The problem with implementing these steps in a conventional manner is that it may take several hours or even days to complete, resulting in unacceptable network downtime leading to customer service impairment. For example, an existing network may be configured as shown in the FIG. 2A. In this example, multiple PVCs are assigned on the DSLAM end to port two on the card in slot five (denoted "C5/P2") of ATM switch 200. The NSP end of these PVC's are assigned to port three of the card in slot eight (C8/P3), port four of the card in slot 6 (C6/P4), and port two of the card in slot 8 (C8/P2) on ATM switch 200. If the ATM network manager needs to move all of these PVCs terminated to the DSLAM through the circuit connected to C5/P2 208 to a different card, for example, to port four on the card in slot seven (C7/P4), the ATM manager must manually reassign each virtual circuit associated with 208 manually as follows:
1. As shown in FIG. 2B, each PVC must be manually relocated to the port C7/P4. For example, PVC 202 is originally assigned a connection between C5/P2 and C8/P3 202, as shown in FIG. 2A. At this point, the new PVC, PVC 204 is an inactive PVC that will not carry traffic on the ATM network. Since the DSLAM 206 has not been connected to the new circuit 209, the PVC is inactive and will not be available to the end-users. This step typically takes about three minutes to perform for each PVC. Accordingly, if there are one thousand affected PVCs, the total downtime for this step alone will be fifty hours.
2. As shown in FIG. 2C, after the PVCs have been terminated to the new physical connection, circuit connection 209 is created by unplugging 208 from the old port. In other words, connection 208 is replaced by connection 209; and
3. As shown in FIG. 2D, the final step in the process is to restore service to each PVC after the physical circuit has been reconnected. At this point in the process, PVC 204 is active and available to NSP 20.
Step 2 is repeated for each PVC that has been moved. Again, this step requires about three minutes per PVC, resulting in a total downtime of fifty hours for this step and creating the unacceptable service condition requiring a different business process to complete the task.
As the above example illustrates, the conventional methods for moving network elements connected to an ATM cloud results in significant downtime for ATM network customers. A need therefore exists for a method of moving network elements with minimal network downtime for end-users associated with an ATM network.

Method for moving network elements with minimal network outages in an active ATM network

AT&T Delaware Intellectual Property, Inc.


A controlling circuit for controlling an operating clock of a logic circuit in an electronic device and the method thereof are disclosed. The controlling circuit includes a storage device, a detector, at least one comparator, and a controller. The storage device stores a first threshold value and a first return value. The detector detects a system load of the electronic device to generate a detection value. The comparator compares the detection value with the first threshold value or the first return value. When the detection value decreases to reach the first threshold value, the comparator generates a first indication signal. When the detection value increase to reach the first return value, the comparator generates a second indication signal. The controller enables underclocking of the logic circuit when receiving the first indication signal, and disables underclocking of the logic circuit when receiving the second indication signal.

1. Field of the Invention
The present invention relates to a logic circuit, especially to a controlling circuit and the corresponding method for controlling an operating clock and/or the driving voltage of a logic circuit.
2. Description of the Prior Art
When a computer is running a complicated program or executing bloat-ware (i.e., big software), sometimes it is necessary to adjust the operating frequency of a logic circuit of the computer, a CPU of the computer especially. When the system load of the computer increases, overclocking of the CPU can be enabled, so the operating frequency of the operating clock is increased to handle the extra system load of the computer. On the other hand, when the system load of the computer decreases, overclocking of the CPU can be disabled, so the operating frequency is decreased to save power.
Please refer to FIG. 1. FIG. 1 shows the system load of the computer and the operating frequency of the CPU, where overclocking of the CPU is originally disabled at an initial time point corresponding to system start-up. As shown in FIG. 1, the system load increases and exceeds a predetermined threshold L1 at the time point t1. At this moment, overclocking of the CPU is enabled so the operating frequency of the CPU starts to rise, where the increment of the operating frequency of the CPU is Δf1. Afterward, the system load decreases. When the system load falls below the predetermined threshold L1 at the time point t2, overclocking is disabled and the operating frequency of the CPU returns to its initial value.
FIG. 2 shows the system load of the computer and the operating frequency of the CPU, where overclocking of the CPU is originally enabled, conversely. As shown in FIG. 2, the system load decreases and falls below a predetermined threshold L2 at the time point t3. At this moment, overclocking of the CPU is disabled so the operating frequency of the CPU starts to fall, where the decrement of the operating frequency of the CPU is Δf2. Afterward, the system load increases. When the system load rises above the predetermined threshold L2 at the time point t4, overclocking is enabled and the operating frequency of the CPU increases to its initial value. Some of those skilled in the art might identify the situations shown in FIG. 2 with enabling underclocking of the CPU at the time point t3 and disabling underclocking of the CPU at the time point t4, respectively.
According to the related art, regarding the case of FIG. 1, it is suggested that while the computer is booting up, the driving voltage inputted into the CPU can be an increased voltage level higher than a normal voltage level that is originally utilized in the case of FIG. 1, in order to satisfy the extra power requirement inside the CPU due to enabling overclocking, where the increased voltage level is not changed until the computer is shut down. However, applying the increased voltage level as the driving voltage is energy inefficient since overclocking might not be enabled all the time. In addition, applying the increased voltage level as the driving voltage usually leads to an extra amount of the increment of the system load, causing the system load idling above the predetermined threshold L1 and therefore causing failure of the threshold detection at the time point t2 mentioned above. That is, by utilizing the predetermined threshold L1 to detect the system load, failing to trigger the decrease of the operating frequency of the CPU at the time point t2 may occur.
On the other hand, regarding the case of FIG. 2, enabling underclocking without applying a decreased voltage level (which is lower than a normal voltage level that is originally utilized in the case of FIG. 2) as the driving voltage is not considered to be real energy efficient since the power saved by merely enabling underclocking (without utilizing the decreased voltage level) is minor.

Controlling circuit for controlling operating clock and/or driving voltage of logic circuit, and method thereof


Apparatus for sanitizing objects by use of ultraviolet light includes an enclosed container defining a first object entry opening and a second object exit opening. A first inclined slide is mounted within the container and is positioned adjacent to the first entry opening, and a second inclined slide is mounted within the container beneath the first slide and positioned adjacent to the second exit opening. The slides are positioned at angles with respect to horizontal such that the pull of gravity on the objects moving down each of the slides is greater than restraining electrostatic or frictional forces on the objects. A baffle is mounted within the container and is positioned with respect to the slides for redirecting objects from the first slide onto the second slide, and ultraviolet light sources are mounted in the container and positioned above the slides for irradiating the objects as they move down the slides.

This invention relates to apparatus for sanitizing objects and more particularly to apparatus for sanitizing objects by use of ultraviolet light.
The use of ultraviolet lamps, and specifically UVC germicidal light tubes or lamps, for sanitizing objects is well known. However, existing ultraviolet sanitizing devices have not provided a compact size without complex moving parts for quickly and thoroughly sanitizing all sides of objects.
Studies have shown that bacteria can live for up to twenty-four hours on surfaces, such as hotel keys, credit cards, identification cards used by hospital personnel and others, coins, poker chips, playing cards, hair combs, etc.
It is, therefore, an object of the present invention to provide apparatus for sanitizing objects by use of ultraviolet light.
Another object is to provide such apparatus which is compact in size for convenient placement adjacent to cash registers, hotel desks, nursing stations or other easily accessible locations.
A further object of the invention is the provision of such apparatus which does not require expensive and complex moving parts for its operation.
Yet another object of the present invention is the provision of such apparatus which can sanitize objects of various sizes and shapes.
A still further object is to provide such apparatus which can be used by hotel or hospital personnel or by the general public to quickly and easily sanitize objects.
Another object is to provide such apparatus which effectively sanitizes all sides of the objects.
Still another object is to provide such apparatus which effectively sterilizes objects of bacteria, viruses and yeasts.
Additional objects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages are realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.


The substrate is used for opto-electric or electrical devices and comprises a layer of nitride grown by means of vapor phase epitaxy growth wherein both main surfaces of the nitride substrate are substantially consisting of non N-polar face and N-polar face respectively and the dislocation density of the substrate is 5×105/cm2 or less. Therefore, the template type substrate has a good dislocation density and a good value of FWHM of the X-ray rocking curve from (0002) plane less than 80, so that the resulting template type substrate is very useful for the epitaxy substrate from gaseous phase such as MOCVD, MBE and HVPE, resulting in possibility of making good opto-electric devices such as Laser Diode and large-output LED and good electric devices such as MOSFET.

The currently used substrates for a vapor phase epitaxy typically include Sapphire, SiC, GaAs and Si and the resulting epitaxy layers grown on the substrate have been still in the unfavorably high dislocation density of 109/cm2. Therefore, there have been proposed an application of ELOG-type structures to the substrate, which allows to decrease the dislocation density down to 106/cm2, but that density is still too high to ensure the correct functioning of many electronic and opto-electronic devices, particularly high power semiconductor lasers. Further, there is another problem that the resulting substrates have a decreased epitaxy face area because of the ELOG structure. Accordingly, we have proposed the other processes for obtaining mono-crystalline gallium-containing nitrides, For example, Polish patent application No. P-347918, where there is proposed a method of obtaining bulk mono-crystalline nitrides, represented by gallium nitride, through their re-crystallization from supercritical ammonia-containing solution. A characteristic feature of the bulk mono-crystalline gallium nitrides obtained using the afore-mentioned supercritical ammonia-containing solution is their low dislocation density (in the case of the bulk GaN: 104/cm2). It is, however, obtained at a low growth rate, in fact many times lower than the growth rate used in the growth methods from the gaseous phase.
1) The inventors of this invention have further discovered from their sharp researches that it is possible to significantly lower the dislocation density of the gaseous or vapor phase epitaxy layer without the ELOG structure if such a gaseous phase growth process is carried out on the surface of a substrate of bulk mono-crystalline gallium-containing nitride made by means of crystallization from supercritical ammonia-containing solution, and also to keep all the main surface of the substrate as the complete Ga-polar face for further epitaxy process of making opto-electric or electric devices. This is quite different from the ELOG-type substrate.
Furthermore, 2) the inventors have discovered that A-axis direction growth of GaN is 4 times or more faster than that of C-axis direction in a supercritical ammono method containing at least one alkali metals and get a mono-crystal nitride substrate having a diameter of 1 inch or more provided with a good quality such as C-axis orientation perpendicular to the C-plane extending at least 30 μm, preferably 50 μm or more. This is also quite different from the ELOG-type substrate.
According to the above findings 1) and 2) of the inventors, if an GaN layer is grown by means of HVPE on a mono-crystal nitride substrate made by the supercritical ammono method to have a thickness of 100 μm or more, preferably 150 μm or more and is sliced off from the mono-crystal nitride substrate, the resulting HVPE GaN have a dislocation density of 5×105/cm2 or less, preferably of 105/cm2, more preferably 104/cm2 or less and one of the surface substantially consists of Ga-polar face and is better than any ELOG GaN substrate.

Substrate for epitaxy and method of preparing the same


A key top comprising a key stem provided at a lower portion of the key top to be inserted into a rubber cup unit; and a first spring provided at a lower end of the key stem, and comprising a plate spring, wherein the key top is pushed down by finger pressure to turn on a contact point, thus executing key-in operation.

1. Field of the Invention
The present invention relates generally to key tops, and more particularly, to a key top which has a dust-proof design and superior sliding action.
2. Description of the Related Art
As well known to those skilled in the art, a key top is a part of each key switch constituting a keyboard. When a key cap of the key switch is pushed down by an operator's finger, the key top attached to the bottom of the key cap is moved down by finger pressure to turn on a contact point of a flexible printed circuit (FPC), thus realizing key-in operation.
A conventional key top is shown in FIG. 1.
In FIG. 1, the reference numeral 1 denotes a key top. The key top 1 is provided to correspond to each key on a keyboard. A key stem 12 extends downward from a central portion of a lower surface of the key top 1. Stoppers 11 are provided at predetermined positions on the lower surface of the key top 1. The reference numeral 2 denotes a housing, and a guide hole 21 is formed at a predetermined position on the housing 2 to guide the key stem 12. The reference numeral 3 denotes a rubber cup, with a protrusion 31 provided on a lower surface of the rubber cup 3. The reference numeral 4 denotes an FPC having at a predetermined position thereof a contact point 41. The reference numeral 5 denotes a frame.
In a key switch constructed as described above, when the key top 1 is depressed by an operator's finger, the key top 1 moves downward while being guided by the guide hole 21. At this time, the key stem 12 moves downward together with the key top 1, thus pressing down the rubber cup 3. Further, the protrusion 31 of the rubber cup 3 pushes down the contact point 41, so that a key is switched to an ON state.
However, the key switch is problematic in that impurities, such as dust, may enter the guide hole 21 for guiding the key stem 12, thus hindering smooth sliding motion of the key stem 12. Also, during operation of a computer, coffee, water or the like may flow into the guide hole 21, with the result that the smooth sliding motion of the key stem 12 may be hindered. Further, when coffee, water or the like flows to the contact point 41, failure of key-in operation occurs.
The key switch has a disadvantage in that noise is generated when the stoppers 11 come into contact with the housing 2 in the course of the downward movement of the key top 1.
In order to overcome the drawbacks, a key switch of FIG. 2 was proposed. The key switch is constructed so that a key stem 12 is surrounded with a hollow rubber cup 3, thus preventing impurities, such as dust, from entering the key switch.
However, the key switch includes a spring 13 made of metal. The spring 13 is mounted to a lower surface of the key stem 12 to press the contact point 41. The key stem 12 integrated with a key top 1 is usually made of resin. Thus, the key switch has a problem in that the spring 13 must be separately manufactured and then mounted to the key stem 12, so that the number of assembly processes is undesirably increased.
A multiple key, such as an enter key or a spacebar, is a key that is obtained by combining two or more key switches with each other. That is, one multiple key uses two or more key stems 12. Further, an operator may not press the exact center of the multiple key. For example, when an end of the multiple key is pushed down, the multiple key is tilted by a rotational moment. Thereby, a key stem 12 which is distant from the pushed end of the multiple key may not smoothly slide in the guide hole 21.
In order to solve the problem, there has been proposed a link bar which is mounted to a predetermined position of the multiple key so as to transmit pressure uniformly. However, this method has a problem in that the number of components is increased, so that additional assembly processes are required.
Further, since one multiple key uses two or more rubber cups, the rubber cups for the multiple key must be separately manufactured in order to make pressing sensation of the multiple key equal to that of a single key. That is, it is inconvenient to reduce the elasticity of two rubber cups used in the multiple key so that the total elasticity of the rubber cups for the multiple key is equal to the elasticity of one rubber cup used in a single key.


Disclosed are a display panel, a driving method and a display device. The display panel includes a strobe circuit, a pixel driving circuit and a light-emitting element; the pixel driving circuit includes a first initialization unit, a driving module, and a first light-emitting control unit; the strobe circuit is electrically connected to an initialization signal end; and the first initialization unit is electrically connected between the initialization signal end and an anode of the light-emitting element; in a write frame, the first initialization unit is configured to provide a first initialization voltage signal Vref1 to the anode of the light-emitting element under the control of a first scan signal; and in a hold frame, the first initialization unit is configured to provide a second initialization voltage signal Vref2 to the anode of the light-emitting element under the control of the first scan signal.

With the development of display technology, organic light-emitting display panels have become mainstream display panels by virtue of advantages of low power consumption, high response speed and the like thereof, and are widely used in an electronic equipment such as mobile phones, laptops, and computers.
How to reduce power consumption has always been a major research hotspot in the display field, and a wide variety of ways to reduce the power consumption have emerged. In some cases, one way to reduce a driving frequency has a significant effect on reducing the power consumption. Specifically, the display panel includes a normal driving mode and a low-frequency driving mode. When a dynamic picture is displayed, the normal driving mode may be adopted, in which the driving frequency is relatively high, such as 60 Hz, and each frame is a write frame in which a data voltage is written into a sub-pixel. When a static picture is displayed, the low-frequency driving mode may be adopted, in which the driving frequency is relatively low, such as 1 Hz, then 1 write frame and 59 hold frames are included within 1 second. The difference between the hold frames and the write frame is that the hold frames hold a data voltage written by the previous write frame without writing a new data voltage into the sub-pixel. In this way, the effect of reducing the power consumption may be achieved.
However, due to the difference between the hold frames and the write frame, there is a brightness difference between the write frame and the hold frame, which causes users to observe a flicker phenomenon.

Display panel, driving method and display device

XIAMEN TIANMA MICRO-ELECTRONICS CO., LTD.


Herein is disclosed a flame-retarded thermoplastic resin composition which comprises an original flame-retarded thermoplastic resin composition comprising certain amounts of a thermoplastic resin and of a brominated flame-retardant, and, in combination therewith, a certain amount of a dolomite compound, or in addition thereto, a certain amount of at least one compound selected from a hydrotalcite, a zinc-substituted hydrotalcite compound, or a zeolite compound, which flame-retarded thermoplastic resin composition of the present invention are remarkably improved in heat stabilizing effects as compared with the original flame-retarded thermoplastic resin composition.

1. Technical Field of the Invention
The present invention relates to a stabilized flame-retarded thermoplastic resin composition obtainable, e.g., by adding a specific additive to an original flame-retarded thermoplastic resin composition composed of a thermoplastic resin and a brominated flame-retardant, and it can be used widely in the fields where flame retardancy or flame retardativeness is required.
2. Prior Art
For flame retardation of a thermoplastic resin, it is the common practice to add thereto a flame retardant or a flame retarding assistant such as halogenated compound, phosphorous compound, antimony trioxide or the like. Among these flame retardants, a halogenated compound, particularly a brominated compound is used frequently.
In general, however, such addition of a brominated flame retardant to a thermoplastic resin is accompanied with the problem that a marked deterioration in heat stability of the resulting flame retarded thermoplastic resin occurs upon forming or molding, thereby lowering the commodity value of the molded or formed product. The below-described techniques have already been disclosed to overcome the above-described problems.
(1) A technique of adding a halogen-containing organic flame-retardant, a hydrotalcite stabilizer and a flame retarding assistant to a thermoplastic or thermosetting resin (Japanese Patent Application Laid-Open (Kokai) No. Sho 60-1241), thereby overcoming various problems such as corrosion generation upon molding or forming of the resulting flame-retarded resin composition, and yellowing, lowering in heat resistance, lowering in weather resistance and the like of the molded or formed product. The hydrotalcite stabilizer used according to this technique is the same as the hydrotalcite (Component (b)) to be used according to the present invention. This disclosure, however, includes neither any description of or even suggestion for the dolomite compound to be used according to the present invention nor any description of or even suggestion for the combined use of the hydrotalcite with the dolomite compound.
(2) A technique of adding a hydrotalcite solid solution to a halogen- and/or acid substance-containing synthetic resin (Japanese Patent Application Laid-Open (Kokai) No. Sho 61-174270), thereby improving rust generation resistance and coloring resistance of the resulting resin composition. The hydrotalcite solid solution used according to this technique is the same as the zinc-substituted hydrotalcite compound (Component (c)) to be used according to the present invention. This disclosure, however, includes neither any description of or even suggestion for the dolomite compound to be used according to the present invention nor any description of or even suggestion for the combined use of the hydrotalcite solid solution with the dolomite compound.
(3) A technique of adding zeolite A to a flame retarded resin composed of a polyolefin resin, styrene resin, polyester resin or nylon resin and a halogenated flame retardant (Japanese Patent Application Laid-Open (Kokai) No. Sho 62-199654), thereby improving heat stability of the resulting flame retarded thermoplastic resin. Zeolite A or zeolite containing a Group II or Group IV metal in the periodic table is the same as the zeolite compound (Component (d)) to be used according to the present invention. This disclosure, however, includes neither any description of or even suggestion for the dolomite compound to be used according to the present invention nor any description of or even suggestion for the combined use of the zeolite with the dolomite compound.
Problems to Be Solved by the Invention
It is impossible to obtain sufficient heat stabilizing effects when in accordance with the conventional technique of adding, to a flame-retarded thermoplastic resin composition composed of a thermoplastic resin and a brominated flame retardant, a hydrotalcite stabilizer as described in Japanese Patent Application Laid-Open (Kokai) No. Sho 60-1241, a hydrotalcite solid solution as described in Japanese Patent Application Laid-Open (Kokai) No. Sho 61-174270 or zeolite A as described in Japanese Patent Application Laid-Open (Kokai) No. Sho 62-199654, singly. There is accordingly a demand for the provision of a flame retarded thermoplastic resin composition excellent in heat stabilizing effects for a flame retarded thermoplastic resin composed of a thermoplastic resin and a brominated flame retardant.
Means to Solve the Problems
With the foregoing in view, the present inventors have proceeded with an extensive investigation on an additive having excellent heat stabilizing effects on a flame-retarded thermoplastic resin composed of a thermoplastic resin and a brominated flame retardant. As a result, it has been found that a flame retarded thermoplastic resin composition obtainable by adding, to an original or initial flame retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin and 1 to 50 parts by weight of a brominated flame retardant, 0.05 to 5.0 parts by weight of a dolomite compound (Component (a)) has excellent heat stabilizing effects. It has also been found that a flame retarded thermoplastic resin composition obtainable by adding to an original or initial flame-retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin and 1 to 50 parts by weight of a brominated flame retardant, 0.05 to 5.0 parts by weight of a dolomite compound (Component (a)), and in combination therewith, 0.01 to 5.0 parts by weight of at least one compound selected from the group consisting of a hydrotalcite (Component (b)), a zinc-substituted hydrotalcite compound (Component (c)) and a zeolite compound (Component (d)), has markedly excellent heat stabilizing effects, leading to completion of the present invention.
Specific examples of the thermoplastic resin to be used according to the present invention include polyolefins such as polyethylene, polypropylene and the like, styrene resins such as polystyrene (PS), high impact polystyrene (HIPS), syndiotactic polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-butadiene-styrene-(xcex1-methyl)styrene copolymer, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-ethylene-styrene copolymer (AES resin), acrylonitrile-acrylic rubber-styrene copolymer (AAS resin) and the like, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyarylate and the like, polyamides such as nylon 6, nylon 12, nylon 46, nylon 66, nylon 610, nylon 612, nylon MXD6 and the like, polycarbonate, polyacetal, vinyl acetate resin, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl acetal, polyphenylene oxide, polysulfone, polyether sulfone and polyphenylene sulfide and blended resins thereof (polymer alloys).
As the brominated flame retardant to be used according to the present invention, those ordinarily employed in this field can be used with no limitations. Among them, popularly employed are flame retardants such as brominated bisphenol A or brominated bisphenol S, brominated phenyl ether, brominated bisphenol A carbonate oligomer, brominated bisphenol A epoxy resin, brominated styrene, brominated phthalimide, brominated benzene and brominated cycloalkane.
As the brominated bisphenol A or brominated bisphenol S, compounds having 1 to 8 bromine atoms bonded to the benzene ring of the bisphenol A residue or bisphenol S residue can be mentioned. Examples thereof include monobromobisphenol A, dibromobisphenol A, tribromobisphenol A, tetrabromobisphenol A, pentabromobisphenol A, hexabromobisphenol A, octabromobisphenol A, tetrabromobisphenol A bis(2-hydroxyethyl ether), tetrabromobisphenol A bis(2-bromoethyl ether), tetrabromobisphenol A bis(1,2-dibromoethyl ether), tetrabromobisphenol A bis(propyl ether), tetrabromobisphenol A bis(3-bromopropyl ether), tetrabromobisphenol A bis(2,3-dibromopropyl ether), monobromobisphenol S, dibromobisphenol S, tribromobisphenol S, tetrabromobisphenol S, pentabromobisphenol S, hexabromobisphenol S, octabromobisphenol S, tetrabromobisphenol S bis(2-hydroxyethyl ether), tetrabromobisphenol S bis(2-bromoethyl ether), tetrabromobisphenol S bis(1,2-dibromoethyl ether), tetrabromobisphenol S bis(propyl ether), tetrabromobisphenol S bis(3-bromopropyl ether), tetrabromobisphenol S bis(2,3-dibromopropyl ether) and the like.
As commercially available brominated bisphenol A or brominated bisphenol S can be mentioned, for example, xe2x80x9cFR-1524xe2x80x9d, ex Bromokem (Far East) Ltd., xe2x80x9cGreat Lakes BA-50xe2x80x9d, xe2x80x9cGreat Lakes BA-50Pxe2x80x9d, xe2x80x9cGreat Lakes BA-59xe2x80x9d, xe2x80x9cGreat Lakes BA-59Pxe2x80x9d and xe2x80x9cGreat Lakes PE-68xe2x80x9d, ex Great Lakes Chemical Corporation, xe2x80x9cSaytex RB-100xe2x80x9d ex Albemarle Corporation, xe2x80x9cFire Guard 2000xe2x80x9d, xe2x80x9cFire Guard 3000xe2x80x9d, xe2x80x9cFire Guard 3100xe2x80x9d and xe2x80x9cFire Guard 3600xe2x80x9d ex Teijin Chemicals Ltd., xe2x80x9cNonnen PR-2xe2x80x9d ex Marubishi Oil Chemical Co., Ltd., and the like.
The brominated phenyl ether are those compounds having at least one bromine atom bonded to the phenyl ether group, and examples thereof include 2,3-dibromopropylpentabromophenyl ether, bis (tribromophenoxy) ethane, pentabromophenylpropyl ether, hexabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether and polydibromophenylene oxide.
As commercially available brominated phenyl ether flame retardants can be mentioned, for example, xe2x80x9cFR-1210xe2x80x9d and xe2x80x9cFR-1208xe2x80x9d ex Bromokem (Far East) Ltd., xe2x80x9cGreat Lakes FF-680xe2x80x9d, xe2x80x9cGreat Lakes DE-83xe2x80x9d, xe2x80x9cGreat Lakes DE-83Rxe2x80x9d and xe2x80x9cGreat Lakes DE-79xe2x80x9d, ex Great Lakes Chemical Corporation, and xe2x80x9cSaytex RB-102Exe2x80x9d and xe2x80x9cSaytex 111xe2x80x9d ex Albemarle Corporation.
The brominated bisphenol A carbonate oligomer is a polymer of the group represented by the following formula:
and the term xe2x80x9coligomerxe2x80x9d as used herein means that having a polymerization degree (n) of 1 to 10. A flame retardant represented by the following formula:
can be mentioned by way of example. Examples of the commercially available flame retardant of the above-described formula can include xe2x80x9cFire Guard 7000xe2x80x9d and xe2x80x9cFire Guard 7500xe2x80x9d ex Teijin Chemicals Ltd.
Examples of the commercially available flame retardant represented by the above-described formula can include xe2x80x9cGreat Lakes BC-52xe2x80x9d and xe2x80x9cGreat Lakes BC-58xe2x80x9d ex Great Lakes Chemical Corporation, and the like.
As examples of the brominated bisphenol A epoxy resin can be mentioned those compounds represented by the following formula:
As the commercially available flame retardant represented by the above-described formula, there are various products depending on the polymerization degree (n). Examples thereof can include xe2x80x9cF-2300xe2x80x9d, xe2x80x9cF-2300Hxe2x80x9d, xe2x80x9cF-2400xe2x80x9d and xe2x80x9cF-2400Hxe2x80x9d ex Bromokem (Far East) Ltd., xe2x80x9cPRATHERM EP-16xe2x80x9d, xe2x80x9cPRATHERM EP-30xe2x80x9d, xe2x80x9cPRATHERM EP-100xe2x80x9d and xe2x80x9cPRATHERM EP-500xe2x80x9d ex Dainippon Ink and Chemicals, Incorporated, and xe2x80x9cSR-T1000xe2x80x9d, xe2x80x9cSR-T2000xe2x80x9d, xe2x80x9cSR-T5000xe2x80x9d and xe2x80x9cSR-T20000xe2x80x9d ex Sakamoto Yakuhin Kogyo Co., Ltd., and the like.
As the brominated bisphenol A epoxy resin can be mentioned those compounds of the above-described formula wherein the epoxy group at each of both ends has been blocked with a blocking agent, and those compounds of the above-described formula wherein the epoxy group at one end has been blocked with a blocking agent. Although no particular limitations are imposed on the blocking agent insofar as it is a compound permitting the ring-opening addition of the epoxy group, examples thereof can include phenols, alcohols, carboxylic acids, amines, isocyanates and the like, each containing a bromine atom. Among them, brominated phenols are preferred for improving flame retarding effects. Examples thereof can include dibromophenol, tribromophenol, pentabromophenol, dibromoethylphenol, dibromopropylphenol, dibromobutylphenol, dibromocresol and the like.
Examples of the above-described polymer having epoxy groups, at both ends thereof, blocked with a blocking agent, as flame retardants, can include flame retardants represented by the following formulas:
Examples of the commercially available flame retardant of the above-described formula can include xe2x80x9cPRATHERM EC-14xe2x80x9d, xe2x80x9cPRATHERM EC-20xe2x80x9d and xe2x80x9cPRATHERM EC-30xe2x80x9d ex Dainippon Ink and Chemicals, Incorporated, xe2x80x9cTB-60xe2x80x9d and xe2x80x9cTB-62xe2x80x9d ex Tohto Chemical Co., Ltd., xe2x80x9cSR-T3040xe2x80x9d and xe2x80x9cSR-T7040xe2x80x9d ex Sakamoto Yakuhin Kogyo Co., Ltd., and the like.
Examples of the polymer having an epoxy group, at one end thereof, blocked with a blocking agent, as flame retardants, can include flame retardants represented by the following formulas:
Examples of the commercially available flame retardant of the above-described formula can include xe2x80x9cPRATHERM EPC-15Fxe2x80x9d ex Dainippon Ink and Chemicals, Incorporated, xe2x80x9cE5354xe2x80x9d ex Yuka Shell Epoxy Kabushiki Kaisha, and the like.
The brominated styrene flame retardant is a brominated styrene monomer of the following formula:
with 1 to 5 bromine atoms being bonded to the benzene ring of the styrene skeleton, and its polymer of the following formula:
with the polymer being preferred. Bromostyrene and brominated polystyrene can be mentioned by way of example. As commercially available brominated polystyrene flame retardants can be mentioned, for example, xe2x80x9cGreat Lakes PDBS-10xe2x80x9d and xe2x80x9cGreat Lakes PDBS-80xe2x80x9d ex Great Lakes Chemical Corporation, and the like. xe2x80x9cPyrochek 68PBxe2x80x9d ex Ferro Inc. can also be mentioned as a brominated polystyrene flame retardant, though it differs from the above-described ones in preparation process.
The brominated phthalimide flame retardant is a compound having 1 to 8 bromine atoms bonded to the benzene ring of 1 or 2 of the phthalimide groups. Examples thereof can include monobromophthalimide, dibromophthalimide, tribromophthalimide, tetrabromophthalimide, ethylenebis(monobromophthalimide), ethylenebis(dibromophthalimide), ethylenebis(tribromophthalimide) and ethylene bis(tetrabromophthalimide) represented by the following formula:
Examples of the commercially available flame retardant can include xe2x80x9cSaytex BT-93xe2x80x9d and xe2x80x9cSaytex BT-93Wxe2x80x9d ex Albemarle Corporation.
The brominated benzene is a compound having at least one bromine atom bonded to the benzene ring. Examples thereof can include monobromobenzene, dibromobenzene, tribromobenzene, tetrabromobenzene, pentabromobenzene, hexabromobenzene, bromophenylallyl ether, pentabromotoluene, bis(pentabromophenyl)ethane, poly(pentabromobenzyl acrylate), and the like. As a commercially available flame retardant, xe2x80x9cSaytex 8010xe2x80x9d ex Albemarle Corporation can be mentioned as an example.
The brominated cycloalkane is a brominated hydrocarbon having 1 to 6 bromine atoms bonded to a C6-12 cycloalkane (cyclic aliphatic hydrocarbon). Examples of the cycloalkane can include cyclohexane and cyclododecane, while those of the brominated cycloalkane can include monobromocyclohexane, dibromocyclohexane, tribromocyclohexane, tetrabromocyclohexane, pentabromocyclohexane, hexabromocyclohexane, monobromocyclododecane, dibromocyclododecane, tribromocyclododecane, tetrabromocyclododecane, pentabromocyclododecane, hexabromocyclododecane, and the like.
As commercially available hexabromocyclododecanes can be mentioned, for example, xe2x80x9cFR-1206xe2x80x9d ex Bromokem (Far East) Ltd., xe2x80x9cSaytex HBCDxe2x80x9d ex Albemarle Corporation, xe2x80x9cGreak Lakes CD-75Pxe2x80x9d ex Great Lakes Chemical Corporation, xe2x80x9cPyroguard SR-103xe2x80x9d ex Dai-ichi Kogyo Seiyaku Co., Ltd., and the like.
In Examples which will be described later, popularly-used, typical brominated flame retardants are employed among them, but the other brominated flame retardants referred to above are expected to exhibit similar effects.
Other than the popularly-used brominated flame retardants as exemplified above, those which are shown in the literature or catalogues of brominated flame retardant makers can also be employed. Flame retarded thermoplastic resin compositions containing such brominated flame retardant are expected to actualize the advantages of the present invention equally. Examples of such brominated flame retardant can include brominated phenols, brominated phenoxytriazines, brominated alkanes, brominated isocyanurates, brominated maleimides, brominated phthalic acids, and the like.
Brominated phenols are compounds having 1 to 5 bromine. atoms bonded to the phenol group, and examples thereof can include monobromophenol, dibromophenol, tribromophenol, tetrabromophenol, pentabromophenol, and the like.
Brominated phenoxytriazines are compounds wherein 1 to 5 bromine atoms have been bonded to each of the phenoxy groups to form a brominated phenoxy froup and 1 to 3 brominated phenoxy groups have been bonded to a triazine ring. Examples thereof can include mono(monobromophenoxy)triazine, mono(dibromophenoxy)triazine, mono(tribromophenoxy)triazine, mono(pentabromophenoxy)triazine, bis(monobromophenoxy)triazine, bis(dibromophenoxy)triazine, bis(tribromophenoxy)triazine, bis(pentabromophenoxy)triazine, tris(monobromophenoxy)triazine, tris(dibromophenoxy)triazine, tris(pentabromophenoxy)triazine and tris(tribromophenoxy)triazine represented by the following formula:
As a commercially available flame retardant represented by the above-described formula, xe2x80x9cPyroguard SR-245xe2x80x9d ex Dai-ichi Kogyo Seiyaku Co., Ltd. can be mentioned.
Brominated alkanes are compounds having 1 to 8 bromine atoms bonded to a C2-6 alkane (chain aliphatic hydrocarbon). Examples of the alkane can include ethane, propane, butane, pentane and hexane, while those of the brominated alkane can include monobromoethane, dibromoethane, tetrabromoethane, monobromopropane, dibromopropane, tribromopropane, pentabromopropane, hexabromopropane, octabromopropane, monobromobutane, dibromobutane, tetrabromobutane, hexabromobutane, octabromobutane, monobromopentane, dibromopentane, tribromopentane, pentabromopentane, octabromopentane, monobromohexane, dibromohexane, tribromohexane, tetrabromohexane, pentabromohexane, hexabromohexane, octabromohexane, and the like.
Examples of the brominated isocyanurate can include compounds wherein the alkyl residue of the above-described brominated alkane and an isocyanuric acid residue are bonded to each other, and compounds wherein a brominated phenoxy group having 1 to 5 bromine atoms bonded to a phenoxy group and an isocyanuric acid residue are bonded to each other. Specific examples thereof can include tris(monobromoethyl)isocyanurate, tris(dibromoethyl)isocyanurate, tris(tetrabromoethyl)isocyanurate, tris(monobromopropyl)isocyanurate, tris(2,3-dibromopropyl)isocyanurate, tris(tribromopropyl)isocyanurate, tris(tetrabromopropyl)isocyanurate, tris(pentabromopropyl)isocyanurate, tris(heptabromopropyl)isocyanurate, tris(monobromobutyl)isocyanurate, tris(dibromobutyl)isocyanurate, tris(pentabromobutyl)isocyanurate, tris(octabromobutyl)isocyanurate, tris(monobromopentyl)isocyanurate, tris(dibromopentyl)isocyanurate, tris(pentabromopentyl)isocyanurate, tris(octabromopentyl)isocyanurate, tris(monobromohexyl)isocyanurate, tris(dibromohexyl)isocyanurate, tris(tribromohexyl)isocyanurate, tris(pentabromohexyl)isocyanurate, tris(monobromophenoxy)isocyanurate, tris(dibromophenoxy)isocyanurate, tris(tribromophenoxy)isocyanurate, tris(pentabromophenoxy)isocyanurate, tris(monobromoethylphenoxy)isocyanurate, tris(dibromoethylphenoxy)isocyanurate, tris(tetrabromoethylphenoxy)isocyanurate, tris(monobromopropylphenoxy)isocyanurate, tris(dibromopropylphenoxy)isocyanurate, tris(tetrabromopropylphenoxy)isocyanurate, and the like.
Brominated maleimides are compounds having 1 to 5 bromine atoms bonded to the phenylmaleimide group. Examples thereof can include monobromophenylmaleimide, dibromophenylmaleimide, tribromophenylmaleimide, pentabromophenyl maleimide, and the like.
Brominated phthalic acids are compounds having 1 to 4 bromine atoms bonded to phthalic anhydride. Examples thereof can include monobromophthalic anhydride, dibromophthalic anhydride, tribromophthalic anhydride, tetrabromophthalic anhydride, and the like.
The amount of the brominated flame retardant to be used according to the present invention varies depending on the relationship between the extent of the flame retardation required of a thermoplastic resin and physical properties. However, the flame retardant is usually used in an amount of 1 to 50 parts by weight based on 100 parts by weight of a thermoplastic resin. In an amount less than 1 part by weight, desired flame retardancy cannot be imparted. Amounts exceeding 50 parts by weight bring about sufficient flame retardancy but may impair the physical properties of the molded or formed product of the resulting resin composition. Amounts outside the above-described range are therefore not preferred. From the viewpoint of keeping good balance between the flame retardancy and physical properties, the amount practically falls within a range of 3 to 30 parts. Depending on the using purpose, two or more brominated flame retardants can be used in combination.
A flame retarding assistant such as antimony oxide is often used in combination with a flame retardant in order to heighten the flame retarding effects further. Addition of such flame retarding assistant does not adversely affect the advantages of the present invention. The flame retarding assistant is usually added in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of a thermoplastic resin, with 1 to 7 parts by weight being preferred judging from the relationship with physical properties and the like.
No particular limitations are imposed on the dolomite compound to be used according to the present invention, said compound being sometimes referred to as Component (a). Any dolomite that is widely produced in nature and used as a wall material or refractory for iron manufacture can be employed. In addition, synthetic dolomite having a chemical composition formed of a complex salt of calcium carbonate and magnesium carbonate can also be employed.
Natural dolomite and/or synthetic dolomite to be used according to the present invention may have a composition wherein magnesium and calcium are mixed at a certain ratio, of which a weight ratio of the magnesium to the calcium falling within a range of 5:95 to 95:5 in terms of MgO:CaO is preferred. When natural dolomite and/or synthetic dolomite having a weight ratio outside the above range is employed, sufficient heat stabilizing effects are not available.
According to the present invention, it is also possible to use a derivative obtained by sintering or lime slaking such natural dolomite and/or synthetic dolomite, thereby modifying it without largely changing its metal element composition. Specific examples can include dolomite cement obtainable by heating dolomite at 700 to 800xc2x0 C., light burned dolomite obtainable by heating at 900 to 1000xc2x0 C., dead burned dolomite obtainable by dead burning at as high as 1600 to 1800xc2x0 C., magnesia slaked lime obtainable by slaking light burned dolomite by adding water, synthetic magnesia-dolomite clinker, and the like. In addition, usable are derivatives obtainable by modifying a natural mineral or synthetic complex, such as akermanite (Ca2MgSi2O7), diopside [CaMg(SiO3)2] or various kinds of slag, which contains calcium and magnesium at a ratio falling within the same range as that of the above-described synthetic dolomite. Any mixture of them may also be employed.
The above-exemplified dolomites and derivatives thereof will hereinafter be collectively called xe2x80x9cdolomite compoundsxe2x80x9d in this specification. These dolomite compounds are produced industrially in a wide field and in a large amount. Since they are used in various industries such as steel manufacture, pottery, building material manufacture, agriculture, and the like, they have a stable quality and available easily at a low cost. A flame retarded, thermoplastic resin composition obtainable by using light burned dolomite, among the above-exemplified flame retardants, exhibits-the best heat stabilizing effects.
According to the present invention, the dolomite compound surface-treated with a surface treating agent can be used for improving the dispersibility, compatibility or the like between the, dolomite compound and the flame retarded thermoplastic resin. Organic acids and metal salts of organic acids can be used as the surface treating agent for the dolomite compound. These compounds may be used either singly or in combination.
Examples of the organic acid to be used as the surface treating agent can include saturated aliphatic monocarboxylic acids, saturated aliphatic dicarboxylic acids, unsaturated aliphatic carboxylic acids, carbocyclic carboxylic acids, heterocyclic carboxylic acids, hydroxy acids, amino acids, amino acid derivatives, and the like.
Specific examples of the saturated aliphatic monocarboxylic acid can include acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, octanoic acid, lauric acid, stearic acid, behenic acid, and the like.
Specific examples of the saturated aliphatic dicarboxylic acid can include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, and the like.
Specific examples of the unsaturated aliphatic carboxylic acid can include acrylic acid, oleic acid, crotonic acid, fumaric acid, and the like.
Specific examples of the carbocyclic carboxylic acid can include benzoic acid, camphoric acid, phthalic acid, toluic acid, hydroatropic acid, cinnamic acid, and the like.
Specific examples of the heterocyclic carboxylic acid can include furoic acid, thenoic acid, pyrrolidonecarboxylic acid, nicotinic acid, and the like.
Specific examples of the hydroxy acid can include lactic acid, malic acid, benzilic acid, salicylic acid, anisic acid, vanillic acid, protocatechuic acid, gallic acid, and the like.
Specific examples of the amino acid and amino acid derivative can include alkoxylic acid, glutamic acid, lysine, aspartic acid, glycine, N-stearoylglycine, N-acetylglutamic acid, N-lauroylleucine, xcex3-methylglutamic acid, and the like.
As the metal salt of an organic acid to be used as the surface treating agent, the metal salts of the above-exemplified organic acids can be mentioned. Specific examples of the metal of the metal salts can include zinc, calcium, magnesium, potassium, sodium, lithium, aluminum, nickel, and the like. A mixture or complex salt of at least two of these metal salts may be used.
Other surface treating agents than the above-exemplified ones and used industrially can be used as needed, in combination with the above-exemplified oness within an extent not impairing the advantages of the present invention. Specific examples can include higher fatty acid esters, coupling agents such as silane-, aluminum- and phosphorous-based ones, surfactants such as anionic, cationic and nonionic ones, higher fatty acid esters, polymer-based dispersants, and the like.
Although the amount of the surface treating agent to be used varies with the kind of the dolomite compound to be employed, specific surface area of its powder particles and moisture content bonded to the surface thereof, the surface treating agent is added or used in an amount of 0.05 to 40 wt. %, preferably 0.1 to 2.0 wt. % based on the dolomite compound to be treated therewith. Amounts of the surface treating agent less than 0.05 wt. % hardly bring about the effects of surface treatment. Amounts exceeding 40 wt. %, on the other hand, do not bring about surface treating effects in proportion to the amount, because the surface of the particles of the dolomite compound powders gets saturated with the treating agent.
No particular limitations are imposed on the surface treating procedures. Examples can include (1) a method of adding a surface treating agent to dolomite compound powders followed by co-grinding the resulting mixture in a grinder such as Henschel mixer, colloid mill, ball mill, atomizer, or the like, and (2) a method of adding a surface treating agent and the dolomite compound in a proper solvent such as toluene, xylene, methyl ethyl ketone, acetonitrile, chloroform, dimethyl ether, water, ethanol, methanol, or the like, followed by stirring the mixture and then removing the solvent therefrom.
The hydrotalcite to be used according to the present invention is a compound composed of magnesium and aluminum, said hydrotalcite being sometimes referred to as Component (b), and examples thereof can include compounds represented by the following general formula (1):
Mg1xe2x88x92xAlx(OH)2(Aqxe2x88x92)x/q.aH2Oxe2x80x83xe2x80x83(1)
The zinc-substituted hydrotalcite compound is a compound of the formula (1) wherein Mg has been partially substituted with Zn, said zinc-substituted hydrotalcite compound being sometimes referred to as Component (c). Examples thereof can include the compounds of the following general formula (2):
xe2x80x83Mgy1Zny2Alx(OH)2(Aqxe2x88x92)x/q.aH2Oxe2x80x83xe2x80x83(2)
A substitution ratio of Zn for Mg is 1 mole % to 50 mole %, preferably 15 mole % to 30 mole %. [In the formulas (1) and (2), q stands for 1 or 2, Aqxe2x88x92 is an anion having a valence of q, that is, (CO3)2xe2x88x92 or (ClO4)xe2x88x92 and x, y1, y2 and a each stands for a real number satisfying the following conditions:
0 less than xxe2x89xa60.5, y1+y2=1xe2x88x92x, y1xe2x89xa7y2, 0xe2x89xa6a less than 1]
Typical examples of the hydrotalcite of the formula (1) can include:
No. 1: Mg0.750Al0.250(OH)2(CO3)0.125.0.5H2O,
No. 2: Mg0.692Al0.308(OH)2(CO3)0.154.0.1H2O,
No. 3: Mg0.683Al0.317(OH)2(CO3)0.159.0.5H2O,
No. 4: Mg0.667Al0.333(OH)2(CO3)0.167.0.1H2O,
No. 5: Mg0.750Al0.250(OH)2(ClO4)0.250.0.5H2O,
No. 6: Mg0.692Al0.308(OH)2(ClO4)0.308.0.1H2O, and
No. 7: Mg0.667Al0.333(OH)2(ClO4)0.333.0.1H2O.
Typical examples of the zinc-substituted hydrotalcite compounds represented by the formula (2) can include:
No. 8: Mg0.625Zn0.125Al0.125(OH)2(CO3)0.125.0.45H2O,
No. 9: Mg0.538Zn0.154Al0.308(OH)2(CO3)0.154
No. 10: Mg0.500Zn0.167Al0.333(OH)2(CO3)0.167.0.54H2O,
No. 11: Mg0.625Zn0.125Al0.250(OH)2(ClO4)0.250.0.3H2O,
No. 12: Mg0.538Zn0.154Al0.308(OH)2(ClO4)0.308.0.5H2O, and
No. 13: Mg0.500Zn0.167Al0.333(OH)2(ClO4)0.333.0.1H2O.
According to the present invention, also usable is the hydrotalcite or zinc-substituted hydrotalcite compound subjected to surface treatment with a surface treating agent, for example, a higher fatty acid, to improve the dispersibility or compatibility of the hydrotalcite or zinc-substituted hydrotalcite compound with the flame-retarded thermoplastic resin. Specific examples of the commercially-available, surface-treated hydrotalcite can include xe2x80x9cAlcamizer 2xe2x80x9d, xe2x80x9cAlcamizer 3xe2x80x9d, xe2x80x9cDHT-4Axe2x80x9d, xe2x80x9cDHT-4A-2xe2x80x9d, and the like, ex Kyowa Chemical Industry Co., Ltd. Those of the commercially-available, surface-treated zinc-substituted hydrotalcite compound can include xe2x80x9cAlcamizer 4xe2x80x9d, xe2x80x9cAlcamizer 4-2xe2x80x9d, xe2x80x9cAlcamizer 7xe2x80x9d, and the like, ex Kyowa Chemical Industry Co., Ltd.
As the surface treating agent, those described in the known literature, for example, those described on page 4 of Japanese Patent Application Laid-Open (Kokai) No. Sho 60-1241 can be used, other than the above-described higher fatty acids.
Surface treating agents as described in this known literature are those ordinarily employed in this field, for example, anionic surfactants, silane coupling agents, titanium coupling agents, higher fatty acid esters, and the like. Specific examples thereof include anionic surfactants such as sodium stearate, sodium oleate, sodium laurylbenzenesulfonate, and the like, silane- or titanium-based coupling agents such as vinyl triethoxysilane, xcex3-aminopropyltrimethoxysilane, isopropyltriisostearoyl titanate, isopropyltridecylbenzenesulfonyl titanate and the like, and higher fatty acid esters such as glycerin monostearate, glycerin monoleate and the like.
As the zeolite compound to be used according to the present invention, said zeolite compound being sometimes referred to as Component (d), usable are zeolite 4A compounds represented by the following general formula (3):
Na12Al12Si12O48.bH2Oxe2x80x83xe2x80x83(3)
[in the formula (10), b stands for a real number satisfying 0xe2x89xa6bxe2x89xa636], zeolite 3A compounds obtainable by substituting potassium for the sodium of the zeolite 4A compounds, zeolite 5A compounds obtainable by substituting calcium for the sodium of the zeolite 4A compounds, zeolite 13X compounds having a composition of Na86Al86Si106O384.264H2O, zeolite 10X compounds obtainable by substituting calcium for the sodium of the 13X type zeolite compounds and zeolite compounds obtainable by partially substituting, for the sodium of the zeolite 4A compound, metal(s) of the Group II or Group IV in the periodic table such as magnesium, zinc, strontium, barium, zirconium, tin or the like (said zeolite compounds being hereinafter called metal-substituted zeolite compounds).
With regards to the metal-substituted zeolite compounds, no particular limitations are imposed on the metal of the Group II or Group IV in the periodic table which is partially substituted for the sodium of the zeolite 4A compound. As the metal to be used for substitution in consideration of effects, toxicity, availability and the like, magnesium, zinc, strontium, barium, zirconium, tin and the like can be mentioned. Specific examples of the metal-substituted zeolite can include synthetic zeolites such as magnesium-substituted zeolite, zinc-substituted zeolite, strontium-substituted zeolite, barium-substituted zeolite, zirconium-substituted zeolite, tin-substituted zeolite, and the like. Among them, magnesium-, zinc- or barium-substituted zeolite compounds are preferred.
Incidentally, the zeolite 3A compounds, zeolite 5A compounds, zeolite 10X compounds and metal-substituted zeolite compounds usually obtainable industrially are zeolite 4A compounds or zeolite 13X compounds whose sodium has been substituted with a metal at a substitution ratio of 10 mole % to 70 mole %.
Among the zeolite compounds to be used according to the present invention, said zeolite compound being sametimes referred to as Component (d), zeolite 4A compounds and zeolite 5A compounds are most preferred.
Specific examples of the zeolite 4A compound can include Na12Al12Si12O48, Na12Al12Si12O48.6H2O, Na12Al12Si12O48.12H2O, Na12Al12Si12O48.21H2O, Na12Al12Si12O48.27H2O, and Na12Al12Si12O48.36H2O.
Specific examples of the commercially available zeolite 4A compound can include xe2x80x9cZeostar NA-100Pxe2x80x9d and xe2x80x9cZeostar NA-100Pxe2x80x9d ex Nippon Chemical Industrial Co., Ltd., xe2x80x9cToyobuilderxe2x80x9d ex TOSOH CORPORATION, and the like.
Specific examples of the commercially available zeolite 3A compound can include xe2x80x9cZeostar KA-100Pxe2x80x9d and xe2x80x9cZeostar KA-110Pxe2x80x9d ex Nippon Chemical Industrial Co., Ltd.; those of the commercially available zeolite 5A can include xe2x80x9cZeostar CA-100Pxe2x80x9d and xe2x80x9cZeostar CA-110Pxe2x80x9d ex Nippon Chemical Industrial Co., Ltd.; those of the commercially available zeolite 13X compound can include xe2x80x9cZeostar NX-100Pxe2x80x9d and xe2x80x9cZeostar NX-110Pxe2x80x9d ex Nippon Chemical Industrial Co., Ltd.; and those of the commercially available zeolite 10X compound can include xe2x80x9cZeostar CX-100Pxe2x80x9d and xe2x80x9cZeostar CX-110Pxe2x80x9d ex Nippon Chemical Industrial Co., Ltd.
The zeolite compounds to be used according to the present invention may each be surface treated with an alkali metal salt of a higher fatty acid, for example, an alkali metal salt of stearic acid, oleic acid, or the like; or the alkali metal salt of an organic sulfonic acid such as dodecylbenzenesulfonic acid or the like.
The above-described synthetic zeolite may be prepared by the known process, for example, the preparation process as described in Japanese Patent Application Laid-Open (Kokai) No. Sho 57-28145.
The dolomite compound to be used according to the present invention (Component (a)) is added in an amount of 0.01 to 5.0 parts by weight, preferably 0.05 to 3.0 parts by weight, based on 100 parts by weight of the thermoplastic resin.
Amounts of the dolomite compound (Component (a)) less than 0.01 part by weight do not bring about sufficient heat stabilizing effects, whereas amounts exceeding 5.0 parts by weight, on the other hand, do not bring about heat stabilizing effects expected from an amount increase.
The at least one compound to be selected for use according to the present invention from the hydrotalcite (Component (b)), the zinc-substituted hydrotalcite compounds (Component (c)) and the zeolite compound (Component (d)) is used or added in an amount of 0.01 to 5.0 parts by weight, preferably 0.05 to 3.0 parts by weight based on 100 parts by weight of the thermoplastic resin.
Incidentally, when the amount of the at least one compound selected from Component (b), Component (c) and Component (d) is less than 0.01 part by weight, marked heat stabilizing effects are not provided, whereas when it exceeds 5.0 parts by weight, on the other hand, heat stabilizing effects expected from an increase in the amount are not provided.
No particular limitations are imposed on the ratio of Component (a) and at least one compound selected from the group consisting of Component (b), Component (c) and Component (d) when used in combination. They may be used at any ratio.
When at least two compounds selected from Component (b), Component (c) and Component (d) are used in combination, no particular limitations are imposed on the ratio. They may be used at any ratio.
The heat stabilizing effects of the present invention are not adversely affected even by the addition of a filler such as glass fiber, carbon fiber, an inorganic substance or the like to the flame-retarded thermoplastic resin composition of the present invention.
If necessary, an antioxidant, ultraviolet absorber, lubricant, pigment and/or the like can be added.
The flame retarded thermoplastic resin composition of the present invention is obtainable by kneading the necessary components in a calendar roll, extruder, Banbury mixer, kneader or the like. Upon kneading, all the components may be kneaded simultaneously or kneaded after separately added.
The following flame-retarded thermoplastic resin compositions can be mentioned as examples, which can be made according to the present invention.
(1) A flame-retarded thermoplastic resin composition obtainable by adding, to an original or initial flame retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): a dolomite compound.
(2) A flame-retarded thermoplastic resin composition obtainable by adding to an original flame-retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt.
(3) A flame-retarded thermoplastic resin composition obtainable by adding, to an original flame-retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 50 parts by weight of-Component (a): natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO.
(4) A flame-retarded thermoplastic resin composition obtainable by adding, to an original flame-retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): light burned dolomite obtainable by light burning natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO.
(5) A flame-retarded thermoplastic resin composition obtainable by adding, to an original flame-retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin and 3 to 30 parts by weight of a brominated flame retardant,
0.05 to 3.0 parts by weight of Component (a): light burned dolomite obtainable by light burning natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO.
(6) A flame-retarded thermoplastic resin composition obtainable by adding, to an original flame retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin selected from the group consisting of polyolefins, styrene resins, polyesters and polyamides and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): a dolomite compound.
(7) A flame-retarded thermoplastic resin composition obtainable by adding, to an original flame retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin selected from the group consisting of polyolefins, styrene resins, polyesters and polyamides and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt.
(8) A flame-retarded thermoplastic resin composition obtainable by adding, to an original flame retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin selected from the group consisting of polyolefins, styrene resins, polyesters and polyamides and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO.
(9) A flame-retarded thermoplastic resin composition obtainable by adding, to an original flame retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin selected from the group consisting of polyolefins, styrene resins, polyesters and polyamides and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): light burned dolomite obtainable by light burning natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO.
(10) A flame-retarded thermoplastic resin composition obtainable by adding, to an original flame retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin selected from the group consisting of polyolefins, styrene resins, polyesters and polyamides and 3 to 30 parts by weight of a brominated flame retardant,
0.05 to 3.0 parts by weight of Component (a): light burned dolomite obtainable by light burning natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO.
(11) A flame-retarded styrene resin composition obtainable by adding, to an original flame-retarded styrene resin composition composed of 100 parts by weight of a styrene resin and 1 to 50 parts by weight of a brominated flame retardant;
0.01 to 5.0 parts by weight of Component (a): a dolomite compound.
(12) A flame-retarded styrene resin composition obtainable by adding, to an original flame-retarded styrene resin composition composed of 100 parts by weight of a styrene resin and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt.
(13) A flame-retarded styrene resin composition obtainable by adding, to an original flame-retarded styrene resin composition composed of 100 parts by weight of a styrene resin and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO.
(14) A flame-retarded styrene resin composition obtainable by adding, to an original flame-retarded styrene resin composition composed of 100 parts by weight of a styrene resin and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): light burned dolomite obtainable by light burning natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO.
(15) A flame-retarded styrene resin composition obtainable by adding, to an original flame-retarded styrene resin composition composed of 100 parts by weight of a styrene resin and 3 to 30 parts by weight of a brominated flame retardant,
0.05 to 3.0 parts by weight of Component (a): light burned dolomite obtainable by light burning natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO.
(16) A flame-retarded thermoplastic resin composition obtainable by adding, to an original flame-retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): a dolomite compound; and, in combination therewith,
0.01 to 5.0 parts by weight of at least one compound selected from the group consisting of:
Component (b): a hydrotalcite,
Component (c): a zinc-substituted hydrotalcite compound, and
Component (d): a zeolite compound.
(17) A flame-retarded thermoplastic resin composition obtainable by adding, to an original flame-retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt; and, in combination therewith,
0.01 to 5.0 parts by weight of at least one compound selected from the group consisting of:
Component (b): a hydrotalcite,
Component (c): a zinc-substituted hydrotalcite compound, and
Component (d): a zeolite compound.
(18) A flame-retarded thermoplastic resin composition obtainable by adding, to an original flame-retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO; and, in combination therewith,
0.01 to 5.0 parts by weight of at least one compound selected from the group consisting of:
Component (b): a hydrotalcite,
Component (c): a zinc-substituted hydrotalcite compound, and
Component (d): a zeolite compound.
(19) A flame-retarded thermoplastic resin composition obtained by adding, to an original flame-retarded thermoplastic resin composition composed of 100 parts by, weight of a thermoplastic resin and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): light burned dolomite obtainable by light burning natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO; and, in combination therewith,
0.01 to 5.0 parts by weight of at least one compound selected from the group consisting of:
Component (b): a hydrotalcite,
Component (c): a zinc-substituted hydrotalcite compound, and
Component (d): a zeolite compound.
(20) A flame-retarded thermoplastic resin composition obtainable by adding, to an original flame-retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin and 3 to 30 parts by weight of a brominated flame retardant,
0.05 to 3.0 parts by weight of Component (a); light burned dolomite obtainable by light burning natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO; and, in combination therewith,
0.05 to 3.0 parts by weight of at least one compound selected from the group consisting of:
Component (b): a hydrotalcite,
Component (c): a zinc-substituted hydrotalcite compound, and
Component (d): a zeolite compound.
(21) A flame-retarded thermoplastic resin composition obtainable by adding, to an original flame retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin selected from the group consisting of polyolefins, styrene resins, polyesters and polyamides and 1 to 50 parts by weight of a brominated flame retardant,
0:01 to 5.0 parts by weight of Component (a): a dolomite; and, in combination therewith,
0.01 to 5.0 parts by weight of at least one compound selected from the group consisting of;
Component (b): a hydrotalcite,
Component (c): a zinc-substituted hydrotalcite compound, and
Component (d): a zeolite compound.
(22) A flame-retarded thermoplastic resin composition obtainable by adding, to an original flame retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin selected from the group consisting of polyolefins, styrene resins, polyesters and polyamides and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt; and, in combination therewith,
0.01 to 5.0 parts by weight of at least one compound selected from the group consistin of:
Component (b): a hydrotalcite,
Component (c): a zinc-substituted hydrotalcite compound, and
Component (d): a zeolite compound.
(23) A flame-retarded thermoplastic resin composition obtainable by adding, to an original flame retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin selected from the group consisting of polyolefins, styrene resins, polyesters and polyamides and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 50 parts by weight of Component (a): natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO; and, in combination therewith,
0.01 to 5.0 parts by weight of at least one compound selected from the group consisting of:
Component (b): a hydrotalcite,
Component (c): a zinc-substituted hydrotalcite compound, and
Component (d): a zeolite compound.
(24) A flame-retarded thermoplastic resin composition obtainable by adding, to an orifinal flame retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin selected from the group consisting of polyolefins, styrene resins, polyesters and polyamides and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): light burned dolomite obtainable by light burning natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO; and, in combination therewith,
0.01 to 5.0 parts by weight of at least one compound selected from the group consisting of:
Component (b): a hydrotalcite,
Component (c): a zinc-substituted hydrotalcite compound, and
Component (d): a zeolite compound.
(25) A flame-retarded thermoplastic resin composition obtainable by adding, to an original flame retarded thermoplastic resin composition composed of 100 parts by weight of a thermoplastic resin selected from the group consisting of polyolefins, styrene resins, polyesters and polyamides and 3 to 30 parts by weight of a brominated flame retardant,
0.05 to 3.0 parts by weight of Component (a): light burned dolomite obtainable by light burning natural dolomite and /or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO; and, in combination therewith,
0.05 to 3.0 parts by weight of at least one compound selected from the group consisting of:
Component (b): a hydrotalcite,
Component (c): a zinc-substituted hydrotalcite compound,and
Component (d): a zeolite compound.
(26) A flame-retarded styrene resin composition obtainable by adding, to an original flame-retarded styrene resin composition composed of 100 parts by weight of a styrene resin and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): a dolomite compound; and, in combination therewith,
0.01 to 5.0 parts by-weight of at least one compound selected from the group consisting of:
Component (b): a hydrotalcite,
Component (c): a zinc-substituted hydrotalcite compound, and
Component (d): a zeolite compound.
(27) A flame-retarded thermoplastic resin composition obtainable by adding, to an original flame-retarded styrene resin composition composed of 100 parts by weight of a styrene resin and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt; and, in combination therewith;
0.01 to 5.0 parts by weight of at least one compound selected from the group consistin of:
Component (b): a hydrotalcite,
Component (c): a zinc-substituted hydrotalcite compound, and
Component (d): a zeolite compound.
(28) A flame-retarded styrene resin composition obtainable by adding to an original flame-retarded styrene resin composition composed of 100 parts by weight of a styrene resin and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO; and, in combination therewith,
0.01 to 5.0 parts by weight of at least one compound selected from the group consisting of:
Component (b): a hydrotalcite,
Component (c): a zinc-substituted hydrotalcite compound, and
Component (d): a zeolite compound.
(29) A flame-retarded styrene resin composition obtainable by adding to an original flame-retarded styrene resin composition composed of 100 parts by weight of a styrene resin and 1 to 50 parts by weight of a brominated flame retardant,
0.01 to 5.0 parts by weight of Component (a): light burned dolomite obtainable by light burning natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO; and, in combination therewith,
0.01 to 5.0 parts by weight of at least one compound selected from the group consisting of:
Component (b): a hydrotalcite,
Component (c): a zinc-substituted hydrotalcite compound, and
Component (d): a zeolite compound.
(30) A flame-retarded styrene resin composition obtainable by adding, to an original flame-retarded styrene resin composition composed of 100 parts by weight of a styrene resin and 3 to 30 parts by weight of a brominated flame retardant,
0.05 to 3.0 parts by weight of Component (a): light burned dolomite obtainable by light burning natural dolomite and/or synthetic dolomite composed of a calcium carbonate-magnesium carbonate complex salt, each having a magnesium to calcium weight ratio of 5:95 to 95:5 in terms of MgO:CaO; and, in combination therewith,
0.05 to 3.0 parts by weight of at least one compound selected from the group consisting of:
Component (b): a hydrotalcite,
Component (c): a zinc-substituted hydrotalcite compound, and
Component (d): a zeolite compound.
As preferred modes for carrying out the present invention, the above-described flame-retarded thermoplastic resin compositions (2) to (5), (7) to (10), (12) to (15), (17) to (20), (22) to (25), and (27) to (30) can be mentioned, with the compositions (4), (5), (9), (10), (14), (15), (19), (20), (24), (25), (29) and (30) being more preferred. The compositions (5), (10), (15), (20), (25) and (30) are most preferred.

Flame-retarded thermoplastic resin composition


An exhaust gas drive system for engine accessories includes a turbine positioned in the exhaust system of the engine of a vehicle for rotation of the turbine by the pressure of the exhaust gas. The turbine is connected through a reduction transmission to a hydraulic pump which is fluidically connected to respective hydraulic motors which drive the accessories. Communication of exhaust gas to the turbine is controlled by a waste gate. The flow of hydraulic fluid to the hydraulic motors is controlled by actuator valves which operate in an on/off manner or are adjustable for variable control of the accessories. A computer monitors engine speed and controls the position of the waste gate to thereby maintain a substantially constant speed of the turbine. Alternatively, a secondary output shaft of the reduction transmission has a drive pulley thereon for belt driving an accessory having a driven pulley on an input shaft thereof.

1. Field of the Invention
The present invention relates generally to internal combustion engines, and in particular to a system for driving engine accessories with exhaust gas.
2. Description of the Related Art
The output power of an automotive engine is used not only to propel the vehicle having the engine mounted therein but also to drive engine subsystems or accessories, such as an alternator, a water pump, the compressor of an air conditioner, power steering, power brakes, pollution control pumps, and the like. Such subsystems and accessories are conventionally driven from the engine shaft, typically by pulleys and belts engaged therebetween. Specialty types of vehicles often have other types of devices which are driven from the power of their engines. Large trucks usually have engine driven compressors to provide compressed air for air brakes. Tow trucks usually have hydraulic pumps to drive winches and hydraulic lift cylinders. Agricultural tractors often have power take-off (PTO) shafts geared from the tractor transmission as well as hydraulic pumps. Construction and excavation vehicles employ hydraulic pumps to drive hydraulic cylinders for the operating devices thereof. The engine power required to drive the accessories of the engine is not available for propelling the vehicle having the engine mounted therein.
One of the problems associated with engine and vehicle accessories which are belt driven from the engine crankshaft is uneven wear of the front and rear main bearings of the engine. The tension in the belt engaged with the main pulley or harmonic balancer/pulley combination usually pulls the front end of the shaft upward, which is reacted to by the rear end of the crankshaft pushing downward on the main rear bearing. The problem is exacerbated if the belts are over-tensioned. Such radial forces on the crankshaft ends accelerate bearing wear which can result in oil leakage through the worn bearings as clearances are enlarged and the circulation of ground bearing materials throughout the engine which increases engine wear and increases the tendency of some oil passages to clog.
Another problem with belt driven accessories and accessories which are otherwise driven directly from the crankshaft is that the accessories must be clustered around and in close proximity to the engine. The result is that the engine compartments of modern vehicles are extremely crowded, making access for maintenance and repair difficult.
Some engine subsystems and accessories are vital to the operation of the engine or the vehicle and are required to be operating or available for use whenever the engine is running. Other accessories are used relatively infrequently and may be effectively disengaged when not in use, by means such as a solenoid operated clutch or the like. Typically, belt driven accessories are driven at a speed which is related to the rotational speed of the engine crankshaft. Further control is usually accomplished in an on/off manner. For example, the alternator is cycled on and off by an internal voltage regulator. The air conditioner compressor has a solenoid clutch which is thermostatically controlled in an on/off manner. Coolant circulation is controlled by a thermostatic valve which bypasses the radiator unless the coolant temperature exceeds the set point of the thermostat. Radiator fans on modern automobiles are often rotated by a thermostatically controlled electric motor, instead of being belt driven from the engine crankshaft as was formerly done.
Conventional automotive engines are not notably energy efficient. Combustion of the fuel, usually gasoline, is incomplete with a small proportion of the consumed fuel being exhausted to the atmosphere uncombusted and a somewhat larger proportion being exhausted to the atmosphere in an incompletely combusted state as carbon monoxide. Of the energy which is derived from the combustion of the fuel, a large proportion is wasted without doing useful work as heated exhaust gases.
In response to the decreasing supplies of crude oil and the resulting rise in prices of automotive fuel and the increasing concerns regarding atmospheric pollution caused by automotive emissions, efforts have been directed to increasing the fuel efficiency and reducing the emissions of automobile engines. Accordingly, passenger cars and engines therefor have been reduced in size, or "downsized". One result of such downsizing is that some aspects of performance, such as start-off and passing acceleration, suffer. Acceleration performance in an automobile is not merely a recreational aspect of driving, but is also a safety concern, particularly in safely entering high speed, congested traffic without disrupting the traffic flow.
In order to increase their acceleration performance, some cars are equipped with turbo-superchargers or turbochargers which supercharge the engine during hard acceleration. A turbocharger includes a turbine driven by exhaust gases and connected to a compressor feeding air to the intake of the engine at superatmospheric pressure to increase the power output from the engine. The communication of exhaust gases to the turbine is controlled by a waste gate in the exhaust system which is often controlled by engine vacuum or which may be linked to the accelerator pedal such that the waste gate is opened to communicate the exhaust gases to the turbine when the accelerator is pressed past a given point. Otherwise, the turbine is bypassed by the waste gate whereby the engine normally operates in a nonsupercharged mode for economy. Many large diesel trucks employ exhaust driven turbochargers in combination with belt driven superchargers to increase the performance of an engine of a given size rather than employing a larger engine.

Exhaust gas turbine drive system for engine accessories


Various embodiments of the present technology comprise a method and apparatus for battery management. In various embodiments, the apparatus comprises a lithium ion battery and a fuel gauge circuit to monitor the resistance and the capacity as the battery ages. The fuel gauge circuit utilizes the resistance and capacity values to compute resistance changes due to both cycle aging and calendar aging separately. The fuel gauge circuit utilizes the change in resistance values to determine aged capacity values. The fuel gauge circuit controls charging/discharging of the battery according to the aged capacity values.

"Battery capacity" is a measure (typically in ampere-hours) of the charge stored by the battery, and is determined by the mass of active material contained in the battery. The battery capacity represents the maximum amount of energy that can be extracted from the battery under certain specified conditions.
The effective storage capacity of the battery, however, diminishes with age and undergoes irreversible damage. This damage is caused by various mechanisms including corrosion and other chemical processes, and aging of the internal battery components contributes to the damage as well. Each charge/discharge cycle of the battery also has a similar effect but at an accelerated rate. Accordingly, battery deterioration may be the result of cycle aging, which occurs due to battery charge/discharge cycles, and/or calendar aging, which occurs when the battery sits idle (e.g., during storage). It is observed that the effects of calendar aging are accelerated when the battery is charged above 50% capacity and/or when the temperature is above 55 degrees Celsius. The end result is that as the battery ages and deteriorates, the effective capacity of the battery decreases, reducing the amount of time the battery can supply power to a device. Improved battery performance may be achieved if the deterioration due to cycle aging and calendar aging are estimated separately.
One indicator of the battery's ability to retain charge and ability to power a device is the battery "state of health" (SOH). Many applications use this parameter to estimate battery performance, for example the "run-time" of the battery, which reflects the amount of time the battery will continue to provide power before it dies. An accurate estimate of the run-time is desired to provide alerts to a user.

Methods and apparatus for battery management

SEMICONDUCTOR COMPONENTS INDUSTRIES, LLC


Particular embodiments may remove a condition check in the semantics for checking a high-precision data flag. This simplifies the semantics used in the encoding and decoding process. In this case, even if the high-precision data flag is not set, the value of the weighted prediction syntax element is set by the BitDepth variable. However, even if the BitDepth is not considered high-precision data, such as 8 bits, the range for the weighted prediction syntax element is still the same as the fixed value. For example, the syntax elements luma_offset_l0[i], luma_offset_l1[i], delta_chroma_offset_l0[i][j], and delta_chroma_offset_l1[i][j] use the variable BitDepth as described above whether the flag extended_precision_processing_flag is enabled and not enabled to indicate whether the bit depth is above a threshold.

The High Efficiency Video Coding ("HEVC") coding standard (also called H.265) is a coding standard promulgated by the ISO/IEC MPEG standardization organizations. HEVC supports resolutions higher than "high definition," which means pixels may be represented by a larger number of bits than the high definition pictures. For example, 4K resolutions may include images that are 4,000 pixels wide compared to high definition images that are 1920 pixels wide.
Temporal motion prediction is an effective method to increase the coding efficiency and provides high compression. HEVC uses a translational model for temporal motion prediction. According to the translational model, a prediction signal for a given current unit in a current picture is generated from a corresponding reference unit in a reference picture. The coordinates of the reference unit are given by a motion vector that describes the translational motion along horizontal (x) and vertical (y) directions that would be added/subtracted to/from the coordinates of the current unit. A decoder needs the motion vector to decode the compressed video.
HEVC may use single prediction using one reference pictures or bi-prediction using two reference pictures. The pixels in reference units of the reference pictures are used as the prediction. In some conditions, such as when fading occurs, pixels of one of the reference units in bi-prediction may not yield the most accurate prediction. To compensate for this, HEVC may use weighted prediction when performing the motion estimation process. Weighted prediction may weight the pixels in one or both of the reference units used as the prediction differently.

Simplified processing of weighted prediction syntax and semantics using a bit depth variable for high precision data