Methods for the reduction or prevention of oxidative stress in an animal comprising administering to the animal an effective amount of a composition comprising astaxanthin and/or Vitamin E are described. Also described are compositions comprising astaxanthin and/or Vitamin E, the compositions being effective for the reduction or prevention of oxidative stress in an animal.

Cells obtain energy from the oxidation of a variety of organic molecules, and oxygen is the primary oxidant in the biochemical reactions that perform this function. Oxidative stress, which results from the metabolic reactions that use oxygen, may be considered a disturbance in the equilibrium status of pro-oxidant/anti-oxidant systems in intact cells. Cells have intact pro-oxidant/anti-oxidant systems that continuously generate and detoxify oxidants during normal aerobic metabolism. When additional oxidative events take place, the pro-oxidant systems outbalance those of the anti-oxidant, which may result in oxidative damage to cell components including lipids, proteins, carbohydrates, and nucleic acids. Mild, chronic oxidative stress may alter the anti-oxidant systems by inducing or repressing proteins that participate in these systems, and by depleting cellular stores of anti-oxidant materials such as glutathione and Vitamin E. Severe oxidative stress may ultimately lead to cell death.
An imbalance in pro-oxidant/anti-oxidant systems may result from a number of different oxidative challenges, including radiation, metabolism of environmental pollutants and administered drugs, as well as immune system response to disease or infection. The immune response is of particular significance since many toxic oxidative materials are generated in order to attack invading organisms. A variety of chemicals called radicals have roles in these processes. A radical species is any atom that contains one or more orbital electrons with unpaired spin states. A radical may be a small gas molecule such as oxygen or nitric oxide, or it may be a part of a large biomolecule such as a protein, carbohydrate, lipid, or nucleic acid. Some radical species are very reactive with other biomolecules and others, like the normal triplet state of molecular oxygen, are relatively inert.
Of interest with respect to oxidative stress are the reactions of partially reduced oxygen products and radical and non-radical species derived from them. A variety of reactive nitrogen species derived from the reactions of nitric oxide also play important roles in oxidative stress.
Oxidative stress has been implicated in human and animal disease. Cells have, however, multiple protective mechanisms against oxidative stress that act in preventing cell damage. Many dietary constituents are important sources of protective agents including anti-oxidant vitamins and minerals as well as food additives that might enhance the action of natural anti-oxidants. The effectiveness of an anti-oxidant in oxidative stress may be dependent on the specific molecules causing the stress, and the cellular or extracellular location of the source of these molecules.
Intense exercise can contribute significantly to oxidative stress in a number of ways. Most individuals have at some time in their lives experienced soreness and fatigue after physical exertion. For animals that undergo intense, frequent exercising, the effects of oxidative stress can have negative effects on performance.
Intense exercise results in a number of physiological changes in the body. First, aerobic respiration is dramatically increased, thereby increasing superoxide anion generation as much as 10-fold or more (Halliwell, B. (1994) Free radicals and antioxidants: a personal view. Nutr. Rev. 52:253-265), in addition to increasing exposure to environmental oxidative insults such as air pollution. Second, muscle and joint inflammation often result from intense exercise, thus triggering tissue infiltration of neutrophils and subsequent release of reactive oxygen species during the "oxidative burst" characteristic of activated neutrophils mediated by the immune response.
Enhanced antioxidant intake in humans has been reported to decrease the risk of developing specific forms of cancer and to enhance immune function. The effects of dietary antioxidant intake on pathological and physiological processes such as the aging process and exercise in dogs have been reported in the scientific literature. The effects of enhanced intakes of Vitamins E and C on immune function, free radical formation and free radical scrubbers have also been reported.
Cataracts may develop due to metabolic disorders such as diabetes, and from exposure to light, followed by subsequent oxidation of the lens. Oxidative stress, therefore, directly contributes to cataract formation. Primary (diene conjugates, cetodienes) lipid peroxidation (LPO) products accumulate during the initial stages of cataract formation while LPO fluorescent end-products are dominant in the later stages (Babizhayev et al. (2004) Drugs R. D. 5(3):125-139). Lens opacity correlates with the LPO fluorescent end-product accumulation in the tissue, and decreased reduced glutathione leads to sulfhydryl group oxidation of lens proteins (Babizhayev et al. (2004) Drugs R. D. 5(3):125-139). It has been shown that direct injection of LPO products into the vitreous induces cataract formation (Babizhayev et al. (2004) Drugs R. D. 5(3):125-139). Thus, peroxide damage of lens fiber membranes appears to initiate the development of cataracts (Babizhayev et al. (2004) Drugs R. D. 5(3):125-139).
Osteoarthritis (OA) is also related to oxidative stress. Free radicals, including nitric oxide, superoxide anion and hydrogen peroxide, lead to upregulation of enzymes responsible for damage to articular cartilage. These enzymes (MMPs) are specific for collagen, elastin and gelatin.
Oxygen radicals with unpaired electrons are produced as a normal part of oxygen metabolism. These reactive molecules may cause damage to, for example, proteins, nucleic acids (i.e., DNA) and/or membranes which may result in serious cell injury and disease in the whole animal. This process has been associated with the aging process, degenerative diseases, and cancer.
Animals that may be particularly vulnerable to oxidative damage or stress include those that are very active. For instance, well-conditioned canine athletes are healthy animals, which by virtue of their tremendous rates of oxygen consumption generate more free radicals each day than their more sedentary counterparts. The changes in immune function, metabolic intermediates, tissue stores of antioxidants and antioxidant enzymes induced by free radical production are greater in canine athletes than sedentary animals.
Previous studies examining hard working dogs revealed that exercise was associated with a significant increase in plasma concentrations of isoprostanes, a stable by product of lipid peroxidation. These same studies also demonstrated a decrease in plasma Vitamin E concentrations during exercise. Further studies examined the effect of Vitamin E supplementation on these parameters. Vitamin E supplementation helped decrease or alleviate the exercise associated drop in plasma Vitamin E concentration but did not decrease the elevations in plasma isoprostanes.
Astaxanthin is a mixed carotenoid which may be found in a number of sources; it is present in high levels in algae. This pigment protects the algal organism from damage due to ultraviolet radiation exposure. Several studies have demonstrated immuno-stimulatory properties of astaxanthin in cultured cells as well as whole animals (mice). It is also used in sunscreen lotions as it has been demonstrated to diminish reddening of the skin after sun exposure. Astaxanthin supplementation has also been associated with increased endurance in untrained human subjects.

Methods and compositions for reducing oxidative stress in an animal


A postcard containing a separable card portion. The postcard has a first sheet and a second sheet which lies on the first sheet. An adhesive layer removably bonds the two sheets together. The first sheet includes a card portion which is surrounded by a cutting line so that it may be separated from the rest of the first sheet. The adhesive layer also firmly holds the card portion in position during mailing so as to avoid the possibility that it becomes separated and lost in mailing. After the postcard is received, the two sheets are peeled apart so that the card portion may then be cut out from the first sheet and used separately from the sheets. The card portion may include a name and address which then can be used as the address information both for the postcard, while it is attached to the sheets, and for the card itself, after it is separated.

The present invention relates to a postcard or an envelope in which a portion filled with name and address may be utilized as membership card, certification card, etc., in addition to being used for postal information.
Recently, among varieties of postal matters, it has been increasingly popular to use a type of postcard comprising a sheet of paper having dimensions twice as large as a conventional postcard, in which a sheet is folded down into half to be the same dimensions as conventional postcard and two backside parts thereof formed by such folding being closely joined each other through adhesion or the like in a separable manner. As is known, because of material properties, the folded sheet with its folded backside parts joined closely in a separable manner cannot be restored to the mentioned closely joined state, once the joined portion is peeled. Since the sheet has a dimension twice as large as a postcard, more information such as product information may be described in the backside of the joined sheet than that of a post card. Moreover, information relating to privacy may be described with a sense of security, because the backside of the joined sheet would not be seen by others.
On the other hand, various kind of methods have been proposed as methods for mailing a card together with a postcard or an envelope. The methods include securing a card to the backside of a postcard by means of a removable adhesive, enclosing a card in an envelope, etc., for example.
However, in the mentioned conventional methods, there is a disadvantage such that it is necessary for a sender of postal matter to fill out a sending card with name and address of addressee (i.e., a card user) either by printing or by hand writing, in addition to a description of the same name and address on the postcard or envelope, otherwise the card user himself must fill up the card with his name and address, etc. after receiving the card. Anyway, repeated description of the same name and address may be rather troublesome work.
Accordingly, the invention was made to solve this problem and has an object of providing a postcard on which a name and address may be utilized also as a part of a card, as it is, and it is not necessary to repeat filling up the card with the same name and address of card user (i.e., addressee information) once filling up the postcard or envelope with required name and address, etc. of the card user.
Another object of the invention is to provide an envelope of which a portion showing name and address of addressee may be utilized or serve also as a recording medium, even in case of a recording medium of a large thickness.


In the reciprocating pump P, the pressure chamber 30 is formed by an atomizing tube 15, a piston 28, and a cylinder 20. The pressure chamber 30 has a check valve 24 that opens and closes the inlet of the said pressure chamber 30 and a ball-shaped stirring material 25 moving freely in the pressure chamber 30 that stirs the mixture in the pressure chamber 30. On the other hand, pumping space is formed by the piston 28 and the cylinder 20 in the reciprocating pump P, apart from the pressure chamber 30. The pumping space 29 is occupied by the mixture pumped up when the push button 17 is returned to its home position and communicating holes are provided through which the mixture is discharged into the container 10 when the push button is pressed. The atomizer of an reciprocating pump type of the present invention can stir sufficiently and atomize a liquid-powder mixture when used.

The present invention relates to an atomizer of the reciprocating pump type that has a reciprocating pump at the mouth of a container. More particularly, it relates to an atomizer for cosmetic and medical use that atomizes a mixture of a liquid such as water, alcohol and powder such as medicines and cosmetics housed in the container by pressing the push button on the reciprocating pump and releasing the pressing of the button.
Conventionally, atomizers that spray a mixture of liquid and powder are available in types such as aerosol bombs that use an atomizing agent. The above aerosol bomb has both a mixture and an atomizing agent housed in a container and a push button at the end of an atomizing tube from the container. When used, the bomb is first held in the user's hand and shaken well to stir a mixture in the container sufficiently. When the push button is pressed with the user's finger, the atomizing tube is pushed in and opens the valve. Then the mixture through the atomizing tube is atomized through the nozzle provided in the push button.
However, such a conventional atomizer has a problem of not being capable of atomizing a mixture stirred sufficiently when used, because the atomizer, even if shaken well before use, allows powder to start to precipitate when the user stops shaking the atomizer.
An object of the invention therefore is to provide an atomizer of reciprocation pump type that is capable of stirring a mixture sufficiently and atomizing both powder and a liquid when used.


A vertical-motion vibration isolator utilizes negative-stiffness-producing mechanism which includes a plurality of compressed flexures, each having a particular length in the compressed direction of the flexure and being oriented in a horizontal direction, wherein the plurality of compressed flexures are positioned relative to each other such that the length of each compressed flexure substantially overlaps the length of each of the other compressed flexures. At least some of the plurality of compressed flexures can be positioned in a stacked arrangement. The arrangement of compressed flexures forming a portion of the negative-stiffness mechanism can reduce the size of the isolator without compromising vibration isolation performance.

The present invention relates generally to suspension systems for isolating and reducing the transmission of vibratory motion between an object or payload and a base and, more particularly, to a compact vibration isolator which exhibits low stiffness in the direction of the weight load to effectively reduce the transmission of vibrations between the object and the base. The present invention represents improvements over my previous isolators which utilize negative-stiffness mechanisms to produce low vertical natural frequencies and which rely on a principle of loading a particular elastic structure which forms the isolator or a portion of it to approach the elastic structure's point of elastic instability.
The problems caused by unwanted vibration on equipment, devices and processes that are extremely motion sensitive have been widely researched and numerous solutions to prevent or reduce the transmission of vibratory motion have been proposed and developed. Many of the devices designed to reduce the transmission of unwanted vibration between an object and its surroundings, commonly called vibration isolators or suspension devices, have utilized various combinations of elements such as resilient pads made from a variety of materials, various types of mechanical springs, and pneumatic devices. There are, however, shortcomings and disadvantages associated with these particular prior art isolation systems which prevent them from obtaining low system natural frequencies and from limiting internal structural resonant responses to low values while providing high isolation performance at the higher frequencies.
These shortcomings and disadvantages of prior art systems were addressed through the development of novel vibration isolation systems devices described in U.S. Pat. No. 5,530,157, entitled "Vibration Isolation System" issued May 10, 1994, U.S. Pat. No. 5,370,352, entitled "Damped Vibration System" issued Dec. 6, 1994, U.S. Pat. No. 5,178,357, entitled "Vibration Isolation System" issued Jan. 12, 1993, U.S. Pat. No. 5,549,270, entitled "Vibration Isolation System" issued Aug. 27, 1996, U.S. Pat. No. 5,669,594, entitled "Vibration Isolation System" issued Sep. 23, 1997, U.S. Pat. No. 5,833,204, entitled "Radial Flexures, Beam-Columns and Tilt Isolation for a Vibration Isolation System issued Nov. 10, 1998, and Improved Vibration Isolation Systems, Ser. No. 13/587,135 filed on Aug. 16, 2012, which are all hereby incorporated by reference in this present application. These vibration isolators exhibit low stiffness, high damping to limit resonant responses of the composite system, effective isolation at the higher frequencies, and can provide high isolator internal structural resonant frequencies.
The particular vibration isolation systems described in these patents provide versatile vibration isolation by exhibiting low stiffness in an axial direction (generally the direction of the payload weight) and any direction substantially transverse to the axial direction (generally a horizontal direction), and may provide tilt or rotation about three mutually perpendicular axes. The present invention, however, is directed only to isolators used to isolate vibratory motion in the axial or vertical direction. It should be appreciated, however, that the present invention could be connected in series with a horizontal-motion isolator and/or a tilt-motion isolator to provide bi-directional or omni-directional isolation as well. In subsequent discussions, an axial-motion isolator will be referred to as a vertical-motion isolator, and a system using multiple axial-motion isolators will be referred to as the vertical-motion isolation system.
In the embodiments described in the above-noted patents, the isolators rely on a particular principle of loading a particular elastic structure which forms the isolator or a portion of it (the loading being applied by either the supported weight or by an external loading mechanism) to approach the elastic structure's point of elastic instability. This loading to approach the point of elastic instability, also called the "critical buckling load" of the structure, causes a substantial reduction of either the vertical or the horizontal stiffness of the isolator to create an isolation system that has low stiffness in the vertical and in any horizontal direction, and increases the damping inherent in the structure. While stiffness is reduced, these isolators still retain the ability to support the payload weight.
In the event that the load on the elastic structure is greater than the critical buckling load, the excessive load will tend to propel the structure into its buckled shape, creating a "negative-stiffness" or "negative-spring-rate" mechanism. By combining a negative-stiffness mechanism with a spring, adjusted so that the negative stiffness cancels or nearly cancels the positive stiffness of the spring, one obtains a device that can be placed at or near its point of elastic instability. The magnitude of the load causing the negative stiffness can be adjusted, creating an isolator that can be "fine-tuned" to the particular stiffness desired.
These above-described isolators provide excellent devices for isolating or reducing the transmission of vibratory motion between an object and the base. It would be particularly beneficial if such vertical-motion isolators which rely on this principle of loading the structure to approach its point of elastic instability could be made in a more compact size and shape which may be more suitable for certain vibration isolation applications. While a more compact geometry would be beneficial, it is important that the performance of such vertical-motion isolators not be compromised. The present inventions solve these and other needs.


A spectroscopic method, preferably Raman scattering, is used to rapidly determine the general health or stress status of living plants and plant products, including agricultural crops, forests, and harvested fruits and vegetables. In the preferred embodiments, carotenoid levels are used to provide an indication of oxidative deterioration. Based upon the results of the analysis, further action may or may not be taken, for example, in terms of choosing, picking, harvesting or sorting the agricultural product in accordance with the carotenoid level. Concentration levels of an analyte substance can be determined relative to an external standard, to each other, or relative to another substance in the item being analyzed. Carotenoids such as lycopene, beta-carotene, lutein, violaxanthin, neoxanthin, antheraxanthin, and zeaxanthin are determined according to the invention, through other plant components may be analyzed such as other terpenes, polyenes, chlorophyll, proteins, starches, sugars, overall nitrogen levels, flavonoids, and vitamins. The hardware associated with the invention may be field portable or mounted on a piece of equipment such as a harvester or sorter.

In plants, carotenoids act as accessory pigments in light harvesting, and more importantly, to detoxify various forms of activated oxygen and triplet state chlorophyll that are produced as a result of the excitation of photosynthetic complexes by light.
The dollar value of fruit and vegetable crops are dependent on freshness and quality. In the agricultural product handling and food processing industry, there is currently no precise method of determining fruit and vegetable quality or antioxidant nutrient content which is rapid enough to be useful in a continuous flow environment. The current quality control method for fruit and vegetable handlers typically consists of an expensive and imprecise manual selection process based on the color or shape of the product. An automated quality control process would be very useful.
In the food product industry, carotenoid levels (usually lycopene or beta-carotene) are determined using high-performance liquid chromatography (HPLC). These measurements are made throughout the food processing line to assure quality control of the final product. The delay in obtaining HPLC data, which is not a real-time process, leads to difficulties in identifying problems as they occur. A rapid and objective measurement of post-harvest fruit and vegetable quality would have several commercial applications within the agricultural product handling and food processing industries, especially with an increased interest in nutritionally specific claims for fruits and vegetables, and processed functional foods.
An improved system to monitor the health status of food crops has broad commercial potential in agricultural crop management. Traditional methods of determining crop stress (observation of wilting, change in coloration, etc.) appear after damage has already occurred, and crop yields may not be recoverable. Currently, chemical analysis using HPLC is one of the few means available to get early indications that a plant or crop is under stress. However, this technique is invasive, requiring a sample of plant matter for analysis. HPLC is also expensive, time-consuming, requires user training, and is inconvenient to perform away from a laboratory. Conventionally, plant samples may be taken to an analysis laboratory, adding time and expense to the analysis. The link between measurement and plant sample location also has to be recorded for later interpretation of results. Ambiguous results from an HPLC may result from a variety of factors, such as plant sample contamination, and are then inconvenient to repeat. The present invention allows non-invasive determination of stress and environmental effects on plant health, allowing crop yields to be increased. Hence, a system allowing automated quality control using a rapid or effectively instantaneous analysis technique would be extremely useful.
In U.S. Pat. No. 5,873,831, Bernstein et al. describe a system for measurement of carotenoid levels within the macula and fovea of the eye. However, the characterization of plants is not described.
In U.S. Pat. No. 6,052,187, Krishnan describes a plant analyzer based on fluorescence. In U.S. Pat. No. 5,576,550, Koppikar describes a phytoluminometer using luminescence techniques. In U.S. Pat. No. 6,114,683 to Spiering, a plant chlorophyll content imager is disclosed. However, the use and advantages of Raman scattering are not disclosed in these disclosures.
In U.S. Pat. No. 5,257,085, Ulich et al. discloses a Raman imaging lidar system. However, this system is restricted to short pulses of laser radiation and imaging applications. The identification of carotenoids is not disclosed.

Optical method and apparatus for determining status of agricultural products


An apparatus includes a component having a shape memory material. The shape memory material has a first shape including a substantially elongate segment. The shape memory material has a second shape including a helix having a first ring and a second ring configured to exert a compressive force on a membrane interleaved between the first ring and the second ring and lying in a plane substantially perpendicular to an axis of the helix, the shape selectable based on an external stimulus.

Age-related macular degeneration (AMD) is a disease that causes loss of vision due to deterioration of delicate photo-receptors in a specialized region of the retina known as the macula. The macula is a 1.5 mm region of the retina that has the greatest density of cone photo-receptors in the eye. Surgical correction of AMD involves reconnecting the macula with the healthy choroid by means of a 3-port par plana vitrectomy. The damaged tissue under the macula is replaced with a healthy graft of retinal pigment epithelium (RPE), Bruch's membrane, and partial or full thickness choroid. Unless the graft is supported during cutting and translocation, the tissue can fold on itself and thus damage the delicate cells of the RPE.
Current technology for performing macular translocation is inadequate.


One particular example includes a system, comprising a processor and a memory to store instructions that when executed by the processor performs operations, comprising displaying a map of a first area on a display; receiving an instruction to designate a second area on the map to be avoided; displaying the second area to be avoided on the map; and generating a route from a first point to a second point, where the route does not go through the second area to be avoided.

Navigation systems, electronic maps (also known as digital maps), and geographical positioning devices are increasingly used by travelers to assist with various navigation functions, such as to find destinations and addresses, calculate optimal routes, and provide real-time driving guidance. Typically, the navigation system includes a small display screen or graphic user interface that portrays a network of roads and a general visual display of an area. To find a route to a specific place or address, typically a user will enter the specific place or address and the navigation system will calculate a route to the specific place or address. Then the navigation system will plan a route based on the software used by the navigation system. However, sometimes a user may not want the route to pass through a certain area or may want the route to go through a certain area. Also, a user may have information about an area that the navigation system does not have, such as a new construction area. It would be beneficial if the user could designate areas to be avoided and/or areas that are preferred.
The FIGURES of the drawings are not necessarily drawn to scale or proportion, as their dimensions, arrangements, and specifications can be varied considerably without departing from the scope of the present disclosure.

Route selection for navigation devices and applications


Disclosed are a method of packet classification and a device thereof. A method for packet classification according to one embodiment of the present invention comprises the steps of: partitioning the entire rule set by using key values corresponding to packet fields, into a plurality of rule subsets; generating recursive flow classification (RFC) tables for each of the plurality of partitioned rule subsets; loading, in the same cache line, both partition information and RFC table information commonly corresponding to key values of received packets; searching for a rule subset by using the partition information on the key values of the received packets, which are loaded in the cache line; and searching for an RFC table for a rule by using the RFC table information on the key values of the received packets, which are loaded in the cache line.

With the rapid advancement in Internet, packet forwarding comes to be a very important task of a router to improve quality of Internet services. Packet forwarding is a work of sending out a packet toward a final destination network using header information of the packet flowing into the router.
Requests on various kinds of services in the Internet make it further difficult to process a packet. For example, an application program such as audio or video streaming sensitive to transfer speed requests quality assurance, and a variety of services such as firewall protection, load balancing, web switching, Intrusion Detection and Security (IDS) and the like are also required. In order to provide such services, packet classification in the router should be preceded.
In packet forwarding, packets should be processed and sent out in accordance with input link speed, and it can be said that packet classification is a work more sensitive to packet processing speed since all the fields in the packet header information should be examined unlike an IP address search which simply confirms and processes only a destination address. Accordingly, studies on various packet classification structures for effectively performing packet classification are actively under progress. The most important criterion for evaluating performance of a packet classification structure is packet processing speed, and the packet processing speed is determined by the number of memory access. The second important criterion is memory size required to store a packet classification table. The required memory size depends on the data structure of the packet classification table.
Recursive flow classification (RFC) algorithm among conventional packet classification algorithms is one of the algorithms capable of classifying a packet at a high speed. However, there is a limit in practically using this algorithm since a memory use amount, a table generation time and a table size are exponentially increased according to the number of rules.
Although a lot of algorithms have been proposed thereafter, most of them have a problem in that search speed, which is the most important, is lowered in return for solving the problems of the RFC algorithm. For example, in a method proposed in a paper entitled "Scalable Packet Classification through Maximum Entropy Hashing", IEEE/ACM Transactions on Networking, published December, 2009. a partitioning technique is used to divide an total rule set into a plurality of small sub rule sets, and if RFC tables are generated for the small sub rule sets, the size and generation time of the RFC tables are reduced greatly.
However, in order to find actually a rule corresponding to a given key, such a partitioning technique needs a process of searching for a sub rule set containing the rule, and a process of searching for an RFC table is performed after the sub rule set is found, and thus overall search performance is lowered compared with a case of simply searching for only an RFC table.
Accordingly, there is a need for a method capable of improving the search speed by reducing the number of memory access.

Method for packet classification and device therefor

Ajou University Industry-Academic Cooperation Foundation


Systems and methods for producing fluorocarbons are provided that include contacting a saturated halogenated fluorocarbon with hydrogen and catalyst to produce a saturated hydrofluorocarbon and an unsaturated fluorocarbon. Aspects of the present invention describe systems and methods for contacting saturated halogenated fluorocarbons such as CF3CClFCF3 and/or CF3CCl2CF3 with hydrogen and catalyst. Systems and methods of the present invention also describe contacting saturated halogenated fluorocarbons with catalysts having one or more of K, Zr, Na, Ni, Cu, Ni, Zn, Fe, Mn, Co, Ti, and Pd. Aspects of the present invention also describe contacting saturated halogenated fluorocarbons with hydrogen under pressure. Saturated hydroflourocarbons and unsaturated fluorocarbons produced in accordance with the systems and methods of the present invention can include one or more of CF3CFHCF3, CF3CH2CF3, CF3CHClCF3, CF3CF═CF2, CF3CH═CF2, and CF3CCl═CF2.

Hydrofluorocarbons and fluoromonomers such as 1,1,1,2,3,3,3-heptafluoropropane (CF3CHFCF3, HFC-227ea) and hexafluoropropene (CF3CF═CF2, FC-1216, HFP) are commercially desired.
HFP is widely employed as a monomer for the production of fluorine-containing polymers, for example, the thermoplastic FEP ("fluorinated-ethylene-propylene") resins, formed via the copolymerization of tetrafluoroethylene and hexafluoropropene (see for example, Fluorine Chemistry: A Comprehensive Treatment, M. Howe-Grant, ed., Wiley & Sons, New York, N.Y., 1995, page 404).
HFC-227ea has found use as a blowing agent (U.S. Pat. No. 5,314,926; U.S. Pat. No. 5,278,196), refrigerant (Chen, J., Sci. Tech. Froid (1994), (2 CFCS, the Day After), 133-145), and propellant for use in metered dose inhalers (Clark, R., Aerosol. Sci. Technol., (1995) 22, 374-391). The compound has also found widespread use as a fire suppression agent, for example, the protection of telecommunication facilities where it is marketed under the tradename FM-200® (Great Lakes Chemical Corporation, Indianapolis, Ind.) (Robin, M. L., Process Safety Progress, Volume 19, No. 2 (Summer 2000), p. 107-111).
Numerous methods are disclosed in the prior art for the preparation of halogenated compounds. These methods vary widely, due in part to the different halogens and functional groups involved. The prior art demonstrates that known methods do not readily translate into predictable applications for other compounds.
Methods have been reported for the production of FC-1216. These processes include the thermal cracking of tetrafluoroethylene (TFE) at reduced pressure and temperatures of 700C to 800C as well as the pyrolysis of polytetrafluoroethylene under vacuum at elevated temperatures can yield HFP.
Methods have been reported for the production of HFC-227ea. The vapor phase reaction between HFP and HF over an active carbon catalyst can produce HFC-227ea (GB 902,590). HFC-227ea has also been produced via the treatment of 1,1,1,3,3,3-hexafluoropropane (CF3CH2CF3, HFC-236fa) with elemental fluorine (U.S. Pat. No. 5,780,691) and via the treatment of 2-chloro-1,1,1,3,3,3-hexafluoropropane (CFC-217ba) with HF (WO 99/40053).
It is desired to develop new methods and systems for economically favorable production of HFP and HFC-227ea, and it would be desired for such methods and systems to have broad utility for the production of saturated and unsaturated fluorocarbons.


A universal tinting concentrate for both solvent- and water-based paints and coatings. The universal tinting concentrate is a composition which includes a colorant component, such as pigment, colorant, tinting agent and/or metal effect agent; a pigment dispersant including a moiety selected from the group consisting of an organic acid, anhydride, salt thereof, and derivative thereof, wherein the dispersant facilitates the dispersal of the colorant component in organic-based and aqueous-based vehicles; and a pH-neutralizing agent. In one embodiment of the invention, the pigment dispersant is represented by the following structure:

Paints and coatings are used to protect a surface from corrosion, oxidation or other types of deterioration and to provide decorative effects. Organic solvent-based paint or coating is a uniformly dispersed mixture ranging in viscosity from a thin liquid to a semi-solid paste and includes a film-forming polymeric binder, an organic solvent, pigment and other additives. The binder and the solvent collectively make what is known as the xe2x80x9cvehicle.xe2x80x9d
Latex or emulsion paint is a water-based paint or coating of a dispersion of dry powders of pigment and dispersed colorant, plus various paint additives such as fillers and extenders, and a resin dispersion. Typically the dry powder dispersion is made by milling the dry ingredients into water. The resin dispersion is either a latex formed by emulsion polymerization or a resin in emulsion form. The two dispersions are blended to form an emulsion, or latex, paint. Thus, the binder for latex paints and coatings is in an aqueous-dispersed form, whereas in a solvent paint or coating, it is in a soluble form. Latex paints and coatings are popular consumer paints, as they are easy to apply, are easy to clean up, are nonflammable, generally lack a disagreeable odor and can be used on both interior and exterior surfaces.
Pigments impart color to both solvent and latex paints and coatings. They also contribute to the opacity, durability and hardness of paint coatings. They are added to paint in the form of dry pigment powders and pigmented tinting concentrate during paint manufacture at the paint plant. In addition, especially for consumer latex paints, they may be added in the form of pigmented paint tinting concentrates at the point of sale, such as at retail paint stores. Essentially, the consumer may choose a custom-made color of the paint by having the retailer add a tinting concentrate to a white or tintable base.
Pigments are ordinarily organic or inorganic dry powders that incorporate a mixture of primary particles, aggregates and agglomerates. Aggregates are primary pigment particles joined face-to-face, and agglomerates are primary pigment particles joined at an edge or a corner. For both industrial and consumer paints, whether solvent- or latex-based, pigment preferably should be dispersed homogeneously throughout the paint. To properly be dispersed, pigments must be wetted, deaggregated and deagglomerated in the paint vehicle. Dry pigments are insoluble in organic solvents and water, therefore necessitating wetting, deaggregation and deagglomeration before dispersion forces can take full effect and enable the production of a stable, colloidal pigmentary dispersion in the paint vehicle. The wetting or deaeration process is physical in nature, as it requires that the vehicle or solvent displace the air on the surface of the pigment particles. An ideal dispersion consists of a homogenous suspension of primary particles, after reducing any aggregates and agglomerates to primary particles.
The wetting process is accomplished through the use of wetting agents, which typically are a type of surface-active agent or xe2x80x9csurfactant.xe2x80x9d As discussed, wetting involves incorporation of the pigment into the vehicle replacing pigment-air interfaces with pigment-vehicle interfaces. Surfactants tend to bring pigment into solution as a result of surface activity at the pigment-solution interface. In general, surfactant molecules are composed of two segregated portions, one of which has sufficient affinity for the solvent (organic or aqueous) to bring the entire molecule into solution. The other portion is rejected by the solvent, because it has less affinity for the solvent than the solvent molecules have for each other. If the forces rejecting this group are sufficiently strong, the solute molecule will tend to concentrate at an interface, so that at least part of the area of the rejected group is not in contact with the solvent molecules. While some organic solvents may be good pignment wetting agents themselves, surfactants are typically added to solvent paints to ensure thorough pigment dispersion throughout the paint vehicle. Water-based systems are poor wetting agents of dry pigments, and thus, latex paints necessarily require the addition of surfactants for pigment dispersion.
Surfactants also stabilize the pigment dispersion from reaggregating and reagglomerating. In strongly polar organic solvents or water, electrostatic stabilization is imparted by charged species adsorbing onto the pigment surfaces. This causes a cloud of oppositely charged counter-ions to form around the particle, thus making an electric double layer that will repel similarly charged surfaces. In nonpolar systems, a steric-stability is imparted by the adsorbed dispersant that prevents close approach of the surfaces.
Surfactants conventionally used with tinting concentrates are primarily nonionic and amphoteric surfactants in conjunction with anionic surfactant. There are disadvantages with the known surfactants. Most notably, the surfactants known for use as pigment dispersants for both solvent, and latex paints or tinting concentrates therefor, can harm the rheological profiles of paints, tending to impart to a greater or lesser degree undesirable properties to the ultimately dried paint film. Surfactants can retard the curing or drying process of the paint and can increase the water sensitivity and reduce the scrub resistance of the dried film. Additionally, they can interfere with and hinder paint and pigment tinting concentrate thickeners and undesirably alter paint viscosity. Further, the primary nonionic surfactants used in conventional pigment dispersant formulations are alkyl phenol ethoxylates, which may be hazardous to human health.
The present invention provides a universal tinting concentrate that may be used with organic solvent-based and latex or emulsion aqueous-based paints and coatings. The tinting concentrate of the present invention preferably provides particularly advantageous compatibility with both types of systems, and exhibits a highly desirable rheological profile. The inventive tinting concentrate provides improvements over the prior art, generally providing tinting concentrates which produce dried paint and coating films with faster curing, increased scrub resistance, better flash rust and corrosion resistance, and/or better rheological profiles than paints produced with known tinting concentrates. It is also an object of the present invention to provide a tinting concentrate that may be used to make paints with extremely low levels of volatile organic compounds (xe2x80x9cVOCxe2x80x9d).
In one embodiment, the present invention is directed to a universal tinting concentrate for both solvent- and water-based paints and coatings. Preferred universal tinting concentrates of the present invention include compositions which include (i) a colorant component (e.g., a pigment, colorant, tinting agent, metal effect agent, etc.); (ii) a pigment dispersant; and (iii) a pH-neutralizing agent. Preferably, the pigment dispersant includes an organic acid, anhydride, salt thereof or derivative thereof. More preferably, the pigment dispersant contains no more than about 70 carbon atoms and most preferably has a total of about 15 to about 50 carbon atoms. In one preferred embodiment, the pigment dispersant is represented by the following structure:
where
r and s are integers and r+s is preferably 6 to 16;
x and y are integers and x+y is preferably 0 to 19;
Z is preferably H or COOH; and
Zxe2x80x2 is preferably H or COOH.
Optional additional components for the universal tinting concentrate include a diluent; a dihydric or polyhydric alcohol; a polyether; a biocide; one or more conventional anionic and/or cationic surfactants; a defoaming agent; carboxyl-containing polymers, such as polyacrylates and/or carboxyl-containing polyurethanes, which can function as conventional dispersing agents; and additional pigment, colorant, tinting agent or metal effect agent. When added to paint, the universal tinting concentrate preferably has a pigment-to-vehicle binder ratio of from about 0.35 to 25.
These and other advantages of the present invention will become more apparent by referring to the detailed description and illustrative examples of the invention.
In one embodiment, this invention relates to a universal tinting concentrate (e.g., for paints and coatings). In a particularly preferred embodiment, this invention relates to a universal tinting concentrate for solvent-based and aqueous paints and coatings. The universal tinting concentrate accomplishes pigment dispersion in these dissimilar coating formulations through the use of a novel pigment dispersant (e.g., a dispersant comprising an organic mono- or polyacid, preferably having ionotropic character).
The advantages of the invention include an ability to use a single set of pigment concentrates for tinting organic- and aqueous-based paints and coatings. Additional advantages include improved dry response of paints and coatings formulated with the inventive tinting concentrate when compared to paint and coating formulations with prior art dispersants. In more preferred embodiments, there are significant (20 to 40%) increases in scrub resistance for paints and coatings formulated with the inventive universal tinting concentrate compared with paints and coatings formulated with prior art pigment dispersants or tinting concentrates. Paints and coatings formulated with the inventive universal tinting concentrate preferably show increased flash rust resistance when used in water-based paints directly over metal. Some paint and coating formulations using the inventive universal tinting concentrate show significantly reduced depression in viscosity when compared to the prior art. A further advantage is the virtual elimination of a VOC-contribution by the colorant to various coatings.
Both solvent-based and water-based paints and coatings include a binder. A xe2x80x9ccoatingxe2x80x9d is a film or a thin layer applied to a substrate, which may be clear or may contain pigment, colorant, tinting agent or metal effect. Paint is a type of coating, and hereinafter, unless otherwise noted, any reference to xe2x80x9cpaintxe2x80x9d means both paint and coating.
Organic solvent-based paint (xe2x80x9csolvent paintxe2x80x9d) is a uniformly-dispersed mixture ranging in viscosity from a thin liquid to a semi-solid paste and includes a polymeric binder; an organic solvent; pigment, colorant, tinting agent and/or metal effect agent; and other additives. The polymeric binder can be a drying oil, natural, semi-synthetic or synthetic resin such as polyacrylate, polyurethane, modified alkyd resin or other film-forming polymer. Included as well in the binder usually is a cross-linking agent, hardener, curing agent and/or secondary resin having cross-linking ability. The polymeric binder and the solvent collectively make what is known as the xe2x80x9cvehicle.xe2x80x9d
xe2x80x9cPigment,xe2x80x9d usually in the form of organic or inorganic dry powder, is a substance that imparts color to another substance or mixture. xe2x80x9cColorantxe2x80x9d is also a substance that imparts color to another substance or mixture, and generally includes pigment and other additives. xe2x80x9cTinting agentxe2x80x9d similarly is a color-imparting agent. xe2x80x9cMetal effect agentxe2x80x9d is an agent that imparts metallic-type luster and associated properties to paint films. Hereinafter, unless otherwise noted, pigment, colorant, tinting agent and metal effect will be referred to collectively as xe2x80x9ccolorant component.xe2x80x9d
Latex or emulsion paint (xe2x80x9clatex paintxe2x80x9d) is a water-based paint consisting of a dispersion of dry powders of pigment, plus various paint additives, such as fillers and extenders, and a resin dispersion. The dry powder dispersion is made by milling the dry ingredients into water. The resin dispersion is either a latex formed by emulsion polymerization or a resin in emulsion form, constituting the binder. The two dispersions are blended to form latex paint. Thus, the binder for latex paints is in an aqueous-dispersed form, whereas in a solvent paint, it is in a soluble form.
Preferred universal tinting concentrates of the present invention provide a single set of tinting concentrate formulations for use with either solvent or latex paints.
Preferred universal tinting concentrates include a suitable pigment dispersant (e.g., an organic acid, anhydride, salt thereof or derivative thereof ). Suitable organic acids, anhydrides, salts thereof or derivatives thereof are typically liquid, but may be a solid, at ambient temperature. More preferred organic acids, anhydrides, salts thereof or derivatives thereof are liquid at room temperature or have a melting point below about 70xc2x0 C. The tinting concentrate preferably also includes a colorant component and a pH-neutralizing agent. Optional additional components for the tinting concentrate include additional colorant component, diluent, a base, a polyether, a biocide, one or more conventional anionic and/or cationic surfactants, a defoaming agent and carboxyl-containing polymers, such as polyacrylates, and/or carboxyl-containing polyurethanes, which can function as conventional dispersing agents.
Suitable organic acids, anhydrides, salts thereof or derivatives thereof used in the universal tinting concentrate, typically function as a pigment dispersant and have an ability to disperse the colorant component in organic-based and aqueous-based vehicles. Suitable pigment dispersants, while not necessarily completely miscible with all organic and aqueous solvents, preferably have at least some solubility in most organic- and aqueous-based solvents.
In one embodiment, the pigment dispersant is an acid or salt thereof. The chemistry of the acid or salt is preferably based upon an aliphatic organic molecule that contains at least one carboxylic acid, sulfonic acid or phosphoric acid group and aliphatic carbons. Saturated and/or unsaturated carbons may be present in the organic acid.
Suitable organic acids, which generally contain no more than about 70 carbon atoms, may function as a pigment dispersant. Typically, the pigment dispersant of the present invention is a polyacid or salt thereof containing a total of 6 to 50 carbon atoms. More typically, it is a polyacid or salt thereof containing 15 to 30 carbon atoms, two to four carboxyl groups and a chain of 14 to 22 aliphatic carbons, which chain may have one or more sites of unsaturation. As the alkylene chain is a hydrocarbon chain which may include portions of a cycloaliphatic ring.
Suitable acids include monoacids, polyacids, or a salt thereof. The mono- or polyacid or salt thereof more preferably contains no more than 60 carbon atoms and has a ratio of acid groups to aliphatic carbons of at least about 1:5 and preferably a ratio of from about 1:6 to about 1:25. Aromatic groups and cycloaliphatic groups may be present. Preferably, the aromatic and cycloaliphatic groups are present within the aliphatic carbon chain, such that these groups confer restricted rotation upon the acid or salt molecule. The acid typically constitutes between about 3 and 13% by weight of the total tinting concentrate. The pigment-to-binder ratio should be between about 0.35 and 25 when the tinting concentrate is mixed with a paint to provide color.
In a first preferred embodiment, the inventive dispersant is a carboxylic acid containing a total of 15 to 44 carbon atoms having the following chemical structure:
where
r and s are integers and r+s is preferably 6 to 16;
x and y are integers and x+y is preferably 0 to 19;
Z is preferably H or COOH; and
Zxe2x80x2 is preferably H or COOH.
For ease of reference, where Z is H and Zxe2x80x2 is COOH, this formula will be referred to as xe2x80x9cFormula I.xe2x80x9d Alternatively, the dispersant is the salt of this dicarboxylic acid. A particularly suitable example of the above-referenced embodiments is a dicarboxylic acid in which r is 5, s is 7, x is 0 and y is 0. A particularly useful commercial example this embodiment is Westvaco Chemical""s Diacid 1550, which is a blend of the above-referenced structure with 8 to 12% fatty acid. Another useful commercial example is Westvaco""s Diacid 1550 XLM, which is the same structure without the fatty acid.
In a second preferred embodiment, the inventive dispersant is the dispersant of Formula I, but where Z is COOH and Zxe2x80x2 is H. This formula will be referred to as xe2x80x9cFormula II.xe2x80x9d Alternatively, the dispersant is the salt of this dicarboxylic acid. A particularly suitable example of this embodiment is a dicarboxylic acid in which r is 5, s is 7, xxe2x80x2 is 0 and yxe2x80x2 is 0.
It should be appreciated that the inventive dispersant may include a mixture of acids represented by both Formula I and Formula II.
Although dicarboxylic acids or their salts have not been known as effective pigment dispersants for paints, the process of making liquid dicarboxylic acids and their salts is known, as they have been used in a number of industrial and commercial applications, including those requiring the use of surfactants, disinfectants or detergents. A method of making C21 dicarboxylic acids, for example, is disclosed in U.S. Pat. No. 4,156,095 to Jevne, which method is incorporated herein by reference. As discussed therein, C21 dicarboxylic acids may be made by reacting polyunsaturated monocarboxylic fatty acid containing 16 to 20 carbon atoms with an unsaturated component, such as acrylic acid, in the presence of crystalline clay at a temperature between about 180 and 260 degrees Celsius. Also as discussed in U.S. Pat. No. 4,156,095, such dicarboxylic acids may also be made by reacting the polyunsaturated acid portion in a fatty acid mixture, such as linoleic acid derived from a tall oil fatty acid source, with an acrylic acid in the presence of an iodine catalyst at a temperature between 200 and 270 degrees Celsius. The resulting fatty acid dicarboxylic acid mixture may then be separated by distillation into oleic-type fatty acid and dicarboxylic acid fractions.
A further embodiment of the pigment dispersant of the inventive tinting concentrate is a polyacid that may include dimers and/or trimers of unsaturated mono- or dicarboxylic acids. Suitable exemplary acids that may be dimerized or trimerized include mid-sized olefinic acids (e.g., C6 to C20 unsaturated carboxylic acids, such as dimers or trimers, or arylaliphatic carboxylic acids, such as C9 to C20 aliphatic carboxylic acids which include a benzene ring or other aryl group). Examples of such arylaliphatic acids include aliphatic monoesters of acid trimelitic acids formed from substitutions of unsaturated carboxylic acid moieties on benzene or another aryl group.
An additional suitable pigment dispersant of this invention includes a Diels Alder adduct of unsaturated monocarboxylic acid and a hydrocarbon diene. An exemplary dispersant is a Diels Alder adduct of a C14 to C22 unsaturated fatty acid and a C4 to C6 dimer. Additional suitable acids include cyclopentadiene carboxylic acid dimer, linoleic acid dimer, the cycloaddition product of a C8 to C20 dienoic carboxylic acid and a C6 to C18 mono-enoic carboxylic acid.
Another embodiment of the inventive dispersant includes a tall oil fatty acid. Examples of such fatty acids include linoleic fatty acids and oleic fatty acids, or combinations thereof with or without other fatty acid. A suitable example is Rxe2x80x94COOH, where R is a combination of about 38% non-conjugated linoleic fatty acid, 7% conjugated linoleic fatty acid, about 50% oleic fatty acid, about 2% saturated fatty acid and about 2% other component. A commercial example of this tall oil fatty acid is Acitnol FA-3.
A further embodiment of the inventive dispersant includes a polyhydroxy aliphatic monocarboxylic acid. An exemplary acid includes dimethylolpropionic acid. Further embodiments include an adduct of fatty acid and dimethylolpropionic acid; an adduct of dimer acid, Cardura E (the glycidyl ester of a linear or branched-chain alkynoic acid) and dimethylolpropionic acid; the adduct of Diacid 1550 and aminomethylolpropane; the adduct of Diacid 1550 and Cardura E; and adducts of any of the foregoing polyacids and Cardura E.
Useful examples of preferable salts of the polyacid include sodium salts, potassium salts, alkali salts generally, ammonium salts, amine salts and alkanolamine salts. A useful commercial example of such a salt is Westvaco""s Diacid H-240, which is a 40% active potassium salt of Diacid 1550.
As previously mentioned, suitable pigment dispersants alternatively may be provided in the form of an anhydride or derivative.
Suitable anhydrides for use in the present invention include liquid or low melting anhydrides. In addition to the anhydride of the previously mentioned acids, other suitable anhydrides include:
dodecenyl succinic anhydride (DDSA, liquid at room temperature);
octadecenyl succinic anhydride (ODSA, m.p. 69xc2x0 C.);
octenyl succinic anhydride (OSA, m.p. xcx9c50xc2x0 C.);
hexahydropthalic anhydride (HHPA, m.p. 35xc2x0 C.);
methylhexahydro phthalic anhydride (MHHPA);
an eutectic blend of MHHPA and HHPA (m.p. xe2x88x9215xc2x0 C.);
tetrahydro phtalic anhydride (THPA, m.p. xcx9c70xc2x0-74xc2x0 C.); and
methyl-5-norborene-2,3 dicarboxylic anhydride (MMDCA, liquid at room temperature).
Suitable pigment dispersants also include derivatives of the aforementioned acids and anhydrides. Derivitization may be employed, for example, to improve a particular dispersant""s dispersing capabilities. For example, an anhydride dispersant may be reacted with a suitable agent (e.g., an amine) to provide a derivative dispersant. By way of example, octenyl succinic anhydride (OSA) may be reacted with: (i) water to provide an acid; (ii) diethanolamine to provide a monoamide; (iii) dimethyl ethanol amine to provide a monoester, a tertiary amine and a free acid; or (iv) Cardura E (a glycidyl ester of Versatic acid), water and dimethyl ethanol amine to provide a quaternary ester.
The tinting concentrate of the present invention is generally compatible with and may be used for both solvent and latex paints. It is useful with both solvent and latex paints because the monovalent aliphatic hydrocarbon portion of the acid gives the pigment dispersant lipophilic properties, while the pendant and terminal carboxyl group or groups, when neutralized, give it hydrophilic properties, allowing it to disperse pigment in both organic solvent and water, respectively. In addition, the unneutralized molecule can be used as a pigment dispersant in solvent-based colorant dispersions for use in solvent paint.
Pigments for use with the pigment dispersant of the present invention are known in the art. Suitable pigments include titanium dioxide white, carbon black, lampblack, black iron oxide, red iron oxide, yellow iron oxide, brown iron oxide (a blend of red and yellow oxide with black), phthalocyanine green, phthalocyanine blue, organic reds (such as naphthol red, quinacridone red and toulidine red), quinacridone magenta, quinacridone violet, DNA orange, and/or organic yellows (such as Hansa yellow).
The pH neutralizing agent of the inventive universal tinting concentrate is used to maintaining pH of the tinting concentrate in the appropriate range, which is generally between about 6 and 10. The pH neutralizing agent is typically a base. When used with aqueous-based paints and many organic-solvent based paints, the base can act as a neutralizing agent for the acid, such that some or all of the acid is converted to salt form, and contributes to pH balance for the pigment. Typically, the base is added during the tinting operation for the paint. In particular, the base may be any organic or inorganic compound that will neutralize the acid and will be compatible with the binder resins, cross-linkers and other components present in the final paint composition. Bases such as alkali and alkali earth metal hydroxides, organic amines such as triethyl amine, pyridine and alkanolamine, can be used. Alkali and amines are particularly useful in the present invention by neutralizing the organic acid and generally buffering the system. Exemplary bases include ammonium hydroxide, sodium hydroxide, potassium hydroxide and sodium carbonate, which may be used in essentially VOC-free systems. In VOC-containing systems, preferable pH neutralizing agents include VOC-containing amine and alkanolamines, such as triethyl amine, dimethylethanol amine and aminomethylpropanol. Ammonium hydroxide is particularly suitable for neutralizing the organic acid of the inventive tinting concentrate.
The polyether component is optional, such that a mixture of polyacid, pigment and neutralizing agent are sufficient for the universal dispersant of the invention. The polyether, however, is an especially preferred component for dilution and polar-control of the dispersant formulation. The classes of compounds encompassed by the polyether include polyalkyl glycols, such as low to moderate molecular weight polyethylene and polypropylene glycols; polyhydroxy ethers, such as those formed from epoxide polymerization; polysaccharide compounds, such as polysorbitan and polysorbitol; polyalkylene oxides, such as polyethylene and polypropylene oxide.
Rather than using a polyether, a dihydric or polyhydric alcohol may be employed. Ethylene glycol is an exemplary dihydric alcohol. Propylene glycol is an exemplary polyhydric alcohol.
The universal pigment dispersant can be combined with organic solvent-based or aqueous-based vehicle formulations to provide colored paint formulations, examples of which are described in Examples 9 through 14 of preferred embodiments, below. A preferable polyether for the present invention is a linear ethylene glycol polyether of low molecular weight. More preferably, the ethylene glycol polyether has a molecular weight of between about 250 and 800. Most preferably, the polyethylene glycol polyether has a molecular weight ranging from 275 to 325. Medium molecular weight polyethylene glycols are advantageous for use as vehicle because they are substantially free of very low molecular weight volatile organic solvents, which are suspected toxins and/or teratogens. A particularly useful commercial polyethylene glycol is Union Carbide""s PEG 300, having a molecular weight of about 285 to 315. Another useful commercial additive is Humectant GRB-2 from Zenica, which is contains glycerine and nonionic surfactant.
One or more co-surfactants known in the art, including conventional anionic, nonionic, amphoteric surfactants and/or cationic co-surfactants, may also be used, typically constituting between zero to about 15% and preferably from zero to about 10% by weight of the tinting concentrate. A particularly useful co-surfactant for the tinting concentrates of the present invention is lecithin, including water-dispersible lecithin, as lecithin has negligible effect on rheology and rheological modifiers. Depending on the particular tinting concentrate being made and the particular pigments needed to be dispersed, other co-surfactants may be used known for being appropriate surfactants for such pigments. Such additional exemplary co-surfactants include phosphate esters or polyacrylate salts, commercial examples of which include Rhodafac LO-529 from Rhone Poulenc or Nopcosperse 44 from Henkel, respectively. Great care must be used in selecting co-surfactants, as they can have a significant detrimental effect in properties.
A thickener or multiple thickeners may be also used to increase the overall viscosity of the dispersion. The thickener or thickeners should account for more thickeners between about zero and 5% by weight of the tinting concentrate. Exemplary thickeners include cellulose ethers; carboxymethyl cellulose; alginates; caseinates; hydrophobically-modified cellulose ethers; polyethylene oxide; polyvinyl alcohol; polyacrylamide; alkali-soluble acrylics and styrene/maleic anhydrides; alkali-swellable crosslinked acrylic emulsions, such as hydrophobically-modified alkali-swellable emulsions; and nonionic associative thickeners, such as hydrophobically-modified polyurethanes and polyethers. Thickeners for solvent-based dispersants include bentonite clays, organoclays, synthetic silicas, castor oil derivatives, modified acrylic copolymers, polyethylene glycol, polymerized oil derivatives, organic esters, and complex polyolefins.
A preferred thickener for use in latex paints pursuant to the present invention include synthetic hectorite. Particularly useful examples of commercial synthetic hectorite include United Catalysts"" Optigel SH and Southern Clay Products"" Laponite RD. A preferred thickener for use in solvent paints is a cross-linked polyacrylic acid, a particularly useful commercial example of which is BF Goodrich""s Carbopol EZ-1.
In water-based dispersions, a defoaming agent may be added for ease of manufacture.
A biocide may also be added to the dispersant of the present invention to eliminate or inhibit the growth of microorganisms in the paint. Biocide will generally account for between 0 and 1% by weight of the tinting concentrate. Biocidal chemicals include chlorinated hydrocarbons, organometallics, halogen-releasing compounds, metallic salts, organic sulfur compounds, quaternary ammonium compounds and phenolics. A useful commercial example of biocide is Troysan 192.
Water may also be added to the tinting concentrates of the present invention, in an amount needed to make up the free volume. Generally, water may make up between about 0 and 75% by weight of the tinting concentrate volume, depending on the particular tinting concentrate.
In another embodiment of the present invention, a tinting concentrate (e.g., a standard tinting concentrate or a tinting concentrate of the present invention) is provided in an easy to use container. Tinting concentrates are conventionally provided in cans or jars. The tinting concentrate is then manually scooped out of the can or jar by the retail clerk and loaded into a tinting machine. This manual loading method suffers from several disadvantages. First, it is messyxe2x80x94not only may spillage occur when opening a can, but there is significant mess involved when scraping the can out. This mess can quickly cause the paint department to look untidy. In addition, the traditional cans are difficult to fully empty, thereby causing waste. Moreover, the not completely empty cans pose a disposal problem for the retailer.
To avoid these disadvantages, the present invention provides a cartridge-style container. Suitable cartridge-style containers for use with tinting concentrates include xe2x80x9ctubes,xe2x80x9d xe2x80x9csyringes,xe2x80x9d and xe2x80x9ccaulkingxe2x80x9d -type cartridges. These containers are preferred over traditional cans and jars. More preferably, the cartridge-style container permits the expressing of the concentrate from the container without the need to reach inside the container to scrape the walls of the container clean. Most preferred containers have a nozzle or adapter orifice that facilitates clean entry of the concentrate into the tinting machine.
Suitable containers for use in the present invention include metal and plastic tubes (e.g., xe2x80x9ctoothpastexe2x80x9d style tubes) and caulking-tube cartridges (e.g., cartridges with plungers such as are described, for example, in U.S. Pat. Nos. 5,622,288; 5,560,521; and 5,297,697, which are herein incorporated by reference).

Abstract: where

Abstract: r and s are integers and r+s is 6 to 16;

Abstract: x and y are integers and x+y is 0 to 19;

Abstract: Z is H or COOH; and

Abstract: Zxe2x80x2 is H or COOH.


An isolated and purified DNA molecule comprising a sugarcane bacilliform virus promoter and expression cassettes comprising said promoter are provided. Also provided is a method of using a sugarcane bacilliform virus promoter to express proteins, RNA transcripts, or mixtures thereof, in transgenic plants.

One of the primary goals of plant genetic engineering is to obtain plants having improved characteristics or traits. These characteristics or traits include virus resistance, insect resistance, herbicide resistance, enhanced stability and improved nutritional value, to name a few. Recent advances in genetic engineering have enabled the incorporation of preselected genes into plant cells to impart the desired qualities to the plant of choice. The introduced gene, i.e., xe2x80x9ctransgene,xe2x80x9d is then expressed in the cells of the regenerated plant, so that the plant will exhibit the trait or characteristic encoded by the transgene.
To express a transgene in a plant cell, the proper regulatory signals must be present and in the proper location with respect to the transgene. These regulatory signals generally include a promoter region, a 5xe2x80x2 non-translated leader sequence and a 3xe2x80x2 polyadenylation sequence. The promoter region influences the rate at which the RNA product of the transgene, and resultant protein product of the transgene, is made. Promoter activity also can depend on the presence of several other cis-acting regulatory elements which, in conjunction with cellular factors, determine strength, specificity, and transcription initiation site (for a review, see Zawel and Reinberg, Curr. Opin. Cell Biol., 4, 488 (1992)). Strong promoters are able to direct RNA synthesis at a higher rate relative to weak promoters. Constituitive promoters direct RNA production in many or all cell types.
The cauliflower mosaic virus 35S promoter (CaMV35S) is a strong, constitutive promoter in plants (Odell et al., Nature, 313, 810 (1985); Jensen et al., Nature, 321, 669 (1986); Jefferson et al., EMBO J., 6, 3901 (1987); Kay et al., Science, 236, 1299 (1987); Sanders et al., Nucl. Acids Res., 4, 1543 (1987)). This had been shown by detecting substantial levels of reporter gene proteins or mRNAs in extracts prepared from the leaves, stems, roots and flowers of transgenic plants. As a result, the CaMV35S promoter is widely used in the field of plant genetic engineering. Although the CaMV35S promoter appears to be a strong, constitutive promoter in assays involving cell extracts, detailed histological analysis of reporter gene products detectable at the cell and tissue level shows a rather high degree of variability of expression of the gene products in tissues of plants.
CaMV is a caulimovirus, a subgroup of pararetroviruses that has icosahedral capsids and infects only dicots, although the CaMV35 S promoter is a strong promoter in monocots. Sugarcane bacilliform virus (ScBV), Commelina yellow mottle virus (CoYMV) and rice tungro bacilliform virus (RTBV) are badnaviruses, a subgroup of pararetroviruses that have bacilliform capsids and infect mainly monocots. A promoter fragment isolated from CoYMV confers a tissue-specific pattern of expression that is different than the pattern conferred by the CaMV35S promoter. Transformed tobacco plants containing the CoYMV promoter linked to the beta-glucuronidase reporter gene (xe2x80x9cGUSxe2x80x9d; uidA) showed that while the CoMYV promoter is active in all organs, beta-glucuronidase activity occurs primarily in the phloem, the phloem-associated cells, and the axial parenchyma of roots, stems, leaves, and flowers (Medberry et al., Plant Cell, 4, 185 (1992); Medberry and Olszewski, Plant J., 3, 619 (1993)). In contrast, the CaMV35S promoter is active in most cell types (Medberry et al., Plant Cell, 4, 185 (1992); Medberry and Olszewski, Plant J., 3, 619 (1993)). Moreover, the CoYMV promoter is 30% as active in tobacco suspension cells and up to 25% as active in maize suspension cells compared to a duplicated CaMV35S promoter (Medberry et al., Plant Cell, 4, 185 (1992)).
Transgenic rice containing the RTBV promoter linked to the GUS gene showed strong phloem-specific promoter activity. This was consistent with the expression of this promoter in rice protoplasts. However, the RTBV promoter showed only weak activity in maize protoplasts (Bhattacharyya-Pakasi et al., Plant J., 4, 71 (1993); Yin et al., Plant J., 7, 969 (1995)). In contrast, the corresponding CaMV promoter shows strong promoter activity in protoplasts and in almost all tissues of transgenic plants (reviewed by Hohn and Fxc3xctterer, Curr. Opin. Genet. Dev., 2, 90 (1992)).
Thus, what is needed is a highly expressed, constitutive promoter to express transgenes in fertile transgenic monocot and dicot plants.
The present invention provides an isolated and purified DNA molecule comprising a preselected DNA segment comprising a sugarcane bacilliform virus (ScBV) promoter, or a biologically active subunit thereof, that confers constitutively high levels of expression of operably linked preselected DNA segments in both monocot and dicot plants, plant tissue, plant parts or plant cells. While the nucleotide sequence of the genome of ScBV is known (Bouhida et al., J. Gen. Virol., 74, 1 (1993)), the location of a promoter for genomic length viral RNA was not apparent, even after nucleotide sequence comparisons of the ScBV genome with promoter sequences of closely related viruses, such as CoYMV and RTBV. Surprisingly, the ScBV promoter is a strong and constituitive promoter in many cell types, unlike the strong tissue specific expression observed for CoMYV and RTBV promoters. A preferred embodiment of the invention is a preselected DNA segment comprising a ScBV promoter comprising SEQ ID NO:3, i.e., a preselected DNA segment that corresponds to nucleotide positions 5999-7420 of the ScBV genome. As described herein below, the ScBV promoter confers constitutive and vascular gene expression in A. sativa and A. thaliana. Thus, the ScBV promoter can be employed for constitutive or tissue-specific plant and non-plant gene expression in monocots and dicots. For example, the ScBV promoter may be linked to genes which confer to crops resistance against pests which attack crop grasses at the stem, e.g., aphids which vector barley yellow dwarf virus, or to confer tissue-specific resistance to dicotyledonous hosts, in which organs such as the roots are targeted by pathogens, e.g., soybean cyst nematode.
As used herein, xe2x80x9cScBVxe2x80x9d includes any non-enveloped, bacilliform, DNA-containing badnavirus capable of systemically infecting Saccharum or related genera. Other distinguishing features of badnaviruses are described by Lockhart and Olszewski, in The Encyclopedia of Virology, Webster and Granoff (eds.), Academic Press, New York, N.Y. (1994)).
As used herein, the term xe2x80x9cScBV promoterxe2x80x9d means a nucleotide sequence which, when that sequence is operably linked to a preselected DNA segment that encodes a protein, RNA transcript, or mixture thereof, results in the expression of the linked preselected DNA segment, i.e., the encoded RNA and/or protein. A preferred ScBV promoter has at least about 60%, preferably at least about 80%, more preferably at least about 90%, and even more preferably at least about 95%, nucleotide sequence identity to SEQ ID NO:3, SEQ ID NO:4 or SEQ ID NO:5. Another preferred embodiment of the invention is a ScBV promoter which comprises the minimum number of contiguous nucleotides which initiate RNA transcription.
As used herein, xe2x80x9cbiologically activexe2x80x9d means that the promoter has at least about 0.1%, preferably at least about 10%, and more preferably at least about 25%, the activity of the ScBV promoter comprising SEQ ID NO:3, SEQ ID NO:4 or SEQ ID NO:5. The activity of a promoter can be determined by methods well known to the art. For example, see Medberry et al., Plant Cell, 4, 185 (1992); Medberry et al., The Plant J., 3, 619 (1993); Sambrook et al., In: Molecular Cloning: A Laboratory Manual (1989); McPherson et al., U.S. Pat. No. 5,164,316.
Further provided is an expression cassette comprising a first preselected DNA segment comprising a ScBV promoter functional in a host cell, operably linked to a second preselected DNA segment encoding a protein, RNA transcript, or a combination thereof. A preferred host cell is a plant cell, e.g., a monocot or dicot cell. Another preferred embodiment of the invention is an expression cassette comprising a ScBV promoter operably linked to a selectable marker gene. Yet another preferred embodiment of the invention is an expression cassette comprising a ScBV promoter which comprises SEQ ID NO:3.
The invention also provides methods of selecting stable genetic transformants from transformed plant cells and methods of producing fertile transgenic plants from said transformed plant cells. The method for producing transformed plant cells comprises introducing into regenemble plant cells a recombinant DNA segment which comprises a first preselected DNA segment comprising a ScBV promoter operably linked to a second preselected DNA segment so as to yield transformed cells. Then a transformed cell line is identified or selected. Exemplary transformation methods include the use of microprojectile bombardment to introduce a preselected DNA segment, encoding a phenotypically observable or detectable trait, operably linked to the ScBV promoter, into regenerable monocot plant cells. A preferred embodiment of the invention is a method whereby the expression of the recombinant DNA segment in the transformed cells imparts a phenotypic characteristic to the transformed cells, such as herbicide or antibiotic resistance.
As used herein, the term xe2x80x9crecombinant DNA segmentxe2x80x9d refers to a nucleic acid, i.e., to DNA, that has been derived or isolated from any appropriate tissue source and isolated from association with other components of the cell, such as nucleic acid or protein. The DNA may be subsequently chemically altered in vitro, so that its sequence is not naturally occurring, or corresponds to naturally occurring sequences that are not positioned as they would be positioned in a genome which has not been transformed with exogenous DNA, so that it can be sequenced, replicated, and/or expressed.
A preferred isolated recombinant DNA segment includes a first preselected DNA segment comprising a ScBV promoter functional in a plant cell operably linked to second preselected DNA segment comprising a selectable marker gene. Another preferred isolated recombinant DNA segment includes a second preselected DNA segment that corresponds to a gene that is already present in the plant genome, or one which is not normally present in the plant genome, which confers an agronomically useful phenotype to the plant, e.g., pest resistance. If the preselected DNA segment is normally present in the plant genome it may not be expressed or not highly expressed. Thus, the preselected DNA segment is introduced so as to alter the expression of the protein or RNA transcript encoded by the preselected DNA segment in the cells of the plant.
The invention also provides a method for producing a fertile transgenic plant. The method comprises introducing a recombinant DNA segment which comprises a first preselected DNA segment comprising a ScBV promoter operably linked to a second preselected DNA segment into regenerable plant cells so as to yield regenerable transformed cells. A population of transformed cells is selected or identified and a fertile transgenic plant is regenerated therefrom. The recombinant DNA segment is transmitted through a complete sexual cycle of said transgenic plant to its progeny so that it is expressed by the progeny plants. Thus, the invention also provides a transgenic plant, and seed, other plant parts, tissue, and progeny plants derived therefrom.
The transgenic plants of the invention include, but are not limited to, a transgenic T0 or R0 plant, i.e., the first plant regenerated from transformed plant cells, a transgenic T1 or R1 plant, i.e., the first generation progeny plant, and progeny plants of further generations derived therefrom which comprise and express the recombinant DNA segment. Microprojectile bombardment can be used to introduce the recombinant DNA segment into regenerable monocot cells, while Agrobacterium-mediated DNA transfer can be used to introduce the recombinant DNA into regenerable dicot cells.
Also provided is a transformed monocot or dicot plant, the cells of which comprise a recombinant DNA segment comprising a first preselected DNA segment comprising a sugarcane bacilliform virus promoter operably linked to a second preselected DNA segment The second preselected DNA segment is expressed in the transformed cells in an amount that is different than the amount in the cells of a plant in which cells only differ from the transformed cells in that the recombinant DNA segment is absent Such cells can include untransformed cells of the same part of the transformed, or transgenic, plant, in some cases. The second preselected DNA segment is expressed so as to render the transformed plant or a part thereof identifiable over the corresponding untransformed plant or part thereof.
The recombinant DNA segment is transmitted through a complete normal sexual cycle of the transformed plant to the next generation.
Also provided is a method comprising obtaining progeny from a fertile transgenic plant obtained by the method described hereinabove.
As used herein, the term xe2x80x9ctransgenicxe2x80x9d or xe2x80x9ctransformedxe2x80x9d with respect to a plant cell, plant part (including seed), plant tissue or plant means a plant cell, plant part, plant tissue or plant which comprises an isolated, purified preselected DNA segment which has been introduced into the genome of a plant cell, plant part, plant tissue or plant by a xe2x80x9cgenetic engineeringxe2x80x9d transformation method. That is, the genome of a transgenic plant cell, plant part, plant tissue or plant has been augmented by at least one preselected DNA segment. The term xe2x80x9cwild type,xe2x80x9d xe2x80x9cnative,xe2x80x9d or xe2x80x9cnontransgenicxe2x80x9d refers to an untransformed plant cell, plant part, plant tissue or plant, i.e., one where the genome has not been altered by the presence of the preselected DNA segment.
The transformation of the plants in accordance with the invention may be carried out in essentially any of the various methods available to those skilled in the art of plant molecular biology. These include, but are not limited to, microprojectile bombardment, microinjection, electroporation of protoplasts or cells comprising partial cell walls, silicon carbide fiber-mediated DNA transfer and Agrobacterium-mediated DNA transfer. Plants useful in the practice of the invention include, but are not limited to, oat, wheat, soybean, corn, tobacco, rice, barley, potato, tomato, lettuce, oilseed rape, cotton, flax, sugar beet, sorghum, sunflower, alfalfa, millet and rye.


An optical semiconductor device includes a silicon oxide layer configured to be formed on a substrate; an optical waveguide part configured to be formed on the silicon oxide layer; a cladding layer configured to be formed covering the optical waveguide part; and a semiconductor laser configured to be disposed on the substrate. Laser light emitted from the semiconductor laser enters the optical waveguide part. The optical waveguide part increases transmittance of light when the wavelength becomes greater within an oscillation wavelength range of the semiconductor laser.

A semiconductor laser is used as a light source for optical communication and data processing in optical fiber communication, optical interconnect, and the like. In general, a semiconductor laser has fluctuation in emitted optical output and wavelength depending on environmental temperature, for example, emitted optical output becomes less when temperatures go higher. To cope with such temperature fluctuations of a semiconductor laser, there are methods with which a stable characteristic can be obtained even when the environmental temperature changes which include a method of adjusting temperature using a TEC (thermoelectric cooler), and a method using an APC (Automatic Power Control) circuit. Also, as a method other than the above, a semiconductor laser is disclosed that uses a reflection mirror having wavelength dependency to make a stable level of emitted optical output in response to wavelength shifts due to environmental temperature changes.


A video frame transmitting system transmitting at least one output video frame to a display based on content of at least one input video frame. The video frame transmitting system has a display driver receiving an active input video frame and outputting the active input video frame as the output video frame to the display. The video frame transmitting system comprises: an application processor, receiving the input video frame, for determining the input video frame as the active input video frame if the content of the input video frame is different from content of a previous input video frame, and for determining the input video frame as a skip input video frame if the content of the input video frame is the same as the content of the previous input video frame. The application processor outputs the active input video frame to the display driver but does not output the skip input video frame.

The present application relates to a video frame transmitting system and a video frame transmitting method, and particularly relates to a video frame transmitting system and a video frame transmitting method that can skip transmitting at least one video frame without a video frame buffer.
A related video displaying system usually comprises an application processor and a display driver. The application processor (ex. a processing unit) receives input video frames and transmits the input video frames to the display driver. The display driver receives input video frames from the application processor and writes the input video frame to each line of the display. The display driver can control the displaying operation of the display as well.
FIG. 1 is a schematic diagram illustrating related art video frame transmitting methods. As shown in FIG. 1, the application processor transmits every video frame to the display driver (i.e. all video frames F_1-F_n are treated as active input video frames). However, the display driver may only transmit part of the input video frames to the display (ex. only video frames F_1, F_4, and F_7). Therefore, the application processor wastes much power to transmit video frames which will be skipped later.
Also, if such video frame transmitting method is applied to a touch control apparatus with a touch control panel (ex. a smart phone), the user may perceive a delay issue for the display. For more detail, if the user touches the touch control panel at a time point t1, and content of the video frame F_6 is correspondingly different from content of the video frame F_5 at a time point t2. However, the video frame F_6 is still skipped by the display driver and not displayed on the display. Therefore, the applicant may feel the displaying operation is delayed. Such delay issue becomes worse if the video frame rate is low.
Furthermore, if the video frame transmitting method follows a MIPI (Mobile Industry Processor Interface) standard, a video frame buffer must be included in the video displaying system to skip the video frame. For more detail, the input video frames from the application processor are registered in the video frame buffer, and the video frames are fetched from the video frame buffer and transmitted to the display when the video frames are active input video frames. Such structure increases the size and cost of the video frame transmitting system.

Video frame transmitting system and video frame transmitting method


A cap for sealing a container having a threaded spout. The cap is arranged so that it can be snapped onto and off the spout and so that it can also be screwed on and off the spout.

In the catering and fast food industries many different food products are purchased in plastic bags, pouches, bladders and bag-in-box containers. Examples of such typical food products include tomato products, citrus products, soft drink syrups, fruit purees, fruit sauces and flavouring. These types of containers are advantageous over other packaging containers because they can be used in ambient, hot fill and aseptic process applications. Additionally, such containers are light weight, easy to transport and cost efficient process.
Typically these plastic bags, pouches, bladders and bag-in-box containers are made from a combination of polymer materials which may, in some instances, be coated with or contain gas barrier materials. The bags or pouches are generally fitted with a plastic pouring spout which is rigidly attached to the bag. The spout is sealed by a cap. The cap is arranged to be secured to the spout in a manner whereby it can be "snapped off" mechanically prior to filling the bag with product and then reapplied or "snapped on" by applying a downward force onto the cap and the axially aligned spout. The cap has a centrally located plug which seals the spout and a skirt extending from the top of the cap. The skirt is provided to prevent foreign matter from entering the exterior of the spout. It is standard practice for the plug to engage in the aperture of the spout in a manner whereby an hermetic seal is formed.
As stated above, during the filling operation the cap is removed mechanically. Removal typically is achieved using a mechanical jaw to uncap the cap. However, when the product is used by the end user, the cap must be removed manually. Given the nature of the connection between the plug and the spout and the configuration thereof, it is extremely difficult to remove the cap by hand. Considerable force is required to lever the cap off the spout. As these types of bags are used in many of the fast food chains, typically, the person trying to remove the cap is a youth who may not be strong enough to remove the cap. In order to overcome this problem uncapping tools are sometimes used. However, it is still quite difficult to remove the cap and often the uncapping tool can't be found when needed.
It is also quite common for users to slash the bag to empty the product, rather than remove the cap and pour the product through the spout. Although this is not a problem when the entire contents of the bag are to be used, in some situations it is desirable to only use a small proportion of the contents and to store the remainder in the bag in a refrigerator. This is particularly a concern to caterers who have a limited turnover. In other situations, it is necessary to pour the contents into a dispenser and thus is not particularly desirable to slash the bag.
The present invention seeks in one aspect to provide an improved cap which can be easily removed by hand from the spout of the bag or container while still enabling the cap to be removed and replaced mechanically on a filling machine.