A lockable filler cap assembly for fuel tanks and other fluid-holding containers. The assembly is readily adaptable to function as a normally operating non-locking filler cap and to function as a locked filler cap. The lockable filler cap assembly includes a cap having a receptacle whereby an insert may be placed and locked into the receptacle. In the locked condition, a shield on the insert covers at least a portion of the cap, thereby discouraging access to the cap for its removal and, in turn, access to the contents of the associated tank.

The present invention relates to a lockable filler cap assembly for fuel tanks and other fluid-holding containers.
Typically, an opening is made into the wall of such a tank. A substantially cylindrical sleeve is inserted into the opening and the sleeve is permanently attached to the tank to become a filler tube. The filler tube can be threaded on its inside surface which is mated with a filler cap having a complementary threaded portion on its outside surface. The threaded segments are typically cut as right hand threads, meaning the filler cap is removed by rotating the cap counterclockwise. Conversely, the filler cap is secured to the filler tube by engaging the complementary threaded portions of the cap and the filler tube and rotating the cap in a clockwise direction. In an alternative arrangement, the cap can be secured by a simple thread on the filler tube engaging lugs on the cap wherein only a quarter turn is required to effect the seal between the cap and the filler tube.
In numerous fluid handling and storage applications, it is desirable to seal the opening of a tank, such as the threaded conduit of a filler tube, with a closure which cannot be readily removed by unauthorized persons. Unauthorized access is desirable to prevent the theft of the contents of the tank as well as to prevent vandalism or sabotage by the addition of materials or foreign fluids to the contents of the tank. Locking caps for fuel tanks and similar containers are well known.
The present invention is an apparatus to provide a lockable cap assembly for fuel tanks and other fluid-holding vessels. The present invention is a lockable cap assembly providing an adaptable, interchangeable, easy to operate, and durable locking mechanism suitable for locking a cap onto the filler tubes of tanks carrying liquids such as motor fuels, water, wastewater, and sewage.
An object of the present invention is to provide an assembly that is readily adaptable to function as a normally operating non-locking filler cap and to function as a locked filler cap. The present invention includes a receptacle whereby an insert may be placed and locked into the receptacle. In the locked condition, a shield on the insert covers at least a portion of the cap, thereby discouraging access to the cap for its removal and, in turn, access to the contents of the associated tank.
Such an arrangement as described above is demonstrated in an example embodiment of the present invention wherein the cap has the profile of a marine deck fill plate. In typical usage, the marine deck fill plate is removed from its associated filler opening by engaging a pair of holes on the deck plate with a pair of complementary sized pins on a tool such as a wrench. Usually by turning the wrench and cap counterclockwise, the cap can be removed from its threaded engagement between an outside diameter of the cap and an inside diameter of the filler tube. Without the insert of the present invention placed into the receptacle of the cap, the cap is removable and replaceable in the same manner as any typical marine deck fill plate. To lock the cap of, the example embodiment to the filler tube of a boat or any other tank using a typical marine deck fill plate, an insert with a lock is placed into the receptacle of the cap. The insert includes a shield that at least covers the pair of holes on the deck plate profile of the cap. By locking the insert into the receptacle, removal of the cap is discouraged since the typical means of removal of the cap, i.e., the wrench or other similar tools as mentioned above, cannot be used since the shield of the insert covers and prevents usage of the pair of holes on the deck plate profile. In addition, the shield of the insert can be sized to completely cover the cap or to form a flushmount with the vicinity of the tank filler opening, thereby making an assembly that is resistant to prying or removal by pliers and other adaptable tools.
The locking of the insert into the cap of the present invention is provided by a lock being placed within a complementary opening inside the insert such that a latch operatively connected to the lock and placed in the locked position will protrude through a second opening to a position beyond the outside diameter of the insert and into an axially aligned groove in the receptacle of the cap. In this manner, the insert is secured within the receptacle of the cap of the present invention.
An object of the present invention is to provide an interchangeable assembly between the cap and the insert with the lock of the present invention. In this regard, the insert with the lock may be removed from a first cap and used in a second cap having the same sized receptacle for receipt of the insert with the lock. In this instance, the filler tubes associated with the first cap and the second cap, respectively, can always remain sealed with a normally functioning filler cap and access to a given tank is restricted only by the decided placement and usage of the locked insert. Such interchangeability can be useful in situations involving access to fuel tanks for rental vehicles and fleet vehicles, or for occasions requiring lockout and tagging procedures.
Another manner for securing the filler cap can be described in a second example embodiment of the present invention. As described earlier with regard to the operation of a marine deck plate, in this embodiment the shield of the insert may include a pair of holes as are found on the typical deck plate. In this example, the insert with the lock rotates freely within the cap when the cap is in the secure or "locked" setting. Since the shield on the insert spins freely within the cap, a wrench designed to engage a pair of holes on the deck plate with a pair of complementary sized pins would only act to spin the insert within the cap. However, when the insert is locked into the cap by engagement of a latch within a latch slot on the cap, the assembly comprised of the insert with lock and the cap will move as an entire unit. As a result, the assembly is removable and replaceable in the same manner as a typical marine deck fill plate.
An object of the present invention is to provide a locking filler assembly that can be readily adapted to pre-existing fillers on tanks. In addition the assembly can be made from any of a variety of materials such as metal, metal alloys, plastic, and reinforced plastic that are typically used to make a filler caps. The present invention is readily adaptable for use in corrosive environments such as in a marine application with exposure to salt water.
As is the state of the art, a mechanical seal between the filler tube and the cap can be obtained by close physical tolerances between the threaded portions of the filler tube and the cap. The seal may also be enabled or supplemented with sealing materials such as rubber, rubber compounds, rubber-containing mixtures, springs, deformable materials, and compressible materials.
In addition to the novel features and advantages mentioned above, other objects and advantages of the present invention will be readily apparent from the following descriptions of the drawings and preferred embodiments.


An olefin metathesis catalyst consists essentially of a transition metal or oxide thereof supported on a high purity silica support possessing low amounts of acidic or basic sites such that in the reaction of pure butene-1 over said catalyst under metathesis reaction conditions the reaction possesses a weight selectivity to hexene-3 of at least 55 wt %.

1. Field of the Invention
The present invention relates to a supported catalyst for the metathesis, or disproportionation, of olefin(s), and to a metathesis process employing the catalyst.
2. Description of the Related Art
The metathesis, or disproportionation, of olefin(s) is a reaction in which one or more olefinic compounds are transformed into other olefins of different molecular weights. The disproportionation of an olefin with itself to produce an olefin of a higher molecular weight and an olefin of a lower molecular weight is also referred to as self-disproportionation. For example, propylene can be disproportionated to ethylene and cis- and trans-2-butene. Another type of disproportionation involves the cross-disproportionation of two different olefins to form still other olefins. An example would be the reaction of one molecule of 2-butene with one molecule of 3-hexene to produce two molecules of 2-pentene.
When olefins are contacted with metathesis catalysts, the reactions proceed according to a specific structural relationship depending upon the character of the feedstock. The reaction is generally considered to proceed using a four-centered active site on the catalyst. The olefinic double bonds line up on opposite sides of the four-centered site. The reaction proceeds under equilibrium conditions with the bonds exchanging sides of the four-centered site and thusly exchanging the hydrocarbon groups attached to one end of the double bond with the groups attached to the other olefin. For example, 2-butene if reacted with ethylene can form two propylene molecules as shown by equation (1) where each corner of each box in equation (1) represents one of the four active sites on the catalyst:
Extending this concept to any number of olefins, one can see that depending upon the nature of the R group attached to the double bonds, different olefins are formed with strict adherence to the exchange of R groups around the double bond. Thus, olefin R1-Cxe2x95x90Cxe2x80x94R2 when reacted with olefin R3-Cxe2x95x90Cxe2x80x94R4 forms an olefin of R1-Cxe2x95x90Cxe2x80x94R3 and an olefin of R2-Cxe2x95x90Cxe2x95x90xe2x80x94R4 This is illustrated in equation (2) where each corner of each box in equation (2) represents one of the four active sites on the catalyst:
One skilled in the art can imagine many potential reactions over the entire range of possible olefin pairs.
In addition to the metathesis reactions, however, it is not uncommon for various side reactions to occur. One such reaction is an oligomerization reaction where olefins combine to form larger olefins. This reaction, if the olefin grows large enough, leads to fouling of the catalyst as the active sites are blocked. Another reaction that could occur is the double bond isomerization of the olefin. In this case, the position of the double bond shifts within the hydrocarbon chain. Examples are the isomerization of 1-butene to 2-butene and 3-hexene to 2-hexene. If this occurs, the number and character of the olefins available for metathesis changes. With olefins having different R groups available, different reaction products can be formed. The isomerization side reaction leads to a loss in the selectivity of the metathesis reaction to the products defined by the structure of the feedstock olefins.
For example, if the feedstock to the metathesis reaction was essentially pure 1-butene, the primary products of that reaction would be ethylene and 3-hexene. No other products would form. If, however, some portion of the 1-butene was isomerized to 2-butene, then 1-butene could react with 2-butene to form propylene and 2-pentene. The propylene and pentene represent non-selective products.
The ability to control unwanted side reactions allows the process designer to selectively produce specific products based upon the purity and character of the feedstocks. In many cases this is important to maximize the value of a particular reaction. An example of such a process where selectivity is critical is the production of linear alpha olefins as described in commonly assigned, co-pending U.S. patent application No. 60/263,924, filed Jan. 25, 2001, incorporated by reference herein. That process requires a catalyst with low isomerization activity as described therein.
Many catalysts have been developed for metathesis. For example, those comprising inorganic oxides containing a catalytic amount of a metal or metal oxide have been employed widely for continuous, fixed-bed conversion of olefins. One such catalyst comprises a silica support and an oxide of tungsten. The present invention is based on the discovery of a way to improve the selectivity of metathesis catalysts to specific products.
In accordance with the present invention, a metathesis catalyst is provided which consists essentially of a transition metal or oxide thereof supported on a high purity silica support. xe2x80x9cHigh purity silicaxe2x80x9d is defined as silica possessing low amounts of acidic or basic sites such that in a reaction of pure 1-butene over said catalyst under metathesis conditions the reaction possesses a weight selectivity to hexene-3 of at least 55 wt %. Specifically, the high purity silica support contains less than about 150 ppm magnesium, less than about 900 ppm calcium, less than about 900 ppm sodium, less than about 200 ppm aluminum and less than about 40 ppm iron.
A critical feature of the catalyst of this invention is the purity of the silica support. Certain impurities adversely affect the activity and selectivity of metathesis catalysts. Activity-affecting and selectivity-affecting impurities such as aluminum and iron form acidic sites that will act as sites for olefin isomerization. Alkali metal impurities such as sodium and alkaline earth metal impurities such as calcium and magnesium form basic sites that also act as double bond isomerization catalysts at temperatures employed in metathesis reactions. The amounts of activity-affecting impurities in the catalyst of the invention are substantially below the amounts of such impurities present in conventional silica supports currently employed in the preparation of metathesis catalysts. As a result, the catalyst of the invention exhibits superior selectivities to the desired metathesis reaction products, and minimizes the production of undesired double bond isomerization reaction products.
The lower impurities levels of the catalysts of this invention also lead to a more environmentally friendly catalyst in which the trace elements leachability rates upon landfilling of the fully spent catalysts will be lower than those of the commercial silica formulations.
The high purity silica support utilized in the preparation of the metathesis catalyst of the invention possesses low amounts of both acidic and basic sites (preferably essentially no acidic and basic sites) and thereby improves the selectivity of the metathesis reaction and minimizes undesirable double bond isomerization.
By xe2x80x9clow amountxe2x80x9d of acidic and basic sites on the support, it is meant that the silica support possesses less than about 150 ppm magnesium (measured as the element), less than about 900 ppm calcium (measured as the element), less than about 900 ppm sodium (measured as the element), less than about 200 ppm aluminum (measured as the element) and less than about 40 ppm iron (measured as the element). Preferably, the high purity support possesses less than about 100 ppm magnesium, less than about 500 ppm calcium, less than about 500 ppm sodium, less than about 150 ppm aluminum and less than about 30 ppm iron. More preferably, the high purity support possesses less than about 75 ppm magnesium, less than about 300 ppm calcium, less than about 300 ppm sodium, less than about 100 ppm aluminum and less than about 20 ppm iron. High purity silica within the scope of this invention can be commercially obtained as chromatographic grade silica.
Transition metals and oxides thereof that can be employed herein are known and include, but are not limited to, tungsten, molybdenum, rhenium, oxides thereof and mixtures thereof. Tungsten oxide is particularly preferred. The oxides of these metals are typically formed from oxide precursors which are subsequently converted to the oxides by calcination. Suitable precursors include compounds which are convertible to the oxide form under calcination, such as, for example, the halides, oxides, sulfides, sulfates, nitrates, acetates, ammonium salts, and the like, and mixtures of any two or more thereof. Ammonium meta tungstate is preferably utilized as the precursor for the tungsten deposited upon the high purity support.
The transition metal or oxide thereof is deposited on the high purity support material in an amount that varies between 1 and 20% by weight, based on the weight of the entire catalyst.
The metathesis catalyst utilized herein should not be intentionally admixed with double bond isomerization catalysts, including supported or unsupported phosphoric acid, bauxite, zinc oxide, magnesium oxide, calcium oxide, cerium oxide, thorium oxide, titanium oxide, cobalt oxide, iron oxide, or manganese oxide, and the like, since such isomerization catalysts will significantly interfere with the desired metathesis reaction.
The high purity silica support and transition metal or oxide thereof can be contacted in any suitable manner. For example, the support and a solution containing the transition metal or oxide thereof (or precursor thereof) (hereinafter referred to simply as the transition metal) can be mixed in an open vessel, then any excess liquid can be decanted or removed by filtration. Alternatively, the technique of incipient wetness can be employed whereby only enough liquid is employed to thoroughly wet the support, with no free residual liquid. Thus, only as much transition metal-containing solution is employed as the support can absorb. This can be accomplished, for example, by spraying the solution over a quantity of support which is being tumbled in a rotating, baffled drum. Such treatment can also be carried out by simply pouring a predetermined quantity of the solution over a quantity of the silica support in an open vessel. Alternatively, a measured quantity of support could be added to a volume of transition metal-containing solution such that all of the liquid is imbibed by the added support. Other techniques are known to those skilled in the art and can also be employed. For example, a quantity of support may be placed in a tubular reactor, a volume of transition metal-containing solution may be percolated there through, followed by further treatment/activation as necessary.
The conditions of high purity silica support/transition metal-containing solution contacting are not critical. Any temperature and any period of contact time are suitable. For convenience, contacting is generally carried out at about room temperature, although higher or lower temperatures can be employed. A time period sufficient to allow the support and reagents to come into intimate contact is all that is necessary. Thus, the support and solution may be brought into contact for as little time as a few seconds to several hours or more, as convenient.
Following contact of the high purity silica support and transition metal-containing solution, any excess liquid can be removed by suitable means, such as, for example, decantation, filtration or the like. The treated support can be dried to removed absorbed solvent. Any suitable means, as well known by those skilled in the art, may be employed such as, for example, oven drying, passing a vigorous stream of dry (moisture-free) gas over the treated support and the like. For example, the supported catalyst can be dried by heating at an elevated temperature of, e.g., about 200xc2x0 C. or higher by passage of an inert gas such as nitrogen over the material. This can be accomplished within the reactor or in other suitable catalyst preparation equipment.
Calcination, when used, is conducted by heating the transition metal oxide or precursor thereof in the presence of an oxygen-containing gas, such as, for example, air, under conditions sufficient to activate the metal oxide, e.g., tungsten oxide, or to convert the transition metal compound present, e.g., tungsten, to the activated metal oxide form. Temperatures in the range of about 350xc2x0 C. to about 800xc2x0 C. are generally satisfactory for such calcinations. The time for subjecting the transition metal oxide to calcination is an amount of time sufficient to activate the catalyst. Anywhere from a few minutes to several hours is suitable. Typically, about 15 minutes to about 20 hours of calcination will be sufficient. Preferably, for the most efficient use of reaction equipment, the transition metal oxide will be subjected to calcination for about 30 minutes to about 6 hours at temperatures less than 650xc2x0 C. Higher temperatures while acceptable can result in loss of support surface area and reduction in catalyst activity. Typically less time is required at higher temperatures and vice versa.
After calcination, the metathesis catalyst is optionally treated under reducing conditions such as, for example, with carbon monoxide, hydrogen, or a hydrocarbon at a temperature in the range of from about 350xc2x0 C. to about 550xc2x0 C. to enhance the metathesis activity of the catalyst. Such reducing treatment is carried out preferably in the range of from about 400xc2x0 C. to about 450xc2x0 C., because good catalyst activation with relatively short activation periods of about one to about six hours can be achieved. Such optional reducing treatment can suitably be carried out for a period of time ranging from about 1 minute to about 30 hours. If desired, the calcined catalyst can be further treated with an inert gas such as nitrogen prior to use in a metathesis reaction to remove adsorbed materials from the catalyst which may have a detrimental effect on the selectivity of the catalyst for metathesis reactions. Such materials are water or CO2 that could be adsorbed by the catalyst through contact with the ambient environment.
Further in accordance with the invention, a process is provided in which one or more olefins capable of undergoing a metathesis reaction are contacted with the catalyst of the invention under metathesis reaction conditions which minimize or eliminate double bond isomerization reactions to provide a metathesis reaction product. In particular, such catalyst and conditions are selected such that in a reaction of pure butene-1 over said catalyst under metathesis reaction conditions the reaction possesses a weight selectivity to hexene-3 of at least 55%, and preferably at least 60% or greater.
Olefins employed in the practice of the process of the invention will generally possess up to about 30 carbon atoms, preferably from about 3 to about 25 carbon atoms, and more preferably from about 4 to about 18 carbon atoms. Some specific examples of olefins which may be employed are propylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 2,4,4-trimethyl-2-pentene, 2,4,4-trimethyl-1-pentene, 1-hexene, 2-heptene, 1-octene, 2-nonene, 1-dodecene, 2-tetradecene, 1-hexadecene, 1-phenyl-2-butene, 4-octene, 3-eicosene, 3-hexene, 2-methy-4-octene, 1,5,9,13,17-octadecapentene, 8-cyclopentyl-4,5-dimetyl-1-decene, 3-heptene, and the like, and mixtures thereof.
The metathesis reaction conditions in accordance with the invention include a temperature of from about 50xc2x0 C. to about 600xc2x0 C., preferably from about 200xc2x0 C. to about 400xc2x0 C., a weight hourly space velocity (WHSV) of from about 3 to about 200, preferably from about 6 to about 40, and a pressure of from about 10 psig to about 600 psig, preferably from about 30 psig to about 100 psig. The reaction may be carried out by contacting the olefin(s) with the catalyst in the liquid phase or the gas phase depending on structure and molecular weight of the olefin(s). If the reaction is carried out in the liquid phase, solvents or diluents for the reaction can be used. Aliphatic saturated hydrocarbons, e.g., pentanes, hexanes, cyclohexanes, dodecanes and aromatic hydrocarbons such as benzene and toluene are suitable. If the reaction is carried out in the gaseous phase, diluents such as saturated aliphatic hydrocarbons, for example, methane, ethane, and/or substantially inert gases, e.g., nitrogen, argon, can be present. Preferably, for high product yield, the reaction is conducted in the absence of significant amounts of deactivating materials such as water and oxygen.
The contact time needed to obtain a desirable yield of metathesis reaction products depends upon several factors such as the activity of the catalyst, temperature, pressure, and the structure of the olefin(s) to be metathesized. Length of time during which the olefin(s) are contacted with catalyst can conveniently vary between 0.1 seconds and 4 hours, preferably from about 0.5 sec to about 0.5 hrs.
The process can be conducted batch-wise or continuously with fixed catalyst beds, slurried catalyst, fluidized beds, or by using any other conventional contacting techniques.
In accordance with a preferred embodiment of the present invention, butene-1 is contacted with the catalyst of the invention and reacted under metathesis reaction conditions under conditions that minimize isomerization of the butene-1 to produce a reaction product that includes ethylene and hexene-3. The reaction is:
1-C4xe2x88x92+1-C4xe2x88x92xe2x86x92C2xe2x88x92+3-C6xe2x88x92
The butene-1 starting material may be a pure or impure feed. The portion of the feed that contains reactive C4 olefins is preferably at least 90% and more preferably at least 95% butene-1. Non-reactive components, for example normal butane, may dilute the olefins in the feedstock. Most preferably, the butene-1 starting material is a pure feed, i.e., the butene-1 is present in an amount of at least 99%.
The invention now will be described with respect to the following examples; however, the scope of the present invention is not intended to be limited thereby.

Catalyst for the metathesis of olefin(s)


A system, method, and computer-readable medium, is described that enables a parallelizing scheduler to analyze database instructions, determine data dependencies among instructions, and provide a multi-threaded approach to running instructions in parallel while preserving data dependencies.

Databases are an essential part of computing and information management. Databases provide data storage and an interface to insert, update, delete, and retrieve the data found therein. Generally, a database processes instructions sequentially, one instruction after another. This is at least in part due to the typical operation of a database. Typically, a user will request information from the database as it is needed, insert a new record in the database as it is created, update a database record as soon as an edit is received, or delete a record as soon as it is no longer needed. Sequential operation of a database does have some advantages. For instance, data dependency is easily maintained. Because each statement executes one after another, there is little worry of retrieving out-of-date information. Not all database operations, however, need to occur sequentially. In fact, most probably do not.
Due to the data integrity requirements of a database, each database vendor has its own methods of providing data quality assurances through the use of locking algorithms to ensure a particular database table, record, or field is not read if it is currently being accessed for a write operation. Processing instructions as they are received results in execution inefficiencies because a read operation may be unrelated to the next write operation or two sequential write operations may be on two different tables; these operations could be executed concurrently, reducing execution cycles, execution time, and execution overhead. The inefficiencies increase the cost of hardware and software required because more database servers are required to handle increased loads.
These inefficiencies are also passed on to a backup database and a developmental database. For example, a production database server or cluster of servers might pass the instructions it receives to a backup database environment or developmental database. The backup database or developmental database must handle the same write load as the production database. This could result in significant costs in secondary database servers or clusters to support the backup or developmental databases. A method is needed to reduce the costs of operating such systems.
With parallelization as an intermediary, the number of instruction cycles on the backup or developmental database can be significantly reduced, allowing for cheaper hardware and less additional software licenses. The database instructions may first be passed to the parallelizing scheduler and then to the secondary database which may then run the instructions in parallel in a multi-threaded operation. Another example where parallelization would be useful is when a database fails, because restoring the database from transaction logs can take a significant amount of time. Parallelization can optimize the transaction logs to significantly reduce the overall number of cycles, allowing for faster recovery. Transaction logs may even be parallelized in advance. Parallelization can also help further reduce costs by enabling the database operator to keep a backup database on a different database platform. For example, the production environment might use an expensive license based database, but with parallelization the backup may use an inexpensive, custom, or free database to greatly reduce operating costs. With the proliferation of dynamic web sites, parallelization implemented at the web site script code level would reduce the load on a database, prolonging the longevity of equipment without the need to upgrade as quickly or expand into more complicated multiple database setups. Finally, a database product could benefit from using a parallelizing scheduler in the processing of commands. Rather than simply processing commands sequentially, the parallelizing scheduler may store the commands in memory, optimize the commands, and run them in parallel.
A simple example is where (i) data is written to Table A and (ii) data is read from Table B. Because these two instructions have no dependency on each other, they can be executed in parallel, rather than sequentially. In general, consider five basic SQL commands: SELECT, INSERT, UPDATE, DELETE, and CREATE. At their core these correspond to operations to READ, WRITE, WRITE, WRITE, and WRITE on the database, respectively. Now, consider a table with two columns, "name" and "phonenum." When a READ statement requests data from the table after a WRITE statement to the table, then a true data dependency exists, i.e., executing the READ statement before the WRITE statement may result in unexpected results. When a WRITE statement to the table follows a READ statement to the table, then anti-dependency exists, i.e. executing the READ statement after the WRITE statement may result in unexpected results. When a WRITE statement to the table follows another WRITE statement to the table, then output dependency exists, i.e., executing the WRITE statements in the reverse order will result in incorrect values in the database. Note that the final combination of statements, the READ after READ statement will never result in a data dependency because the data is the same for each execution. Using these data dependency relationships, sequential database instructions may be construed into in parallel execution levels.

Parallelizing scheduler for database commands


The present invention relates to compositions for the washing of laundry fabrics, the compositions containing anionic surfactants and a cationic detergency enhancing polymer which may be homopolymer or copolymer.

The present invention relates to compositions for the washing of laundry fabrics, the compositions containing anionic surfactants.
Compositions for the washing of laundry items traditionally contain one or more surfactants as well as other components. The most common class of surfactant in such compositions comprises the anionic surfactants, especially synthetic non-soap anionics Often, one or more such anionic surfactants are used together in a blend with one or more nonionic surfactants. Further, although anionic and cationic surfactants are often incompatible, due to the their tendency to form a complex, recently, there have been several proposals to utilise certain compatible anionic and cationic surfactant combinations in laundry wash products.
Nevertheless, there is still a need to find surfactant systems based on anionic surfactant which give better removal of oily/greasy soil from cotton fabrics. The present invention solves this problem by incorporation of certain cationic polymers (as defined herein below). One preferred such polymer is a dimethyldiallyl ammonium chloride polymer (poly-DMDAAC). Previously, cationic polymers in general have been used in a wide range of household cleaning and personal wash applications.
For example, cationic polymers have been widely used in dishwasher rinse aid products. For example, it is known from EP-A-0 167 382, EP-A-0 342 997 and DE-A-26 16 404 to mix cationic polymers with surfactant in such product, in order to obtain clean surfaces as free from streaks as possible.
EP-A-0 167 382 describes liquid detergent compositions which can contain cationic polymers as thickeners. Hydroxypropyltrimethyl ammonium guar, copolymers of aminoethylmethacrylate and acrylamide, and copolymers of DMDAAC and acrylamide are described as particularly suitable cationic polymers.
DE-A-26 16 404 describes cleaning preparations for glass and, containing cationic cellulose derivatives. These materials are said to give better drainage of water, to produce clean, streak-free glass.
WO-A-97/09408 discloses use of cationic polymers selected from cationic polymers of copolymers of monomers such as trialkyl ammonium alkyl(meth)acrylate or -acrylamide, DMDAAC and with other counter-ions; polymer-like reaction products of ethers or esters of polysaccharides with ammonium side groups, in particular guar, cellulose and starch derivatives; polyadducts of ethylene oxide with ammonium groups; quaternary ethylene imine polymers and polyesters and polyamides with quaternary side groups as soil-release compounds in dishwasher rinse aids.
Cationic polymers are also usable in hard surface cleaners. For example, EP-A-0 467 472 describes e.g. cleaning preparations for hard surfaces, containing cationic homopolymers and/or copolymers as soil-release polymers. These polymers comprise quaternised ammonium alkyl-methacrylate groups as monomer units. These compounds are used in order to render the surfaces such that the soil can be removed more easily during the next cleaning process.
EP-A-0 342 997 describes all-purpose cleaners which can contain cationic polymers, wherein in particular polymers with imino groups are used.
Another known use of such polymers is in hair shampoos. WO 97/42281 discloses compositions containing sugar-based nonionic surfactants and copolymers of acrylamide and DMDAAC to improve the tactile properties of such surfactants. Use in dishwashing applications is also mentioned.
In laundry washing/rinsing applications, several uses for cationic polymers have been proposed. Thus, JP-A-04 153300 discloses use of poly-DMDAAC in compositions containing cationic/amphoteric surfactants to enhance softness in the washing of delicate items.
Use of poly-DMDAAC as a greying-inhibitor in laundry products in disclosed in DD-A-296 307. The surfactant in these compositions is all nonionic.
JP-A-62 018500 discloses laundry detergent creams based on soap blends and cationic polymers such as poly-DMDAAC.
There is also a very large number of prior disclosures of cationic polymers used as dye fixers in laundry cleaning products, i.e. as materials for reducing the amount of dye released from fabrics, have been described in a number of references. For example, EP-A-0 462 806 describes use of such materials in rinse phase products to give protection against dye transfer during subsequent washes. Although non-soap anionic surfactant is speculatively mentioned as one optional ingredient in the product, all of the preferred product forms and specific examples thereof, either contain no surfactant or else cationic surfactant.
JP-A-07 316590 discloses detergent compositions containing cationic polymers, including poly-DMDAAC for anti-dye transfer and/or anti-soil redeposition aids. These compositions are typically bends of anionic and nonionic surfactants. In one example, detergent composition contains 25% by weight of anionic surfactant, and 25% of zeolite builder. Although sodium carbonate is also included, sodium carbonate in the absence of calcite as a crystal seed material does not contribute to calcium binding and therefore, cannot be regarded as a builder, but rather, as a pH buffer. The composition as disclosed does not contain calcite. Of the anionic surfactant, 10% by weight (based on the weight of the total composition) is linear alkylbenzene sulphonate which is a V-branched surfactant having linear alkyl limbs. In the wash liquor 10% by weight of the detergent composition of a polymer of DMDMC is added on top. The mole ratio of anionic surfactant to total cationic units in the polymer can be calculated to be substantially 0.88:1. Moreover, there is no disclosure of using such a polymer to assist removal of oily/greasy stains.
GB-A-2 323 385 discloses detergent compositions with a cationic dye-fixing ingredient. A small number of examples contains poly-DMDAAC with a molecular weight in the range 2,000 to 20,000, as a cationic dye fixing agent.
The structure and composition of an aqueous solution of a pure laboratory grade (non-branched) primary alkyl sulphate anionic surfactant namely sodium dodecyl sulphate, in the presence of poly-DMDAAC, at the air-water interface, has been described in a number of references, namely J. Penfold et al, Langmuir 1995, 11, 2496-2503, J. Penfold et al, Colloids and Surfaces A, 1997, 128, 107-117, A. Creeth et al, J. Chem. Soc., Faraday Trans., 92, 4, 589-594, and L. Yingjie et al, Langmuir 1995, 11, 2486-2492. A wide range of model compositions to explore these phenomena are disclosed in these references.
The present inventors have now found that certain polymers containing DMDAAC and its analogues can be combined with a branched anionic surfactant to enhance oily/greasy soil removal from cotton fabrics. However, none of the aforementioned reference discloses this novel use, nor a mole ratio of branched anionic surfactant to total cationic monomer units in the polymer of greater than 1:1.
Thus, a first aspect of the invention now provides a laundry washing composition comprising:
(a) anionic surfactant comprising at least one surfactant compound of formula (I):
R1xe2x80x94Zxe2x88x92M+xe2x80x83xe2x80x83(I)
xe2x80x83wherein
R1 is a branched hydrophobic group;
Zxe2x88x92 is a hydrophilic anion; and
M+ is a counter cation, preferably an alkali metal ion such as sodium;
(b) a detergency enhancing polymer which is a homopolymer or copolymer containing one or more monomer units independently selected from those of formula (II)
xe2x80x83wherein
xe2x80x94Axe2x80x94 is selected from groups of formula xe2x80x94R5xe2x80x94, xe2x80x94R5xe2x80x94(CO)xe2x80x94R6xe2x80x94, xe2x80x94R5xe2x80x94(CO)xe2x80x94Oxe2x80x94R6, xe2x80x94R5xe2x80x94Oxe2x80x94(CO)xe2x80x94R6xe2x80x94, xe2x80x94R5xe2x80x94(CO)xe2x80x94NHxe2x80x94R6xe2x80x94, xe2x80x94R5xe2x80x94NHxe2x80x94(CO)xe2x80x94R6xe2x80x94, wherein R5 and R6 are independently absent, or represent C1-3 alkyl groups;
R1, R2 and R3 are independently selected from hydrogen, C1-3 alkyl, C1-3 alkenyl, hydroxy-C1-3 alkyl and C5-8 cycloalkyl groups; and
R4 is selected from groups as defined for A above;
wherein R3 may also represent a bridging group to the group R4, said bridging group being selected from groups as defined for A above; and
Xxe2x88x92 is a monovalent anion or an n""th part of an n-valent anion; and
(c) optionally, one or more other ingredients;
wherein, when the composition comprises sodium tripolyphosphate builder, the composition is particulate and has a bulk density of at least 650 g/liter and when the composition comprises zeolite builder the amount of zeolite builder is no more than 19% by weight of the composition.
A second aspect of the present invention provides a laundry washing composition comprising:
(a) anionic surfactant comprising at least one surfactant compound of formula (I):
R1xe2x80x94Zxe2x88x92M+xe2x80x83xe2x80x83(I)
xe2x80x83wherein
R1 is a branched hydrophobic group;
Zxe2x88x92 is a hydrophobic anion; and
M+ is a counter cation, preferably an alkali metal ion such as sodium;
(b) a detergency enhancing polymer which is a homopolymer or copolymer containing one or more monomer units independently selected from those of formula (II)
xe2x80x83wherein
xe2x80x94Axe2x80x94 is selected from groups of formula xe2x80x94R5xe2x80x94, xe2x80x94R5xe2x80x94(CO)xe2x80x94R6xe2x80x94, xe2x80x94R5xe2x80x94(CO)xe2x80x94Oxe2x80x94R6, xe2x80x94R5xe2x80x94Oxe2x80x94(CO)xe2x80x94R6xe2x80x94, xe2x80x94R5xe2x80x94(CO)xe2x80x94NHxe2x80x94R6xe2x80x94, xe2x80x94R5xe2x80x94NHxe2x80x94(CO)xe2x80x94R6xe2x80x94, wherein R5 and R6 are independently absent, or represent C1-3 alkyl groups;
R1, R2 and R3 are independently selected from hydrogen, C1-3 alkyl, C1-3 alkenyl, hydroxy-C1-3 alkyl and C5-8 cycloalkyl groups; and R4 is selected from groups as defined for A above;
wherein R3 may also represent a bridging group to the group R4, said bridging group being selected from groups as defined for A above; and
Xxe2x88x92 is a monovalent anion or an n""th part of an n-valent anion; and
(c) optionally, one or more other ingredients;
wherein the detergency enhancing polymer has a weight average molecular weight of from 50,000 to 150,000.
Hereinafter, the anionic surfactant component (a) based on the anionic surfactants of formula (I) will be referred to as the xe2x80x9cbranched anionic surfactantxe2x80x9d.
Compositions according to the present invention contain the branched anionic surfactant, the polymer in the amount specified and optionally one or more other ingredients. As demonstrated in the examples, the polymer has been found to enhance the detergency of the anionic cotton in removal of oil/greasy stains from cotton fabrics.
More specifically, it has now been found that fatty/oily soil removal is especially effective if not only does the anionic surfactant contain at least some branched anionic surfactant but also if the amount of anionic surfactant relative to cationic monomer units in the polymer is higher than in the compositions where such polymers have been used for dye fixation or other purposes. Without being bound by any particular theory or explanation, it is believed that this is because the branched anionic surfactant mitigates against the formation of liquid crystalline phases at the soil/wash liquor interface. Moreover only relatively small amounts of total anionic surfactant-polymer complex are needed to exert the effect, leaving the remainder of the anionic free to assist other cleaning functions in the wash liquor.
Component (c) in compositions according to the invention stipulates optionally, one or more other ingredients. In other words, these other ingredients do not have to be present. Preferably however, compositions according to the invention contain one or more other ingredients typically found in laundry wash products. Preferably, these are selected from one or more of surfactants (other than the anionic surfactant), builders, bleaches, enzymes and minor ingredients.
The Polymer
The detergency enhancing polymer can be a homopolymer or copolymer. Random, block and mixed block/random copolymers are all possible. The polymer may include one or more polymer species which include a monomer unit of formula (II).
Preferably, the monomer units of formula (II) are those where A is methylene (xe2x80x94CH2xe2x80x94) or carbonyl (xe2x80x94COxe2x80x94) and R4 is methylene (xe2x80x94CH2xe2x80x94) or ethylene (xe2x80x94CH2CH2xe2x80x94).
Especially preferred are polymers containing at least some monomer units of formula (I) in which A is methylene, R1 and R2 are methyl, and R3 and R4 together represent xe2x80x94(CHxe2x80x94)xe2x80x94CH2xe2x80x94, i.e. DMDAAC. Preferably at least 50% of the monomer units of formula (I), more preferably at least 80%, more preferably at least 90%, most preferably substantially 100% are DMDAAC units.
For the avoidance of doubt, it should be noted that the DMDAAC unit can also exist in the polymer in the form
i.e. where the second allyl group remains unsaturated and does not form a ring closing bridging group constituted by groups R2 and R4 of formula (I). The double bond of this allyl group can also cross-link with other polymers in the sample and it can also form block co-polymers comprising the monomer unit xe2x80x94CH2xe2x80x94CH2xe2x80x94CH2xe2x80x94(CH3)2N+xe2x80x94CH2xe2x80x94CH2xe2x80x94CH2xe2x80x94. Thus, polymers formed of monomer units of formula (I) in which any of R1xe2x80x94R3 is/are alkenyl groups may contain monomers with any one or more of the aforementioned structural transformations, including ring-closures, cross linking, block co-polymer formations, as well as the unpolymerised terminal unsaturated groups.
Thus, for example, where R2 and R4 together form a linking group R5 by virtue of breakage of a double bond when R2 is C2-4 alkenyl, the resultant monomer unit may be represented thus:
For the example of the DMDAAC monomer unit mentioned above, the corresponding cyclic structure would therefore be:
In the case of copolymers, a wide range of other monomer units may be used, for example selected from those derived from unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and the like, and their esters and salts, olefins such as ethylene, propylene and butene, alkyl esters of unsaturated carboxylic acids such as methylacrylate, ethylacrylate, methylmethacrylate, their hydroxy derivatives such as 2-hydroxyethylmethacrylate, unsaturated aromatic compounds such as styrene, methyl styrene, vinyl styrene, and heterocyclic compounds such as vinylpyrrolidone. However, most preferred are xe2x80x94CH2xe2x80x94CH2xe2x80x94 co-monomer units.
The monomer units of formula (I) are cationic. Optionally one or more other cationic monomer units may also be incorporated. For example, these may be chosen from any other cationic monomer unit structures disclosed in JP-A-07 316 590.
Preferably, the proportion of all cationic monomer units is from 40 mol % to 95 mol %, in order for the polymers to have adequate water-solubility.
It is preferred that the weight average molecular weight of the polymer is from 320 to 10,000,000, more preferably from 5,000 to 500,000, most preferably from 50,000 to 150,000. This weight average molecular weight is typically determined by the method of laser light scattering in combination with gel permeation chromatography (GPC).
In formula (II), counter anions Xxe2x88x92 may be the same of different and may include mixtures of such anions. They may for example be halide ions such as chloride or bromide, SO42xe2x88x92 or CH3SO4xe2x88x92.
Generally speaking, the amount of polymers in the composition will usually be from 0.05% to 10% by weight, although from 0.1% to 5% will be typical.
Synthesis of the Polymer
Many polymers based on DMDAAC and analogous monomer units are commercially available. However, formula (I) also embraces monomer units, polymers of which cannot be obtained commercially. The detergency enhancing polymers utilised in the present invention may be obtained from polymerisation of respective monomers corresponding to the monomer unit of formula (I), optionally other cationic monomer units and optionally, any other, e.g. neutral (uncharged), monomer units, each respectively being ethylenically unsaturated. The different available means of copolymerising such ethylenically unsaturated monomers will be well known to those skilled in the art of polymer chemistry. Depending on the order of addition of reactants, the resulting polymers may be block, random or mixed block/random copolymers.
Surfactants
Compositions according to the invention comprises one or more surfactants at least one of which is a branched anionic surfactant suitable for use in laundry wash products.
Where other surfactants are included in a blend with the anionic surfactant(s), these may be chosen from one or more of cationic, nonionic amphoteric and zwitterionic surface-active compounds and mixtures thereof. Many suitable surface-active compounds are available and are fully described in the literature, for example, in xe2x80x9cSurface-Active Agents and Detergentsxe2x80x9d, Volumes I and II, by Schwartz, Perry and Berch.
The total level of all surfactant(s) in the composition as a whole may for example be from 0.1% to 70% by weight the total composition but is preferably from 5% to 40%.
Anionic Surfactants
At least one of the surfactants must be a branched anionic surfactant. The mole ratio of all anionic surfactant to the total of cationic monomer units in the detergency enhancing polymer is preferably at least 1:1, more preferably at least 2.5:1, still more preferably from 25:1 to 2.5:1, yet more preferably from 20:1 to 3:1, especially from 10:1 to 5:1.
The branched anionic surfactant is an essential component of compositions according to the present intention. However, in general, the anionic surfactant in compositions according to the present invention may comprise one or more soap and non-soap anionic surfactant materials e.g. selected from one or more of the types disclosed in the aforementioned reference of Schwartz, Perry and Berch.
Preferably, R1 is a branched group selected from branched alkyl, alkylaryl (e.g. alkylbenzene or alkylnaphthyl) and alkenyl groups most preferably having from 6 to 24 carbon atoms in the aliphatic part thereof.
Preferably also, Zxe2x88x92 represents a sulphate, sulphonate, carboxylate or phosphonate group, any at which is optionally linked to R1 via a linking moiety, such as a (poly) C2-4 alkyleneoxy moiety, forming part of Zxe2x88x92. In the latter example (when present) preferably there may for example be from 1 to 7 alkyleneoxy groups (which may be the same or different) and which are preferably selected from alkyleneoxy and/or propyleneoxy groups.
As all or part (e.g at least 50%, 60%, 70%, 80%, 90% or 95% by weight) of the branched anionic surfactant component, most preferred are the linear alkylbenzene sulphonate anionic surfactants having an average alkyl component of C8-C15, especially those having a V-shaped hydrophobe group R1, i.e. branching at the point of attachment to the benzene sulphonate group but each arm of the V is linear. Commercial products contain a mixture of different chain lengths for each arm length. Paradoxically, such V-branched materials are sometimes referred to as xe2x80x9clinearxe2x80x9d alkylbenzene sulphonates.
Typically, the branched anionic surfactant represents from 30% to 100% by weight of the total anionic surfactant preferably from 40% to 70%. It is also preferred if the level of branched anionic surfactant is from 0.5 wt % to 30 wt %, more preferably 1 wt % to 25 wt %, most preferably from 2 wt % to 20 wt % of the total composition.
Another preferred class of branched anionic surfactant comprises those disclosed in WO-A-99/19428 in which R1 is attached to the Zxe2x88x92 moiety via a group xe2x80x94Rxxe2x80x94 (wherein Rx is absent or is a linking group such as phenylene), R1 being a hydrophobic mid-chain branched alkyl moiety, having in total 9 to 22 carbons in the moiety, preferably from 12 to about 18, having: (1) a longest linear carbon chain attached to the xe2x80x94Rxxe2x80x94Zxe2x88x92 moiety in the range of from 8 to 21 carbon atoms; (2) one or more C1-C3 alkyl moieties branching from this longest linear carbon chain; (3) at least one of the branching alkyl moieties is attached directly to a carbon of the longest linear carbon chain at a position within the range of the position 2 carbon, counting from position 1 carbon (#1) which is attached to the xe2x80x94Rxxe2x80x94Zxe2x88x92 moiety, to the position of the terminal carbon minus 2 carbons, (the (xcfx89-2) carbon); and (4) when more than one of these compounds is present, the average total number of carbon atoms in the R1xe2x80x94Rxxe2x80x94 moieties in the above formula is within the range of greaterthan 14.5 to about 18, preferably from about 15 to about 17. Preferred R1 groups as defined in WO-A-99/19428 are branched primary alkyl moieties having the formula:
wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula (including the R, Ra, and Rb branching) is from 13 to 19; R, Rx is as hereinbefore defined Ra, and Rb are each independently selected from hydrogen and C1-C3 alkyl (preferably methyl), provided R, Ra, and Rb are not all hydrogen and, when z is 0, at least R or Ra is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer from 0 to 13; and w+x+y+z is from 7 to 13.
Yet other suitable branched anionic surfactants include secondary alkylsulphonates, secondary alcohol sulphates and secondary alkyl carboxylates.
The laundry wash compositions of the invention may additionally or alternatively contain one or more other anionic surfactants in total amounts corresponding to percentages quoted above for branched anionic surfactants, provided that at least some branched anionic surfactant is present. Suitable anionic surfactants are well-known to those skilled in the art. These include primary alkyl sulphates, particularly C8-C15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates. Sodium salts are generally preferred. Such other anionic surfactants typically are used at from 5% to 70% by weight of the total anionic surfactant, preferably from 10% to 30%. Moreover, they typically represent from 1% to 15% by weight of the total composition.
Nonionic Surfactants
The compositions of the invention preferably also contain nonionic surfactant. Nonionic surfactants that may be used include fatty acid methyl ester ethoxylates (FAMEE""s), e.g. as supplied by Lion Corp., Henkel KGA, Condea or Clairant, the primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
It is preferred if the level of total non-ionic surfactant is from 0 wt % to 30 wt %, preferably from 1 wt % to 25 wt %, most preferably from 2 wt % to 15 wt % by weight of the total composition.
Other Surfactants
Another class of suitable surfactants comprises certain mono-long chain-alkyl cationic surfactants for use in main-wash laundry compositions according to the invention. Cationic surfactants of this type include quaternary ammonium salts of the general formula R1R2R3R4N+ Xxe2x88x92 wherein the R groups are long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a counter-ion (for example, compounds in which R1 is a C8-C22 alkyl group, preferably a C8-C10 or C12-C14 alkyl group, R2 is a methyl group, and R3 and R4, which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters).
The choice of surface-active compound (surfactant), and the amount present in the laundry wash compositions according to the invention, will depend on the intended use of the detergent composition. In fabric washing compositions, different surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine. The total amount of surfactant present will also depend on the intended end use and may be as high as 60 wt %, for example, in a composition for washing fabrics by hand. In compositions for machine washing of fabrics, an amount of from 5 to 40 wt % is generally appropriate. Typically the compositions will comprise at least 2 wt % surfactant e.g. 2-60%, preferably 15-40% most preferably 25-35%.
Surfactant Blends
Preferred blends comprise the anionic surfactant(s) and one or more nononic surfactants. Compositions suitable for use in most automatic fabric washing machines will generally contain anionic non-soap surfactant, or non-ionic surfactant, or combinations of the two in any suitable ratio, optionally together with soap. Typical blends contain total anionic to total nonionic surfactant in a weight ratio of from 5:1 to 1:1, preferably from 4:1 to 2:1.
It is also generally preferred that the weight ratio of total anionic surfactant to total builder is from 1:5 to 10:1, more preferably from 2:1 to 10:1, especially from 3:1 to 7:1. Regardless of these ratios, it is also preferred if the weight ratio of total branched anionic surfactants to total builder is from 1:5 to 10:1, more preferably from 1:1 to 7:1.
Detergency Builders
The compositions of the invention, when used as laundry wash compositions, will generally also contain one or more detergency builders. The total amount of detergency builder in the compositions will typically range from 5 to 80 wt %, preferably from 10 to 60 wt % by weight of the total composition.
Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB-A-1 437 950; crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB-A-1 473 201, amorphous aluminosilicates as disclosed in GB-A-1 473 202 and mixed crystalline/amorphous aluminosilicates as disclosed in GB-A-1 470 250; and layered silicates as disclosed in EP-A-164 514. Inorganic phosphate builders, for example, sodium orthophosphate, pyrophosphate and tripolyphosphate are also suitable for use with this invention.
The compositions of the invention preferably contain an alkali metal, preferably sodium, aluminosilicate builder. Sodium aluminosilicates may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably from 25 to 50 wt %.
When the aluminosilicate is zeolite, the maximum amount is 19% by weight.
The alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8-1.5 Na2O. Al2O3. 0.8-6 SiO2.
These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5-3.5 SiO2 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter and Gamble). The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
The zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders. However, according to a preferred embodiment of the invention, the zeolite builder incorporated in the compositions of the invention is maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP-A-384 070. Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
Especially preferred is zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00. The calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di and trisuccinates, carboxymethyloxy succinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
Especially preferred organic builders are citrates, suitably used in amounts of from 5 to 30 wt %, preferably from 10 to 25 wt %; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt %, preferably from 1 to 10 wt %.
Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
Bleaches
Laundry wash compositions according to the invention may also suitably contain a bleach system. Fabric washing compositions may desirably contain peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. Preferred inorganic persaits are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.
Especially preferred is sodium percarbonate having a protective coating against destabilisation by moisture. Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB-A-2 123 044.
The peroxy bleach compound is suitably present in an amount of from 0.1 to 35 wt %, preferably from 0.5 to 25 wt %. The peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures. The bleach precursor is suitably present in an amount of from 0.1 to 8 wt %, preferably from 0.5 to 5 wt %.
Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and pernoanoic acid precursors. Especially preferred bleach precursors suitable for use in the present invention are N,N,Nxe2x80x2,Nxe2x80x2,-tetracetyl ethylenediamine (TAED) and sodium noanoyloxybenzene sulphonate (SNOBS). The novel quaternary ammonium and phosphonium bleach precursors disclosed in U.S. Pat. Nos. 4,751,015 and 4,818,426 and EP-A-402 971, and the cationic bleach precursors disclosed in EP-A-284 292 and EP-A-303 520 are also of interest.
The bleach system can be either supplemented with or replaced by a peroxyacid. examples of such peracids can be found in U.S. Pat. Nos. 4,686,063 and 5,397,501. A preferred example is the imido peroxycarboxylic class of peracids described in EP-A-325 288, EP-A-349 940, DE-A-382 3172 and EP-A-325 289. A particularly preferred example is phtalimido peroxy caproic acid (PAP). Such peracids are suitably present at 0.1-12%, preferably 0.5-10%.
A bleach stabiliser (transition metal sequestrant) may also be present. Suitable bleach stabilisers include ethylenediamine tetra-acetate (EDTA), the polyphosphonates such as Dequest (Trade Mark) and non-phosphate stabilisers such as EDDS (ethylene diamine di-succinic acid). These bleach stabilisers are also useful for stain removal especially in products containing low levels of bleaching species or no bleaching species.
An especially preferred bleach system comprises a peroxy bleach compound (preferably sodium percarbonate optionally together with a bleach activator), and a transition metal bleach catalyst as described and claimed in EP-A-458 397, EP-A-458 398 and EP-A-509 787.
Enzymes
Laundry wash compositions according to the invention may also contain one or more enzyme(s). Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation in detergent compositions. Preferred proteolytic enzymes (proteases) are, catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.
Proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available and can be used in the instant invention. Examples of suitable proteolytic enzymes are the subtilisins which are obtained from particular strains of B. Subtilis B. licheniformis, such as the commercially available subtilisins Maxatase (Trade Mark), as supplied by Gist Brocades N. V., Delft, Holland, and Alcalase (Trade Mark), as supplied by Novo Industri A/S, Copenhagen, Denmark.
Particularly suitable is a protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available, e.g. from Novo Industri A/S under the registered trade-names Esperase (Trade Mark) and Savinase (Trade-Mark). The preparation of these and analogous enzymes is described in GB 1 243 785. Other commercial proteases are Kazusase (Trade Mark obtainable from Showa-Denko of Japan), Optimase (Trade Mark from Miles Kali-Chemie, Hannover, West Germany), and Superase (Trade Mark obtainable from Pfizer of U.S.A.).
Detergency enzymes are commonly employed in granular form in amounts of from about 0.1 to about 3.0 wt %. However, any suitable physical form of enzyme may be used.
Other Optional Minor Ingredients
The compositions of the invention may contain alkali metal, preferably sodium carbonate, in order to increase detergency and ease processing. Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt %, preferably from 2 to 40 wt %. However, compositions containing little or no sodium carbonate are also within the scope of the invention.
Powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate copolymer, or sodium silicate. One preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt %.
Yet other materials that may be present in detergent compositions of the invention include sodium silicate; antiredeposition agents such as cellulosic polymers; inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; dyes; coloured speckles; perfumes; foam controllers; fluorescers and decoupling polymers. This list is not intended to be exhaustive.
Product Form
Compositions according to the first aspect of the present invention may be formulated in any convenient form, for example as powders, liquids (aqueous or non-aqueous) or tablets.
Particulate detergent compositions are suitably prepared by spray-drying a slurry of compatible heat-insensitive ingredients, and then spraying on or post-dosing those ingredients unsuitable for processing via the slurry. The skilled detergent formulator will have no difficulty in deciding which ingredients should be included in the slurry and which should not.
Particulate detergent compositions of the invention preferably have a bulk density of at least 400 g/1, more preferably at least 500 g/1. Especially preferred compositions have bulk densities of at least 650 g/liter, more preferably at least 700 g/liter.
Such powders may be prepared either by post-tower densification of spray-dried powder, or by wholly non-tower methods such as dry mixing and granulation; in both cases a high-speed mixer/granulator may advantageously be used. Processes using high-speed mixer/granulators are disclosed, for example, in EP-A-340 013, EP-A-367 339, EP-A-390 251 and EP-A-420 317.
Liquid detergent compositions according to the invention can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations. Liquid compositions according to the present invention can also be in compact form which means it will contain a lower level of water compared to a conventional liquid detergent.
Tablet compositions according to the invention may for example be prepared by mixing a base powder comprising the anionic surfactant, the polymer of formula (I) and other optional ingredients and tabletting the base powder in a Carver hand press to form cylindrical tablets of approximately 44 mm diameter, as described in WO-A-98/42817 and WO-A-99/20730.
The present invention will now be explained in more detail by way of the following non-limiting examples.

Unilever Home and Personal Care USA division of Conopco Inc.


Slot machines for enabling team play by a plurality of slot machine players are disclosed. The game results of each team player are combined in a predefined manner to obtain a team game result. The game results of each player may be combined on a "per-spin" basis, or collected for each team player over an entire play session, with the net result of each team player combined on a "per-session" basis. In a "per-spin" embodiment, each team player initiates play, and the individual game results of each team player are combined in a predefined manner to obtain the best team game result, with the highest resulting payout, for each spin. In a "per-session" embodiment each team player continues play for an entire play session, and the net result of each team player is analyzed in a predefined manner on a "per-session" basis to obtain the team session result. A session can be defined, for example, in terms of (i) the number of plays per session; (ii) the duration of the session; or (iii) all plays until a predefined event occurs.

Gambling is becoming an increasingly popular form of entertainment, offering gamblers many game alternatives, including numerous table games, such as poker, blackjack and roulette, and various electronic gaming devices, including slot machines, video poker devices, video keno devices and video blackjack devices (hereinafter, collectively referred to as "slot machines"). Slot machines are an important source of income for the gambling industry. Accordingly, casinos constantly search for new gaming strategies and features to distinguish their slot machines from competitors in the industry, and to provide additional incentives for slot machine players to play longer and to return to the casino on their next trip.
Unlike table games, where a group of players typically play against one another or against the casino (often referred to as the "house"), conventional slot machines have traditionally been an individual game. A number of table games, such as blackjack and craps, encourage a team-like mentality, where a group of players play against the house. The success of slot machines can be attributed, at least in part, to their passive and isolated nature, relative to the more competitive and social nature of table games. Many potential players, however, are averse to the isolation typically associated with slot machine play and the inability to interact with other people for help or moral support.
In order to increase the maximum award that can be profitably awarded by an individual slot machine, many casinos have introduced progressive slot machines. Progressive slot machines are a group of linked slot machines that permit players to win a relatively large progressive jackpot prize, in addition to their nonjackpot winnings at each individual gaming machine. The progressive jackpot prize is determined by allocating a portion of the money wagered at each individual linked slot machine to the progressive jackpot prize sum. Thus, the progressive jackpot value continues to increase until a player hits the progressive jackpot prize at one of the linked machines. Progressive slot machines may have the unintended result of encouraging a quasi-competitive environment where players compete against each other for the progressive jackpot prize. Once the progressive jackpot prize is awarded to a player, the progressive jackpot prize amount is reset, typically to a predefined initial progressive jackpot prize value.
Unfortunately, however, progressive slot machines have experienced only marginal success in increasing slot machine play at many casinos, since the large progressive jackpot prize is typically awarded infrequently. In addition, the play of progressive slot machines continues to be primarily an individual game. Even though progressive slot machine players compete, to a certain extent, for the progressive jackpot prize, the primary competitive component of progressive slot machine play remains the player against the individual slot machine. Furthermore, to the extent that progressive slot machine players compete for the progressive jackpot prize, there is no cooperative effort among players or other positive social interaction. Thus, it has been found that the competitive and social aspects of progressive slot machine play do not fully satisfy the expectations of many players.
In addition, while playing progressive or conventional slot machines, players can easily hit an "unlucky streak" and lose a significant amount of money in a short period of time. There is currently no effective way for players to protect themselves. The successful play of one progressive slot machine player, for example, will typically not help reduce the losses of other progressive slot machine players. Although gambling loss insurance programs are available, such programs are not widely utilized and require an advance payment that some players are reluctant to provide.
Sports are another popular form of entertainment, offering both active and passive sports enthusiasts many game alternatives. Many people, of course, are attracted to sports for their competitive and social aspects. Golf, for example, is often played in a tournament environment where players compete against one another, with many golf tournaments incorporating a team component. The popular "better ball" golf tournament format, for example, permits the team score for each golf hole to be the lowest number of strokes obtained by any team player for a given hole. Another variation is the "best ball" format, where the best field position of any team player on each stroke is utilized by all team players for the subsequent stroke. Thus, in both tournament formats, a group of players are able to play a round of golf as part of a cooperative team, competing against other teams. While the "better ball" format spreads the risk of one or more bad holes among all the players on the team, the "best ball" format spreads the risk of one or more bad strokes among all the players on the team.
As apparent from the above-described deficiencies with conventional slot machine systems, a need exists for a system that permits team play of slot machines and increases player interaction. A further need exists for a system that increases the competitive and social aspects of slot machine play. Yet another need exists for a system that spreads the financial risk associated with slot machine play among a plurality of players.

Method and apparatus for team play of slot machines


Gels stable in a subterranean formation at a temperature greater than about 175.degree. F. are formed using, inter alia, a stabilizing agent (e.g., a buffer having a buffering capacity at a pH of at least about 8 and/or a chelating agent).

The present invention relates to (a) methods for forming gels that are stable in a high temperature subterranean formation, (b) high temperature subterranean formations containing the stable gel, and (c) high temperature stable gels.
More and more wells are being drilled into subterranean formations which are at temperatures greater than about 175.degree. F. This phenomenon is due to (a) the increasing depth to which wells are drilled to penetrate oil- and gas-bearing subterranean formations and (b) the drilling of wells in regions having shallow, high temperature, oil- and/or gas-bearing or geothermal subterranean formations, e.g., the Pacific Rim and the North Sea.
While hard water-containing gels are suitable for use (e.g., in enhanced oil and gas operations) in low temperature formations, they are unsuitable for use in subterranean formations at a temperature greater than about 175.degree. F. due to gel degradation (e.g., syneresis and polymer precipitation). (As used in the specification and claims, the term "hard water" means an aqueous liquid having a total divalent cation content of at least about 80 parts per million by weight (ppmw).) Accordingly, one current practice is to import soft water (e.g., surface water, potable water) to the drilling site at considerable expense. (As used in the specification and claims, the term "soft water" means an aqueous liquid having a total divalent cation content of less than about 75 ppmw.) Another current practice is to use more expensive polymer systems that allegedly are capable of forming hard water-containing gels stable at temperatures up to about 250.degree. F.
In addition, even when soft water is used for forming gels to be employed in subterranean formations at temperatures above about 175.degree. F., soft water-containing gels tend to gradually degrade when contacted by hard water (e.g., brine) that is prevalent in many subterranean formations.