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July 4th Festivities @ Noble County Fairgrounds
From July 04, 2014 11:00 am until July 04, 2014 11:00 pm Save to calendar
At Noble County Fairgrounds, directly off of EXIT 25, Caldwell OH. Caldwell, OH
Posted by Becky
Categories: Holiday Events
Tags: auxc
The Noble County 4-H Council will sponsor July 4th Festivities @ Noble County Fairgrounds....traditional chicken dinner served starting at 11 am...dinners are $8.00 & include- 1/2 chicken, green beans, applesauce, roll, ice cream, & beverage. Whole chicken are $9.00. The Noble County Cruzers Car Club will sponsor a Cruise-in Car, Truck, Bike, & Trike Show with registration starting at 10 am & the show from 11-3 pm. Fireworks display at 10 pm. All proceeds from the 4th of July activiites will benefit the Noble County 4-H Youth Development program.
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text:
Deviant Art
The Residual Organization Ch7The Contract, Roxas's story
"Mr. Juusan."
Really? Just when I was about to leave After forcing a smile, I turn to see the person calling me. It's an unfamiliar Goth around my age. His dark hair partially covers his face and expression is difficult to read.
"My name is Zexion Roku. I was ordered by Big Boss to give you this before you leave for the day."
He's pretty mature for his age. He hands me a few sheets of paper.
"What's this for?"
"It's a contract," Zexion says. "You see we need to ensure your ability to keep our company's secrets."
"So I'm one of you guys now?"
"Oh no, not yet. This is merely a precaution. Now, I strongly encourage you to read this contract to the letter before signing it."
I nod as I pretend to look over the document. It's just basic work regulations. Dress formally, respect your employees, yadda, yadda, yadda I sign on whatever line I see and write any information it asks for before giving it back to Zexion.
The Residual Organization Ch4Attraction, Axel's story
Cigarette I need a cigarette
With a cancer stick in hand, I fumble through my desk drawer for my beloved lighter. Eight must've hidden it again. He'll do whatever it takes to make me give in to my temptation
~Looking for something, Redhead?~ I hear Eight ask mockingly.
"Where's my lighter, Eight?"
~Lighter? What lighter?~
"Please don't toy with me "
~Why do you need to smoke anyway? You only do it when you need to distract yourself from you-know-what.~
" "
~I get it You wanna eat that Roxas kid, don't you?~
"That's none of your concern." I search more vigorously for my lighter.
~You want him all to yourself ~
Where the hell is that damn lighter?!
~Well, you're gonna have to fight me for that sweet, sweet blo-~
"Found it!" I announce rather loudly before igniting my cigarette and slowly taking in a drag. I exhale, feeling relieved and v
The Residual Organization Ch3Suspicious Behavior, Roxas's story
Let me out
I can hear the mysterious voice and Mr. Hachi's mumbling, but I'm used to it. Whenever I walk by the red-haired man's desk, he smiles at me. I return the gesture rather enthusiastically. Kairi's passing still lingers in my mind. I should be a bit more sad that Kairi's dead, but I can't stop grinning. I admit I was a bit shocked when I saw her headless body the other day, and sure, I felt bad for her, but I decided to be more optimistic about the matter. I mean, she's the same girl who sabotaged my science project and laughed at me as I received an F The same girl who pretended to be gay and stole my first girlfriend The same girl who "accidentally" dropped my laptop Thank God she's gone.
"Roxas, please watch where you're going." Axel states softly, massaging his temples. I'm not sure why he said that until I head-butt a wall. I was in such a contentment-induced daze that I comple
|Sta.sh Submit

subset: commoncrawl


text:
Book your room at Tropicana Laughlin
Get an overview of this hotelNevada casino hotel on the Colorado River
Lucky in Laughlin
Situated in sunny Laughlin about a block from the Colorado River, this 1,495 room resort features a round-the-clock casino, nightly entertainment, and several restaurants, including a steakhouse and buffet.
Jumbo TV by the pool
Tropicana Express Hotel & Casino's pool has a jumbo screen and Bose surround-sound, perfect for movie-watching, music videos, and sport events. The Poolside Café and Malibu Bar serves up cocktails and sandwiches close by.
Air conditioning and direct-dial phones
All guestrooms offer air conditioning, direct-dial phones, and TVs. Bathrooms are outfitted with a combination of shower and tub.Information missing or incorrect? Tell us!
Renovations & Closures
- Bar/lounge
- Dining venue
Hotel Amenities
Hotel Amenities
Lots more than gaming awaits guests at the Tropicana Express Hotel & Casino on the Laughlin Strip. The hotel includes an outdoor pool with poolside jumbo TV. There are adults-only swim hours. Cabanas are available (surcharge), as is poolside food and beverage service.
The Pavilion Theater hosts entertainment from hilarious comedians to big name entertainers.
The Caboose Lounge offers free entertainment serving up the hottest bands.
Complimentary valet and self-parking are available in a secure garage and outdoors. Wireless Internet access is complimentary in the public areas.
- 24-hour front desk
- Arcade/game room
- ATM/banking
- Breakfast available (surcharge)
- Business center
- Casino
- Coffee shop or café
- Computer station
- Concierge services
- Conference space
- Elevator/lift
- Express check-out
- Free long-term parking
- Free self parking
- Free valet parking
- Free WiFi
- Gift shops or newsstand
- Meeting rooms
- Multilingual staff
- Number of bars/lounges - 3
- Number of floors - 24
- Number of restaurants - 6
- Outdoor pool
- Poolside bar
- Porter/bellhop
- RV, bus, truck parking
- Free shopping center shuttle
- Shopping on site
- Spa tub
- Terrace
- Total number of rooms - 1495
Family Friendly Amenities
- Arcade/game room
- Free Wi-Fi
- Outdoor pool
Available in all rooms: Wireless internet access ( 7 USD per stay )
Available in some public areas: Free WiFi
Free long-term parking, Free self parking, Free valet parking, RV, bus, truck parking
Room Amenities
- Air conditioning
- Cable TV service
- Climate control
- Free toiletries
- Cribs/infant beds (surcharge)
- Daily housekeeping
- Hair dryer
- Iron/ironing board (on request)
- Shower/tub combination
- Television
- WiFi (surcharge)
Where to Eat
The Steakhouse Restaurant - Open for dinner, this venue serves steak and seafood.
Passaggio Italian Garden - Open for dinner, this restaurant serves pizza and pasta.
Roundhouse Buffet - This restaurant serves breakfast and dinner buffets.
Poolside Cafe - Offers sandwiches and baked items.
Carnegie's Café - This restaurant serves breakfast, lunch, dinner and late-night dining, open 24 hours.
Taqueria Del Rio - Authentic Mexican cuisine is served at affordable prices.
Eclipse Bar - This celestial-themed bar with a unique ceiling that morphs into a kaleidoscope of colors has exotic drinks, video poker machines, and plasma TVs.
Caboose Lounge - Come here for live entertainment nightly with no cover charge and no minimum. There are also dancing and casino games.
Grand Junction Premium Slot Lounge and Bar - Located in the casino, this bar serves 31 "flavors" of martinis, as well as wine, premium drinks, and full service.
The Pavilion Theater - Entertainment, from comedians to big-name entertainers.
Nearby Things to Do
The hotel offers an outdoor pool in the shape of a locomotive, with a spa tub in the "wheel." Adults-only swim hours are in the morning and evening.
The hotel is about a block from the Colorado River, where guests can rent boats, water skis, and personal watercraft. Sightseeing cruises on old-time steamboats are another popular option. The Laughlin Ranch, Desert Lakes, and Mojave golf courses are within 10 miles.
The recreational activities listed below are available on site or nearby; fees may apply.
- Golfing nearby
- Personal motorized watercraft on site
- Kayaking nearby
- Water skiing nearby
- Rafting nearby
- Hiking/biking trails nearby
- Mountain biking nearby
To make requests for specific accessibility needs, complete the "Special or Accessibility Requests" section of "Trip Preferences" when you book your hotel.
- Accessible path of travel
- Accessible bathroom
- Roll-in shower
- Accessible parking
- In-room accessibility
- Accessibility equipment for the deaf
- Braille or raised signage
Hotel Policies
Check-in time starts at 3 PM
Minimum check-in age is 21
Check-out time is 11 AM
Children and extra beds
- Children are welcome.
- Rollaway/extra beds are available for USD 15.00 per stay.
- Cribs (infant beds) are available for USD 10.00 per stay.
You need to know
Extra-person charges may apply and vary depending on hotel policy.
Government-issued photo identification and a credit card or cash deposit are required at check-in for incidental charges.
Special requests are subject to availability upon check-in and may incur additional charges. Special requests cannot be guaranteed.
Optional extras
- Breakfast fee: USD 8.99 per person (approximately)
- Fee for in-room wireless Internet: USD 7 per stay (rates may vary)
- Early check-in fee: USD 15.00
- Late check-out fee: USD 20.00
- Deposit: USD 50 per night
- Refrigerator fee: USD 10.00 per stay
- Crib (infant bed) fee: USD 10.00 per stay
- Rollaway bed fee: USD 15.00 per stay


text: North America 25 July 2011 Glenn Beck: youth camp attacked in Norway sounds "like the Hitler Youth" The US shock jock says it is "disturbing" that Utoya youth camp, where 68 were murdered, was focused Print HTML Never one to shy away from controversial remarks, US right-wing pundit Glenn Back has caused an outcry with comments on his Premiere Radio Networks' show, The Glenn Beck Program. Discussing the massacre in Norway, he says: As the thing started to unfold, and then there was a shooting at a political camp, which sounds a little like, you know, the Hitler Youth or whatever -- I mean, who does a camp for kids that's all about politics? Disturbing. But anyway, so there's this political camp, and some crazy man goes and starts shooting kids. Media Matters for America have extracted the clip: › Web Only: the best of the blogs Samira Shackle is a freelance journalist, who tweets @samirashackle. She was formerly a staff writer for the New Statesman. Subscribe More Related articles Margaret Atwood on how an inspired polymath resurrected Native America's epics The last British Guantanamo detainee Shaker Aamer will be released When should you start caring about the US presidential election?


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Trois essais de méthodologie quantitativePresses de l''niversite du Quebec 1994; US$ 16.50
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text:
|Publication number
|Publication type
|Application number
|Publication date
|Dec 16, 1997
|Filing date
|May 19, 1995
|Priority date
|May 19, 1995
|Fee status
|Publication number
|Petrus Andrianus Angevaare, Richard Gerald Gary
|Original Assignee
|Lever Brothers Company, Division Of Conopco, Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (13), Referenced by (32), Classifications (26), Legal Events (4)
|External Links: USPTO, USPTO Assignment, Espacenet
This invention relates to automatic dishwashing detergent compositions containing an aluminum species which inhibits corrosion of fine tableware.
It is well known in the art that automatic dishwashers corrode glassware particularly when cleaned with highly alkaline detergent compositions. See Newton, R. G., The Durability of Glass-A Review, Glass Technology Vol. 26 No. 1, Feb. 1985, pp. 21-38 and U.S. Pat. No. 4,933,101 (Cilley et al.). The visible forms of glassware corrosion are generally caused by hydrolysis and therefore dissolution of the glassware's silicate network. This dissolution is known to be very low at pH values below 9.5 and increases with increasing pH (see Kruger, A. A., The Role of the Surface on Bulk Physical Properties of Glasses, in Surface and Near-Surface Chemistry of Oxide Materials, eds. Nowotny, J., and Dufour, L. -C., pp. 413-448). Thus detergent compositions having an alkalinity of less than about pH 10 were conventionally believed to exert very low corrosivity towards glassware.
Cleaning restrictions forced prior art formulators to seek solutions to tableware corrosion while maintaining high alkalinity in detergent products. The art teaches that silicate in combination with fast dissolving aluminum salts avoids high alkalinity corrosion of glassware. See U.S. Pat. No. 3,350,318, issued on Oct. 31, 1967 to Green and U.S. Pat. No. 3,255,117 issued Jun. 7, 1966 to Knapp et al.
As detergent compositions have increasingly become based on enzymes allowing the products to be milder and more environmentally friendly, it was believed that glassware corrosion would not be a problem especially at pH values of less than about 10.
It has now been discovered that detergent formulations having neutral pH or low alkalinity significantly corrode fine tableware, particularly lead crystal glassware. It is believed that the lead and boron minerals of the tableware take part in the formation of the silicate network. When such minerals are extracted the silicate network falls apart readily. This corrosion is especially pronounced in the absence of silicate which is not always incorporated in low alkalinity or neutral pH products. It has further been observed that detergent compositions incorporating aluminum salts to inhibit corrosion compromise cleaning and leave significant stains on washed tableware.
It has been surprisingly discovered that by utilizing certain slow dissolving aluminum salts in automatic dishwashing compositions that tableware corrosion can be inhibited and that cleaning efficiency can be improved.
It has also been surprisingly discovered that by utilizing certain sequestrants in combination with any water soluble aluminum salt that both tableware corrosion and the negative impact on cleaning efficiency can be minimized.
It is thus an object of the present invention to provide improved pH-neutral to mildly alkaline automatic dishwashing detergent compositions which not only protect against tableware corrosion but also provide good cleaning performance in removing stains from tableware.
Another object of the invention is to provide a process for incorporating aluminum salts in automatic dishwashing detergent compositions to provide effective cleaning performance without tableware corrosion. Although the preparation of the compositions containing the slow dissolving aluminum salts may be by any conventional method, a premix of aluminum-sequestrant complexes must be prepared before the remaining components are added to form the aluminum-sequestrant compositions.
The compositions of the invention are automatic dishwashing detergent compositions comprising:
a) 1 to 20 wt. % of a bleaching agent selected from a peroxygen agent, hypohalite agent, corresponding salts and mixtures thereof;
b) 0.01 to about 25 wt. %, preferably 1 to 15, of an aluminum containing species characterized by a controlled transfer of aluminum(III) ions from the product to the surface of the tableware, either:
i) by being slow dissolving, the definition of slow dissolving aluminum salt being an aluminum salt dissolving at a rate to yield less than 0.56 mM aluminum(III) per minute at 42° C. to a wash liquor or;
ii) by being part of an aluminum-sequestrant complex in which the aluminum is bound by a sequestrant, said complex preventing for at least one hour, the precipitation of any aluminum compound from an aqueous solution of pH ranging from 7 to 10;
c) 1 to 75 wt. % of a builder, and
d) 0 to 40 wt. % of a surfactant.
The automatic dishwashing composition has low levels or no added silicates and has a pH in the range of less than about 10.
The compositions containing the aluminum-sequestrant complexes are prepared by forming a premix of sequestrant and aluminum salt. It is essential that the premix be prepared in a specific order of steps, namely, forming a solution of sequestrant in water, where the solution has a pH not less than one pH unit greater than the pKa of at least one of the ionizable groups on the sequestrant; adding the aluminum salt to this solution; and adjusting the pH of the resulting solution to the same pH as during the initial dissolution of the sequestrant. Remaining components of the compositions are then added in a conventional manner.
The compositions of the invention may be in any variety of physical forms, namely, liquid, powder or gel.
The compositions of the invention are effective cleaners which do not corrode tableware, particularly tableware for entertainment or decorative purposes. Such glassware generally has a high refractive index which gives the classic "sparkle" when cut into decorative shapes. For purposes of this invention, the lead content of such tableware is more than about 20% by weight.
Slow Dissolving Aluminum Salts
The term "slow dissolving aluminum salt" refers to an aluminum salt that dissolves at a rate to yield less than 0.56 mM aluminum(III) per minute at 42° C.
Slow dissolving aluminum salts within the scope of the invention include: aluminum stearate, aluminum tartrate, aluminum acetate, aluminum acetotartrate, aluminum salicylate, aluminum bis(acetylsalicylate), aluminum formate, aluminum octoate, aluminum borate, aluminum oleate, aluminum palmitate, aluminum acetylacetonate, aluminum phosphate and mixtures thereof. Preferred aluminum salts include aluminum acetate, aluminum acetylacetonate, aluminum octoate and aluminum phosphate. Most preferred aluminum salts include aluminum acetate, aluminum acetylacetonate and aluminum octoate.
The aluminum salt should be incorporated in the detergent composition in an amount to deliver about 0.1 mM to about 10 mM, preferably 0.5 mM to about 5 mM, most preferably about 1 mM to 2 mM Al(III) in the wash.
Aluminum-Sequestrant Complexes
The term "aluminum-sequestrant complex" refers to a system containing an aluminum salt and a sequestrant which, when prepared properly, results in a reduced release rate of Al(III) ions.
Aluminum salts useful to form the aluminum-sequestrant complexes within the scope of the invention include: aluminum sulfate, sodium aluminate, aluminum acetate, aluminum acetylacetonate, aluminum formate, aluminum borate, aluminum octoate, aluminum oleate, aluminum palmitate, aluminum tartrate, aluminum acetotartrate, and mixtures thereof. Preferred aluminum salts include: aluminum sulfate, sodium aluminate, aluminum acetate, aluminum acetylacetonate, and aluminum borate. Most preferred aluminum salts include: aluminum sulfate, sodium aluminate, and aluminum acetylacetonate.
Sequestrants within the scope of the invention include the following acids and their alkali metal salts: EDTA, oxalic acid, citric acid, cyanuric acid, NTA, sodium orthophosphoric acid, malonic acid, succinic acid, tartaric acid, aspartic acid, glutamic acid, phosphonic acid, and polyphosphoric acid. Preferred sequestrants include: EDTA, oxalic acid, sodium citrate, and cyanuric acid. Most preferred sequestrants include: sodium citrate, oxalic acid, and cyanuric acid.
The aluminum-sequestrant complex is prepared as follows: with stirring, the desired amount of the selected sequestrant is added to water. During dissolution of the sequestrant, the pH of the solution is adjusted with an inorganic acid, or an inorganic base, preferably NaOH or H2 SO4 to a pH of not less than one pH unit above the pKa of at least one of the ionizable groups on the sequestrant. This mixture is allowed to stir until the sequestrant is completely dissolved. The aluminum salt is dosed into the solution of the sequestrant and allowed to dissolve. During the dissolution of the aluminum salt, the pH of the system is adjusted to the same pH as during the initial dissolution of the sequestrant with NaOH or H2 SO4, as necessary. After the aluminum salt is completely dissolved, the complex is ready for use.
The alkalinity of an aqueous solution of the compositions should be neutral to low alkalinity, preferably less than a pH of 10, most preferably 7 to 9. Maintenance of the composition's pH within the desired range provides stain removal while inhibiting corrosion of fine tableware.
The aluminum salts can interact with tea stains so that the incorporation of slow dissolving aluminum salts in the compositions allows effective bleaching before substantial levels of Al(III) are released into the wash water.
In the aluminum-sequestrant complexes, on the other hand, the aluminum is bound to the sequestrant strongly enough to delay interaction of Al(III) with tea stains.
Any number of conventional buffer agents may be used to maintain the desired pH range. Such materials can include, for example, various water soluble inorganic salts such as the carbonates, bicarbonates, sesquicarbonates, silicates, pyrophosphates, phosphates, tetraborates and mixtures thereof.
The buffering agents should be present in the compositions in a amount of from about 2 to about 30 wt. %, preferably from 5 to about 25% by wt. of the total composition.
Detergent Builder Materials
The compositions of this invention can further contain all manner of detergent builders commonly taught for use in automatic dishwashing of compositions to increase the effectiveness of the detergent by in part, binding calcium salts to act as a softener. The builders can include any of the conventional inorganic and organic water-soluble builder salts, or mixtures thereof and may comprise 1 to 75%, and preferably, from about 5 to about 70% by weight of the cleaning composition.
Typical examples of phosphorus-containing inorganic builders, when present, include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates and polyphosphates. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates, pyrophosphates and hexametaphosphates.
Suitable examples of non-phosphorus-containing inorganic builders, when present, include water-soluble alkali metal carbonates, bicarbonates, sesquicarbonates, borates, silicates, metasilicates, and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites.
Particularly preferred inorganic builders can be selected from the group consisting of sodium tripolyphosphate, potassium pyrophosphate, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium silicate and mixtures thereof. When present in these compositions, sodium tripolyphosphate concentrations will range from about 2% to about 40%; preferably from about 5% to about 30%. Sodium carbonate and bicarbonate when present can range from about 5% to about 50%; preferably from about 10% to about 30% by weight of the cleaning compositions. Sodium tripolyphosphate and potassium pyrophosphate are preferred builders in gel formulations, where they may be used at from about 3 to about 30%, preferably from about 10 to about 20%.
Organic detergent builders can also be used in the present invention. Examples of organic builders include alkali metal citrates, succinates, malonates, fatty acid sulfonates, fatty acid carboxylates, nitrilotriacetates, phytates, phosphonates, alkanehydroxyphosphonates, oxydisuccinates, alkyl and alkenyl disuccinates, oxydiacetates, carboxymethyloxy succinates, ethylenediamine tetraacetates, tartrate monosuccinates, tartrate disuccinates, tartrate monoacetates, tartrate diacetates, oxidized starches, oxidized heteropolymeric polysaccharides, polyhydroxysulfonates, polycarboxylates such as polyacrylates, polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/ polymethacrylate copolymers, aminopolycarboxylates and polyacetal carboxylates such as those described in U.S. Pat. Nos. 4,144,226 and 4,146,495.
Alkali metal citrates, oxydisuccinates, polyphosphates and acrylate/maleate copolymers are especially preferred organic builders. When present they are preferably available from about 1% to about 35% of the total weight of the detergent compositions.
The foregoing detergent builders are meant to illustrate but not limit the types of builders that can be employed in the present invention.
Useful surfactants include anionic, nonionic, cationic, amphoteric, zwitteronic types and mixtures of these surface active agents. Such surfactants are well known in the detergent art and are described at length in "Surface Active Agents and Detergents", Vol. II, by Schwartz, Perry & Birch, Interscience Publishers, Inc. 1959, herein incorporated by reference.
Anionic synthetic detergents can be broadly described as surface active compounds with one or more negatively charged functional groups. Soaps are included within this category. A soap is a C8 -C22 alkyl fatty acid salt of an alkali metal, alkaline earth metal, ammonium, alkyl substituted ammonium or alkanolammonium salt. Sodium salts of tallow and coconut fatty acids and mixtures thereof are most common. Another important class of anionic compounds are the water-soluble salts, particularly the alkali metal salts, of organic sulfur reaction products having in their molecular structure an alkyl radical containing from about 8 to 22 carbon atoms and a radical selected from the group consisting of sulfonic and sulfuric acid ester radicals. Organic sulfur based anionic surfactants include the salts of C10 -C16 alkylbenzene sulfonates, C10 -C22 alkane sulfonates, C10 -C22 alkyl ether sulfates, C10 -C22 alkyl sulfates, C4 -C10 dialkylsulfosuccinates, C10 -C2 acyl isothionates, alkyl diphenyloxide sulfonates, alkyl napthalene sulfonates, and 2-acetamido hexadecane sulfonates. Organic phosphate based anionic surfactants include organic phosphate esters such as complex mono- or diester phosphates of hydroxyl-terminated alkoxide condensates, or salts thereof. Included in the organic phosphate esters are phosphate ester derivatives of polyoxyalkylated alkylaryl phosphate esters, of ethoxylated linear alcohols and ethoxylates of phenol. Also included are nonionic alkoxylates having a sodium alkylenecarboxylate moiety linked to a terminal hydroxyl group of the nonionic through an ether bond. Counterions to the salts of all the foregoing may be those of alkali metal, alkaline earth metal, ammonium, alkanolammonium and alkylammonium types.
Nonionic surfactants can be broadly defined as surface active compounds with one or more uncharged hydrophilic substituents. A major class of nonionic surfactants are those compounds produced by the condensation of alkylene oxide groups with an organic hydrophobic material which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. Illustrative, but not limiting examples, of various suitable nonionic surfactant types are:
(a) polyoxyethylene or polyoxypropylene condensates of aliphatic carboxylic acids, whether linear- or branched-chain and unsaturated or saturated, containing from about 8 to about 18 carbon atoms in the aliphatic chain and incorporating from about 2 to about 50 ethylene oxide and/or propylene oxide units. Suitable carboxylic acids include "coconut" fatty acids (derived from coconut oil) which contain an average of about 12 carbon atoms, "tallow" fatty acids (derived from tallow-class fats) which contain an average of about 18 carbon atoms, palmitic acid, myristic acid, stearic acid and lauric acid,
(b) polyoxyethylene or polyoxypropylene condensates of aliphatic alcohols, whether linear- or branched-chain and unsaturated or saturated, containing from about 6 to about 24 carbon atoms and incorporating from about 2 to about 50 ethylene oxide and/or propylene oxide units. Suitable alcohols include "coconut" fatty alcohol, "tallow" fatty alcohol, lauryl alcohol, myristyl alcohol and oleyl alcohol. Particularly preferred nonionic surfactant compounds in this category are the "Neodol" type products, a registered trademark of the Shell Chemical Company.
Also included within this category are nonionic surfactants having a formula: ##STR1## wherein R is a linear alkyl hydrocarbon radical having an average of 6 to 18 carbon atoms, R1 and R2 are each linear alkyl hydrocarbons of about 1 to about 4 carbon atoms, x is an integer of from 1 to 6, y is an integer of from 4 to 20 and z is an integer from 4 to 25.
One preferred nonionic surfactant of formula I is Poly-Tergent SLF-18® a registered trademark of the Olin Corporation, New Haven, Conn, having a composition of the above formula where R is a C6 -C10 linear alkyl mixture, R1 and R2 are methyl, x averages 3, y averages 12 and z averages 16. Also suitable are alkylated nonionics as are described in U.S. Pat. No. 4,877,544 (Gabriel et al.), incorporated herein by reference.
Another nonionic surfactant included within this category are compounds of formula:
R3 --(CH2 CH2 O)aH (II)
wherein R3 is a6 -C24 linear or branched alkyl hydrocarbon radical and q is a number from 2 to 50; more preferably R3 is a C8 -C18 linear alkyl mixture and q is a number from 2 to 15.
(c) polyoxyethylene or polyoxypropylene condensates of alkyl phenols, whether linear- or branched-chain and unsaturated or saturated,containing from about 6 to 12 carbon atoms and incorporating from about 2 to about 25 moles of ethylene oxide and/or propylene oxide.
(d) polyoxyethylene derivatives of sorbitan mono-, di-, and tri-fatty acid esters wherein the fatty acid component has between 12 and 24 carbon atoms. The preferred polyoxyethylene derivatives are of sorbitan monolaurate, sorbitan trilaurate, sorbitan monopalmitate, sorbitan tripalmitate, sorbitan monostearate, sorbitan monoisostearate, sorbitan tripalmitate, sorbitan monostearate, sorbitan monoisostearate, sorbital tristearate, sorbitan monooleate, and sorbitan trioleate. The polyoxyethylene chains may contain between about 4 and 30 ethylene oxide units, preferably about 20. The sorbitan ester derivatives contain 1, 2 or 3 polyoxyethylene chains dependent upon whether they are mono-, di- or tri-acid esters.
(e) polyoxyethylene-polyoxypropylene block copolymers having formula:
HO(CH2 CH2 O)a (CH(CH3)CH2 O)b (CH2 CH2 O)c H (III)
HO(CH(CH3)CH2 O)d (CH2 CH2 O)e (CHCH3 CH2 O)f H (IV)
wherein a, b, c, d, e and f are integers from 1 to 350 reflecting the respective polyethylene oxide and polypropylene oxide blocks of said polymer. The polyoxyethylene component of the block polymer constitutes at least about 10% of the block polymer. The material preferably has a molecular weight of between about 1,000 and 15,000, more preferably from about 1,500 to about 6,000. These materials are well-known in the art.
They are available under the trademark "Pluronic" and "Pluronic R", a product of BASF Corporation.
(f) Alkyl glycosides having formula:
R4 O(R5 O)n (Z1)p (V)
wherein R4 is a monovalent organic radical (e.g., a monovalent saturated aliphatic, unsaturated aliphatic or aromatic radical such as alkyl, hydroxyalkyl, alkenyl, hydroxyalkenyl, aryl, alkylaryl, hydroxyalkylaryl, arylalkyl, alkenylaryl, arylalkenyl, etc.) containing from about 6 to about 30 (preferably from about 8 to 18 and more preferably from about 9 to about 13) carbon atoms; R5 is a divalent hydrocarbon radical containing from 2 to about 4 carbon atoms such as ethylene, propylene or butylene (most preferably the unit (R5 O)n represents repeating units of ethylene oxide, propylene oxide and/or random or block combinations thereof); n is a number having an average value of from 0 to about 12; Z1 represents a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms (most preferably a glucose unit); and p is a number having an average value of from 0.5 to about 10 preferably from about 0.5 to about 5.
Within the compositions of the present claim, alkyl polyglycosides will be present in amounts ranging from about 0.01 to about 20% by weight, preferably from about 0.5 to about 10%, optimally between about 1 and 5%.
Examples of commercially available materials from Henkel Kommanditgesellschaft Aktien of Dusseldorf, Germany include APG® 300, 325 and 350 with R4 being C9 -C11, n is 0 and p is 1.3, 1.6 and 1.8-2.2 respectively; APG® 500 and 550 with R4 is C12 -C13, n is 0 and p is 1.3 and 1.8-2.2, respectively; and APG® 600 with R4 being C12 -C14, n is 0 and p is 1.3. Particularly preferred is APG® 600.
(g) Amine oxides having formula:
wherein R5, R6 and R7 are saturated aliphatic radicals or substituted saturated aliphatic radicals. Preferable amine oxides are those wherein R5 is an alkyl chain of about 10 to about 20 carbon atoms and R6 and R7 are methyl or ethyl groups or both R5 and R6 are alkyl chains of about 6 to about 14 carbon atoms and R7 is a methyl or ethyl group.
Amphoteric synthetic detergents can be broadly described as derivatives of aliphatic and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contain from about 8 to about 18 carbons and one contains an anionic water-solubilizing group, i.e., carboxy, sulpho, sulphato, phosphato or phosphono. Examples of compounds falling within this definition are sodium 3-dodecylamino propionate and sodium 2-dodecylamino propane sulfonate.
Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium compounds in which the aliphatic radical may be straight chained or branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulpho, sulphato, phosphato or phosphono. These compounds are frequently referred to as betaines. Besides alkyl betaines, alkyl amino and alkyl amido betaines are encompassed within this invention.
If silicates are present in the compositions of the invention, they should be in an amount to provide neutral or low alkalinity (less than pH 10) of the composition. Preferred amounts of silicates present should be from about 1 to about 5%. Especially preferred is sodium silicate in a ratio of SiO2 :Na2 O up from about 1.0 to about 3.3, preferably from about 2 to about 3.2.
An inert particulate filler material which is water-soluble may also be present in cleaning compositions in powder form. This material should not precipitate calcium or magnesium ions at the filler use level. Suitable for this purpose are organic or inorganic compounds. Organic fillers include sucrose esters and urea. Representative inorganic fillers include sodium sulfate, sodium chloride and potassium chloride. A preferred filler is sodium sulfate. Its concentration may range from 0% to 60%, preferably from about 10% to about 30% by weight of the cleaning composition.
Thickeners and Stabilizers
Thickeners are often desirable for liquid cleaning compositions. Thixotropic thickeners such as smectite clays including montmorillonite (bentonite), hectorite, saponite, and the like may be used to impart viscosity to liquid cleaning compositions. Silica, silica gel, and aluminosilicate may also be used as thickeners. Salts of polyacrylic acid (of molecular weight of from about 300,000 up to 6 million and higher), including polymers which are cross-linked may also be used alone or in combination with other thickeners. Use of clay thickeners for automatic dishwashing compositions is disclosed for example in U.S. Pat. Nos. 4,431,559; 4,511,487; 4,740,327; 4,752,409. Commercially available synthetic smectite clays include Laponite supplied by Laporte Industries. Commercially available bentonite clays include Korthix H and VWH ex Combustion Engineering, Inc.; Polargel T ex American Colloid Co.; and Gelwhite clays (particularly Gelwhite GP and H) ex English China Clay Co. Polargel T is preferred as imparting a more intense white appearance to the composition than other clays. The amount of clay thickener employed in the compositions is from 0.1 to about 10%, preferably 0.5 to 5%. Use of salts of polymeric carboxylic acids is disclosed for example in UK Patent Application GB 2,164,350A, U.S. Pat. No. 4,859,358 and U.S. Pat. No. 4,836,948.
For liquid formulations with a "gel" appearance and rheology, particularly if a clear gel is desired, a chlorine stable polymeric thickener is particularly useful. U.S. Pat. No. 4,260,528 discloses natural gums and resins for use in clear autodish detergents, which are not chlorine stable. Acrylic acid polymers that are cross-linked manufactured by, for example, B.F. Goodrich and sold under the trade name "Carbopol" have been found to be effective for production of clear gels, and Carbopol 940 and 617, having a molecular weight of about 4,000,000 is particularly preferred for maintaining high viscosity with excellent chlorine stability over extended periods. Further suitable chlorine-stable polymeric thickeners are described in U.S. Pat. No. 4,867,896 incorporated by reference herein.
The amount of thickener employed in the compositions is from 0 to 5%, preferably 0.5-3%.
Stabilizers and/or co-structurants such as long chain calcium and sodium soaps and C12 to C18 sulfates are detailed in U.S. Pat. Nos. 3,956,158 and 4,271,030 and the use of other metal salts of long chain soaps is detailed in U.S. Pat. No. 4,752,409. Other co-structurants include Laponite and metal oxides and their salts as described in U.S. 4,933,101, herein incorporated by reference. The amount of stabilizer which may be used in the liquid cleaning compositions is from about 0.01 to about 5% by weight of the composition, preferably 0.01-2%. Such stabilizers are optional in gel formulations. Co-structurants which are found especially suitable for gels include trivalent metal ions at 0.01-4% of the compositions, Laponite and/or water-soluble structuring chelants at 1-60%. These co-structurants are more fully described in the co-pending U.S. Pat. No. 5,141,664 by Corring et al., filed Dec. 30, 1987, which application is hereby incorporated by reference.
The formulations of the cleaning composition comprising surfactant may further include a defoamer. Suitable defoamers include mono- and distearyl acid phosphate, silicone oil and mineral oil. Even if the cleaning composition has only defoaming surfactant, the defoamer assists to minimize foam which food soils can generate. The compositions may include 0.02 to 2% by weight of defoamer, or preferably 0.05-1.0%.
Minor amounts of various other components may be present in the cleaning composition. These include bleach scavengers including but not limited to sodium bisulfite, sodium perborate, reducing sugars, and short chain alcohols; solvents and hydrotropes such as ethanol, isopropanol and xylene sulfonates; flow control agents (in granular forms); enzyme stabilizing agents; soil suspending agents; antiredeposition agents; anti-tarnish agents; anti-corrosion agents; colorants; other functional additives; and perfume. The pH of the cleaning composition may be adjusted by addition of strong acid or base. Such alkalinity or buffering agents include sodium carbonate and sodium borate.
Enzymes capable of facilitating the removal of soils from a substrate may also be present in the invention in an amount of from 0 to 10 weight percent, preferably 1 to about 5 weight percent. Such enzymes include proteases (e.g., Alcalase®, Savinase® and Esperase® from Novo Industries A/S), amylases (e.g., Termamyl® from Novo Industries), and lipases (e.g.. Lipolase® from Novo Industries).
Bleaching Agent
A wide variety of halogen and peroxygen bleach sources may be used in the present invention. Examples of such halogen and peroxygen bleaches are described in U.S. Pat. No. 5,200,236 issued to Lang et al., herein incorporated by reference.
Among suitable reactive chlorine or bromine oxidizing materials are heterocyclic N-bromo and N-chloro imides such as trichloroisocyanuric, tribromoisocyanuric, dibromoisocyanuric and dichloroisocyanuric acids, and salts thereof with water-solubilizing cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also quite suitable.
Dry, particular, water-soluble anhydrous inorganic salts are likewise suitable for use herein such as lithium, sodium or calcium hypochlorite and hypobromite. Chlorinated trisodium phosphate is another core material. Chloroisocyanurates are, however, the preferred bleaching agents. Potassium dichloroisocyanurate is said by Monsanto Company as ACL-59®. Sodium dichloroisocyanurates are also available from Monsanto as ACL-60®, and in the dihydrate form, from the Olin Corporation as Clearon CDB-56®, available in powder form (particle diameter of less than 150 microns); medium particle size (about 50 to 400 microns); and coarse particle size (150-850 microns). Very large particles (850-1700 microns) are also found to be suitable for encapsulation.
Peroxy Bleaching Agent
The oxygen bleaching agents of the compositions include organic peroxy acids and diacylperoxides. Typical monoperoxy acids useful herein include alkyl peroxy acids and aryl peroxy acids such as:
(i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g., peroxy-alpha-naphthoic acid, and magnesium monoperphthalate
(ii) aliphatic and substituted aliphatic monoperoxy acids, e.g., peroxylauric acid, peroxystearic acid, epsilon-phthalimido peroxyhexanoic acid and o-carboxybenzamido peroxyhexanoic acid, N-nonenyl-amidoperadipic acid and N-nonenylamidopersuccinic acid.
Typical diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as:
(iii) 1,12-diperoxydodecanedioic acid
(iv) 1,9-diperoxyazelaic acid
(v) diperoxybrassylic acid; diperoxysebacic acid and diperoxy-isophthalic acid
(vi) 2-decyldiperoxybutane-1,4-dioic acid
(vii) N,N'-terephthaloyl-di(6-aminopercaproic acid).
A typical diacylperoxide useful herein includes dibenzoylperoxide.
Inorganic peroxygen compounds are also suitable for the present invention. Examples of these materials useful in the invention are salts of monopersulfate, perborate monohydrate, perborate tetrahydrate, and percarbonate.
Preferred oxygen bleaching agents include epsilon-phthalimido-peroxyhexanoic acid, o-carboxybenzamidoperoxyhexanoic acid, and mixtures thereof.
The oxygen bleaching agent is present in the composition in an amount from about of 1 to 20 weight percent, preferably 1 to 15 weight percent, most preferably 2 to 10 weight percent.
The oxygen bleaching agent may be incorporated directly into the formulation or may be encapsulated by any number of encapsulation techniques known in the art to produce stable capsules in alkaline liquid formulations.
A preferred encapsulation method is described in U.S. Pat. No. 5,200,236 issued to Lang et al., herein incorporated by reference. In the patented method, the bleaching agent is encapsulated as a core in a paraffin wax material having a melting point from about 40° C. to about 50° C. The wax coating has a thickness of from 100 to 1500 microns.
Bleach Precursors
Suitable peroxygen peracid precursors for peroxy bleach compounds have been amply described in the literature, including GB Nos. 836,988; 855,735; 907,356; 907,358; 907,950; 1,003,310 and 1,246,339; U.S. Pat. Nos. 3,332,882 and 4,128,494.
Typical examples of precursors are polyacylated alkylene diamines, such as N,N,N',N'-tetraacetylethylene diamine (TAED) and N,N,N',N'-tetraacetylmethylene diamine (TAMD); acylated glycolurils, such as tetraacetylglycoluril (TAGU); triacetylcyanurate, sodium sulphophyl ethyl carbonic acid ester, sodium acetyloxybenene sulfonate (SABS), sodium nonanoyloxy benzene sulfonate (SNOBS) and choline sulfophenyl carbonate. Peroxybenzoic acid precursors are known in the art, e.g., as described in GB-A-836,988. Examples of suitable precursors are phenylbenzoate; phenyl p-nitrobenzoate; o-nitrophenyl benzoate; o-carboxyphenyl benzoate; p-bromo-phenylbenzoate; sodium or potassium benzoyloxy benzene-sulfonate; and benzoic anhydride.
Preferred peroxygen bleach precursors are sodium p-benzoyloxybenzene sulfonate, N,N,N',N'-tetraacetylethylene diamine, sodium nonanoyloxybenzene sulfonate and choline sulfophenyl carbonate.
The compositions containing the slow dissolving aluminum salts as defined herein may be prepared in any conventional manner known in the art to form any variety of physical forms of the compositions.
For the compositions containing the aluminum-sequestrant complex, it is essential that a premix of the sequestrant material and the aluminum salt be prepared prior to the incorporation of other components of the compositions of the invention. Once the premix is prepared, it may be processed with other detergent components in any conventional manner to form any variety of physical forms of automatic dishwashing detergent compositions, such as liquid, tablet, powder, gel.
To prepare the premix, the selected sequestrant should be completely dissolved in water to form a solution with a pH at least one pH unit greater than the pKa of at least one of the ionizable groups of the sequestrant. The pH must be maintained at this level during the entire dissolution step and the alkalinity of the solution may be adjusted by the addition of either an inorganic acid or an inorganic base, such as NaOH or H2 SO4.
While maintaining the solution at a pH as described above, the selected aluminum salt is added to the solution and the pH is again adjusted to as close to the same pH as during the initial dissolution of the sequestrant as possible. Once the aluminum salt is dissolved into the sequestrant solution, the premix can be incorporated with other components to form the composition.
The following examples will serve to distinguish this invention from the prior art and illustrate its embodiments more fully. Unless otherwise indicated, all parts, percentages and proportions referred to are by weight.
It was surprisingly observed that at low and neutral pH levels (less than about pH 10) lead mineral from lead containing glassware was more substantially extracted than at higher pH. Specifically, lead containing glass tiles obtained from Q-Glass, Inc. of Towaco, N.J. and having a 50% lead content were soaked for 24 hours at 65° C. in one liter soft water containing 6.8 grams of an automatic dishwashing composition having the following formula:
______________________________________Ingredient % of Active______________________________________CDB capsules1 4.3Potassium tripolyphosphate 34Polymer2 1Buffering agents 9Non-ionic surfactant 2Potassium hydroxide (45% soln.) 1Enzymes 0.8Water to balance______________________________________ 1 Chlorine supplied as CDB56, which is 56% available chlorine, and encapsulated according to U.S. Pat. No. 5,200,236 issued to Lang et al. The resulting capsules are 50% CDB56 and 50% wax coating. 2 Carbopol 627, a high molecular polymer having a molecular weight o about one million supplied by B. F. Goodrich Company.
The pH's of the four solutions were adjusted to 7.5, 8.6, 9.5, and 10.5 with NaOH and H2 SO4. After soaking, the lead containing glass tiles and an aliquot of each detergent solution were withdrawn. The lead tiles were weighed to determine weight loss. The aliquots were analyzed for metals using Inductively Coupled Plasma (ICP) spectrometry. The results of each analysis are presented in Table 1 below:
TABLE 1______________________________________pH Value Weight loss (%) Lead Extracted (ppm)______________________________________7.5 0.30 1708.6 0.30 1559.5 0.20 9010.5 0.07 30______________________________________
Thus, as the alkalinity of the detergent compositions increased above about 10, the amount of lead extracted from the lead articles significantly decreased.
It was observed that the addition of selected aluminum salts to the automatic dishwashing composition of Example 1 significantly reduced the lead extracted from the lead containing glass tiles after soaking in a detergent solution.
Detergent solutions according to Example 1 and further containing various aluminum salts to deliver 2.2 millimoles Al(III) per liter were prepared. Lead containing glass tiles were soaked in the detergent solutions under the conditions described in Example 1 except that the pH's of the detergent solutions were maintained at 8.6. After soaking, aliquots of the solutions were analyzed using ICP to determine the amount of lead extracted into the detergent solution. The results of the experiment are presented in Table 2 below:
TABLE 2______________________________________Detergent Compositions Extracted Lead in ppm______________________________________Control (No aluminum salt) 155Aluminum stearate 35Aluminum acetate 35Aluminum acetylacetonate 65Aluminum phosphate 70______________________________________
It was thus observed that the addition of aluminum salts to the low alkalinity detergent solutions significantly reduced the amount of lead extracted from the lead containing articles.
To observe the effect of the presence of aluminum salts in an automatic dishwashing detergent composition, lead containing articles of having decors of various colors were washed in a dishwasher and the fading of the decor of the articles was scored.
Compositions according to Example 1 were prepared using various aluminum salts to deliver Al(III) in an amount of 2.2 millimoles Al(III) per liter in the dishwasher. A 1% solution of each of the compositions had a pH of 8.6. The following articles were washed in a Bauknecht dishwasher for 15 washes in soft water: 1 yellow plate, 1 red plate, 1 blue glass, 1 tweety glass and 1 orange glass. After the 15 washes, the articles were removed and scored for fading of decor from 0 (no fading) to 6 (substantially faded). The scored results are exhibited in Table 3 below:
TABLE 3______________________________________ Yellow Red Blue Tweety OrangeComposition Plate Plate Glass Glass Glass______________________________________Control (No 5 5 5 5 5aluminumsalt)Aluminum 1 1.5 1.5 1.5 1.5sulfateAluminum 0 0.5 1.5 0.5 2acetateAluminum 0.5 1.5 1 1.5 0.5acetylace-tonateAluminum 1 1.5 1.5 3 3.5ocotateAluminum 4.5 3.5 4 5 5phosphate______________________________________
It was observed that all the aluminum salt containing compositions exhibited less decor fading than those compositions which did not contain aluminum salts.
It has been surprisingly found that the presence of an aluminum salt can negatively impact the removal of stains, particularly tea stain, under the conditions obtained by using these detergent compositions. This is most likely caused by a direct interaction between aluminum and the stain. It has been also surprisingly found that controlling the release of aluminum can minimize this negative impact.
To observe the effect of the presence of aluminum salts in an automatic dishwashing detergent composition on tea stain removal, tea stained cups and saucers were washed in the dishwasher and scored with regard to stain removal.
Compositions according to Example 3 were prepared using various aluminum salts to deliver Al(III) in an amount of 2.2 millimoles Al(III) per liter in the dishwasher. A 1% solution of each of the compositions had a pH of 8.6. For each experiment, eight cups and eight saucers were stained in a tea liquor and allowed to dry. Four cups and four saucers of the original eight were stained an additional three times, yielding four cups and saucers stained once, and four cups and saucers stained four times. These articles were washed one (1) time in water containing 250 ppm permanent/320 ppm temporary hardness with the compositions described above. The scored results are exhibited in Table 4 below:
TABLE 4______________________________________Composition 4× cup 4× saucer 1× cup 1× saucer______________________________________Control (No 0 0 0 0aluminumsalt)Aluminum 5 5 5 5sulfateAluminum 1 0 0 0acetateAluminum 3 0 1 0.75acetylace-tonateAluminum 0.25 0 0 0octoateAluminum 0.5 0 0 0phosphate______________________________________
From the above, it was observed that using slow-dissolving aluminum salts (i.e. aluminum acetate, aluminum octoate and aluminum phosphate) in the wash results in the bleaching of tea stains from stained articles significantly better than using fast-dissolving aluminum salts.
Another option to control the release of aluminum is by binding the aluminum to a sequestrant. Surprisingly, it has been found that this way aluminum can be prevented to interact with the stain, while still delivering its benefit of preventing lead leaching of decorated tableware.
For this option, the order of processing detergent compositions incorporating aluminum salts is critical in order to provide compositions which both effectively remove stains from articles and which inhibit extraction of minerals. To demonstrate the criticality of processing, selected cups and saucers were stained in tea, the most difficult stain to remove from tableware. Twelve cups and saucers were stained in a concentrated tea liquor, allowed to dry and then stained three additional times for a total of four tea stainings. For each of the detergent compositions described below, four cups and saucers were placed in a Bauknecht dishwasher and washed one (1) time:
Composition 1 was prepared by adding aluminum sulfate to deliver Al(III) in an amount to deliver of 0.8 millimoles Al(III) per liter in the dishwasher to the composition described in Example 1.
Composition 2 was not prepared according to the invention. Sodium citrate having pKa values of pK1 =3.1, pK2 =4.8 and pK3 =6.4 was selected as the sequestrant. Aluminum sulfate, in an amount to deliver 0.8 mM Al(III) in the wash was dosed into deionized water; during dosing, the pH of the solution was maintained at 9.5. After dosing the aluminum salt, sodium citrate to deliver 0.8 mM in the wash was added to the system. The pH of the resulting system was adjusted to 8.9 to form the premix. This premix was added to the composition described in Example 1 to generate Composition 2.
Composition 3 was prepared according to the invention. Sodium citrate in an amount to deliver 0.8 mM in the wash was completely dissolved in water; during dissolution, the pH of the solution was maintained at 9.5. Once the sequestrant completely dissolved, aluminum sulfate to deliver 0.8 mM Al(III) in the wash was added to the solution. The pH of the resulting solution was adjusted to 8.9 to form the premix. This premix was added to the composition described in Example 1 to generate Composition 3.
The stained articles were evaluated for residual tea stain. A score of 0 indicated that no tea stains were observed while a score of 5 indicated that a large amount of residual tea stain on the washed articles was observed. The results are presented in Table 5 below:
TABLE 5______________________________________Composition Residual Tea Stain______________________________________Composition 1-no sequestrant 5Composition 2-incorrect premix process 4Composition 3-correct premix process 0______________________________________
It was thus observed that incorrect processing of the aluminum salt and sequestrant components produces an inactive premix which interferes with the removal of tea stain from washed articles.
Various sequestrant materials were combined with aluminum sulfate to form a premix according to the invention and the effect of the premix on tea stain removal was observed.
Cups and saucers were stained as described in Example 5 above. Four samples of premix formulations were prepared to deliver 1.2 millimoles per liter of various sequestrant materials and 0.4 millimoles per liter of aluminum sulfate. The stained articles were washed in a Bauknecht dishwasher according to Example 5 above and the washed articles were rated for residual tea stain with 0 being no stain remaining and 5 being significantly stained. The results are presented in Table 6 as follows:
TABLE 6______________________________________Composition Cups Saucers______________________________________No sequestrant/aluminum salt 5 4Succinic acid/aluminum salt 3 0Malonic acid/aluminum salt 2 0Cyanyric acid/aluminum salt 1 0______________________________________
It was thus observed that a premix of various sequestrant materials and the aluminum sulfate significantly reduced tea stain on washed articles when compared to articles washed with aluminum sulfate alone.
Various sequestrant materials were combined with sodium aluminate to form a premix according to the invention and the effect of the premix on tea stain removal was observed.
Cups and saucers were stained as described in Example 5 above. Four samples of premix formulations were prepared to deliver 1.2 millimoles per liter of various sequestrant materials and 0.4 millimoles per liter of sodium aluminate. The stained articles were washed in a Bauknecht dishwasher according to Example 5 above and the washed articles were rated for residual tea stain with 0 being no stain remaining and 5 being significantly stained. The results are presented in Table 7 as follows:
TABLE 7______________________________________Composition Cups Saucers______________________________________no sequestrant 5 4EDTA 0 0Sodium orthophospate 1 0______________________________________
It was thus observed that the use of a premix of sequestrants with different aluminum salts according to the invention significantly reduces residual tea stain relative to the use of the aluminum salts alone.
Benzoic acid was combined with aluminum sulfate at differing ratios to form a premix according to the invention. The effect of these premixes on tea stain removal was observed.
Cups were stained as described in Example 5. Five samples of premix formulations were prepared to deliver 0.4 millimoles per liter of aluminum sulfate at differing ratios to benzoic acid. The stained articles were washed in a Bauknecht dishwasher according to Example 5. The washed articles were rated for residual tea stain with 0 being no stain remaining and 5 being significantly stained. The results are presented in Table 8 as follows:
TABLE 8______________________________________Ratio of benzoic acid to Al(III) Cups______________________________________1:2 1.251:1 1.01.5:1 03:1 0______________________________________
It was thus observed that as the ratio of benzoic acid to aluminum is increased, the tea stain removal performance of the resulting premix improves.
Sodium citrate was combined with aluminum sulfate to form a premix according to the invention. The percent transmittance of each of these premixes was determined by using a Brinkmann PC800 Colorimeter. The effect of pH on percent transmittance of the premix, relative to deionized water, was observed.
Five solutions of premix formulations were prepared to deliver 10 millimoles per liter of sodium citrate and 5 millimoles per liter of aluminum sulfate. The pH of these solutions was adjusted with sulfuric acid or sodium hydroxide, as necessary, to pH values ranging from 7 to 11.
The percent transmittance of these solutions, relative to deionized water, was analyzed. The results are presented in Table 9 as follows:
TABLE 9______________________________________ pH % Transmittance______________________________________ 7 95 8 98 9 98 10 97 11 100______________________________________
It was thus observed that premixes prepared correctly show no precipitation of any aluminum compound at the pH's evaluated.
One sample of inactive premix was prepared to deliver 5 millimoles aluminum sulfate per liter and 10 millimoles sodium citrate per liter. This premix was not prepared according to the invention. The pH of this premix was adjusted to 9 with sodium hydroxide and the percent transmittance of this premix was observed to be 65%. It was thus shown that the incorrect preparation of the premix leads to precipitation of an aluminum compound.
|Cited Patent
|Filing date
|Publication date
|Jul 1, 1959
|Apr 7, 1964
|Calgon Corp
|Corrosion and china pattern fading inhibitor
|Oct 8, 1963
|Jun 7, 1966
|Fmc Corp
|Low-foaming dishwashing composition
|Feb 18, 1964
|Oct 31, 1967
|Fmc Corp
|Method of producing detergent composition
|Mar 5, 1976
|Jul 25, 1978
|Colgate-Palmolive Company
|Automatic dishwasher detergent with improved effects on overglaze
|May 4, 1978
|Apr 22, 1980
|The Procter & Gamble Company
|Alkaline dishwasher detergent
|Jan 2, 1979
|Oct 7, 1980
|The Drackett Company
|Dishwashing detergent gel composition
|Dec 29, 1980
|Dec 22, 1981
|Basf Wyandotte Corporation
|Low-foaming nonionic surfactant for machine dishwashing detergent
|Nov 6, 1981
|Oct 25, 1983
|Basf Wyandotte Corporation
|Low-foaming nonionic surfactant for machine dishwashing detergent
|Feb 13, 1989
|Jun 12, 1990
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|Liquid automatic dishwashing compositions compounds providing glassware protection
|May 21, 1990
|Mar 24, 1992
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|Thixotropic aqueous automatic dishwasher detergent compositions with improved stability
|Apr 24, 1991
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|Lever Brothers Company, Division Of Conopco, Inc.
|Method for wax encapsulating particles
|May 19, 1995
|Apr 29, 1997
|Lever Brothers Company, Division Of Conopco, Inc.
|Process for incorporating aluminum salts into an automatic dishwashing composition
|Jun 25, 1980
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|Dishwashing detergent compsn. contg. aluminium soap - having reduced silicate content, inhibits dish decoration corrosion and damage to glass
|Citing Patent
|Filing date
|Publication date
|Jan 16, 1997
|Jul 21, 1998
|Lever Brothers Company
|Process for incorporating aluminum salts into an automatic dishwashing composition
|Apr 18, 2002
|Nov 26, 2002
|Colgate-Palmolive Company
|Antibacterial cleaning compositions in the form of a tablet
|Jul 2, 2003
|Nov 14, 2006
|Ecolab Inc.
|Warewashing composition for use in automatic dishwashing machines, comprising a mixture of aluminum and zinc ions
|Jun 25, 2004
|Mar 27, 2007
|Ecolab, Inc.
|Warewashing composition for use in automatic dishwashing machines, comprising a zinc ion and aluminum ion corrosion inhibitor
|Feb 2, 2006
|Mar 27, 2007
|Ecolab Inc.
|Warewashing composition comprising a corrosion inhibitor with Al and Zn ions
|Oct 24, 2006
|Jul 15, 2008
|Rohm And Hass Company
|Formulation and method for chlorinating recreational water
|Aug 7, 2006
|Nov 18, 2008
|Ecolab Inc.
|Warewashing composition comprising zinc and aluminum ions for use in automatic dishwashing machines
|Jan 30, 2007
|Apr 28, 2009
|Ecolab Inc.
|Warewashing composition for use in automatic dishwashing machines comprising an aluminum/zinc ion mixture
|Oct 13, 2008
|Dec 29, 2009
|Ecolab Inc.
|Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
|May 2, 2008
|May 4, 2010
|Ecolab Inc.
|Compositions including Ca and Mg ions and gluconate and methods employing them to reduce corrosion and etch
|Oct 31, 2008
|Jun 22, 2010
|Ecolab Inc.
|Compositions including hardness ions and gluconate and methods employing them to reduce corrosion and etch
|May 2, 2008
|Jul 6, 2010
|Ecolab Inc.
|Cleaning compositions containing water soluble magnesium compounds and methods of using them
|Jul 24, 2006
|Jul 20, 2010
|Ecolab Inc.
|Warewashing composition for use in automatic dishwashing machines
|Nov 12, 2009
|Nov 9, 2010
|Ecolab Usa Inc.
|Warewashing composition comprising a Zn/Al corrosion inhibitor for use in automatic dishwashing machines
|Jun 8, 2010
|Dec 28, 2010
|Ecolab Usa Inc.
|Method for using warewashing composition comprising AI and Ca or Mg IONS in automatic dishwashing machines
|Mar 17, 2010
|Apr 5, 2011
|Ecolab Usa Inc.
|Compositions including hardness ions and gluconate and methods employing them to reduce corrosion and etch
|May 24, 2010
|Apr 12, 2011
|Ecolab Usa Inc.
|Cleaning compositions containing water soluble magnesium compounds and methods of using them
|May 2, 2008
|Jun 14, 2011
|Ecolab Usa Inc.
|Compositions including magnesium ion, calcium ion, and silicate and methods employing them to reduce corrosion and etch
|May 2, 2008
|Sep 20, 2011
|Ecolab Usa Inc.
|Method of reducing corrosion using a warewashing composition
|May 2, 2008
|Dec 6, 2011
|Ecolab Usa Inc.
|Cleaning compositions with water insoluble conversion agents and methods of making and using them
|May 2, 2008
|Jun 26, 2012
|Ecolab Usa Inc.
|Compositions including hardness ion and threshold agent and methods employing them to reduce corrosion and etch
|Mar 27, 2009
|Jan 1, 2013
|Ecolab Usa Inc.
|Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
|Oct 9, 2012
|Sep 3, 2013
|Ecolab Usa Inc.
|Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents (PSOA)
|Sep 28, 2009
|Aug 19, 2014
|Ecolab Usa Inc.
|Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
|Aug 30, 2011
|Oct 28, 2014
|Ecolab Usa Inc.
|Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
|Sep 24, 2002
|Jun 26, 2003
|Hutton Howard David
|Cleaning composition
|Nov 14, 2003
|Jul 29, 2004
|The Procter & Gamble Company
|Rinse aid containing encapsulated glasscare active salt
|Jul 2, 2003
|Jan 6, 2005
|Ecolab Inc.
|Warewashing composition for use in automatic dishwashing machines, comprising a mixture of aluminum and zinc ions
|Jun 25, 2004
|Jan 27, 2005
|Smith Kim R.
|Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
|Jul 21, 2004
|Jan 26, 2006
|Johnsondiversey. Inc.
|Paper mill cleaner with taed
|Feb 1, 2006
|Aug 10, 2006
|Acoba, Llc
|Method and system of leak detection in application of positive airway pressure
|Aug 7, 2006
|Nov 30, 2006
|Ecolab Inc.
|Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
|U.S. Classification
|510/222, 510/223, 510/374, 510/229, 510/224, 510/226, 510/379, 510/372, 510/375, 510/380
|International Classification
|Cooperative Classification
|European Classification
|May 19, 1995
Owner name: LEVER BROTHERS COMPANY, DIVISION OF CONOPCO, INC.,
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ANGEVAARE, PETRUS ANDRIANUS;GARY, RICHARD GERALD;REEL/FRAME:007498/0037
Effective date: 19950519
|Jul 10, 2001
|Maintenance fee reminder mailed
|Dec 17, 2001
|Lapse for failure to pay maintenance fees
|Feb 19, 2002
|Expired due to failure to pay maintenance fee
Effective date: 20011216


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Email: email@example.com
Tel: 01634 250254
The Windmill
The Windmill is a traditional English pub offering a warm, friendly and inviting atmosphere located just outside the village of Hoo, four miles from the historic town of Rochester. Recently under new ownership a complete refurbishment both internally and externally has been undertaken offering an atmosphere that is welcoming to all. We have now opened our new play area to keep the children occupied for hours We also have our brand new marquee available for hire for parties, weddings and funerals..Our menu offers a choice of traditional English dishes as well something a little more special like steaks and salmon. We pride ourselves on using local suppliers for our meat and vegetables. All in all we aim to serve good quality locally produced food at value for money prices.
Warm friendly atmosphere
Fine Ales
Good pub food
The pub is situated at the top of the Windmill Hill and shares stunning views over the River Medway.The pub car park has room for more than 50 cars.We often gets walkers, hikers and horse riders calling in for a pub lunch, in our side bar we have a dart board and pool table and hold regular quiz nights.
Visit us on Facebook
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01634 250254
The WindmillRatcliffe HighwayHooRochesterKentME3 8QBTel: 01634 250254© The White Horse 2014 [All Rights Reserved] Legal


text:
Okay I have been having chest pains 24/7 for the last 8 years a constant I take a deep breath it hurts when I press on my ribs it I squeeze in my ribs the pain do have severe anxiety but my attacks just makes it have a0 replies 0 votes Reply to Toadboy1
Can you help? Discussions needing a reply
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Omneprazole - does taking a high dose now and again have any serious effects?
I have severe dyspepsia, and have done for about 15 years ( i am 36). The doctor (after 2 endoscopies) diagnosed non dysf ulceritous. I take omprezole when I get stomach pain, but usually have to take 2 or 3 20mg tablets to get any relief. Does anyone know if osteoporosis would still be a risk0 replies 0 votes Reply to terriL
Ive Tried something new other than Omeprazole
I forgot to collect my Perscription last week Omeprazole , as my usual Chemist was closed I spoke to a Chemist in my local supermarket , she recommended Esomeprazole 20mg once a day , day 2 and ive had no problems, on Omeprazole my sence of smell and taste were messed up , dinner last night i had suasages,...0 replies 1 vote Reply to mag2
All discussions in this group
Magensium Deficiency and Omeprazole
I have been taking Omeprazole for many years, mainly to protect my stomach from the occasional use of Naproxen for arthritis. I take max dosage now as I was diagnosed with a small hiatus hernia about 12 months ago. Over the last few months I have had the odd episode of feeling a little sick,15 replies 0 votes
Young adult suffering from horrible heartburn and a due to a hiatal hernia! Please help :)
Ok so a bit of a background on my situation. At 22 years of age I went through a stressful time in my life where I lost about 20 pounds because was not eating much. Stress lasted about a year and was down to 100 pounds at 5'5. Well at 23 started to experience horrible heartburn and reflux, got an6 replies 0 votes
my omeprazole experience
I was only taking 20mg daily,but the side effects that crept up on me were in buttocks,backs of thighs,tired aching at times when in limbs and outside of head,slight dizziness,irregular overall feeling of23 replies 1 vote
Omeprazole Side Effects? Light headed? Anxiety Attacks
My Mother was experiencing severe pain across her ribs and back which the doctors say is indigestion but only now and again. She was put on Omeprazole about a month ago and after taking one in the morning she starts to feel light headed, dizzy and generally unwell. She then seems to panic about125 replies 4 votes
Omeprazole and Amoxicillin
Hey, I'm a 17 year old girl and on Saturday night I had a horrible pain in my belly so a nurse came out and said that I have blood and protein in my urine. So she gave me Omeprazole and Amoxicillin. She said that the Omerprazole is used to protect my belly from the antibiotics and said have 14 replies 0 votes
omeprozol …side effects ….
Hi bit of history ,im 43 and iv had IBS for several yrs ,, but over last months iv been off my food a little as been getting indigestion a lot , so went to see my gastrologist whom iv seen over the years about my IBS , as i suffer with health anxiety i like to se him to check all ok , he has2 replies 0 votes
Sudden onset indigestion/acid reflux - gone in 5 months
I hope this is the optimistic upbeat post someone is looking for. I'm writing it because there was nothing similar for me when I suddenly (overnight) developed acid reflux (acid high in the throat, rather than the mid chest pain). I'm not overweight, stressed etc. In fact, I'm vegetarian and10 replies 3 votes
i have h pylori i accidentally took too much omeprazole
I have h pylori. Ive been on meds for 6 days but i berely noticed i was suppose to take 20mg omeprazole once a day not twice. Can this mest up my procedure to getting rid of the bacteria. I was told by farmacist to take it twice daily with the other meds but when i read the lavels it says once2 replies 0 votes
On omeprazole for 3 weeks, so unwell!
Pain in stomach few hours after eating, severe diarrhea, losing weight, doctor suspects ulcer or heading that way! Got put on tablets 20mg twice a day, initially helpled with stomach, able to eat again. However, week 2, started to feel extremely dizzy, heavy head. also now experiencing fluttering5 replies 0 votes
Long term use of Omeprazole
Hello, I am a long term user of this medicine and wanted to share my experience of this medicine and my condition which was diagnosed some 15 years ago. I was diagnosed with IBS (Irritable Bowel Syndrome), I have for many years suffered with diahorea stomach bloating and general pain and78 replies 4 votes
Dr Reddy omeprazole
has anyone had any problem with these? My pharmacist recently started supplying Dr Reddy instead of the previous brand the name of which I cant remember but they were yellow/orange coloured I think. These previous tablets worked well and took away my symptoms. However since taking the Dr Reddy I'8 replies 0 votes
omeprazole side effects eyes and mental
Still experincing side effects from 2 capsules of this poison Ive had a lot of side effects: burning eyes double vision brain fog heart flutters eyebrow loss anxiety sinus issues constipation mental changes My mental health seems to have changed a lot almost like im dissconnected from life i8 replies 0 votes
Omeprazole not working
Can anyone help? I have suspected Acid Reflux and I have been taking Omeprazole for 3 weeks, I have only noticed a very slight improvement in my condition and I'm wondering if I should stop taking them or do they take much longer to take effect. I have to say I'm not too happy taking them with all54 replies 3 votes
Gallstones, h. Pylori, in so much pain, what shall I do?
Around may the 12th so a month ago I started feeling really sick, it was bareable but then I was nauseous every single minute of the day, i went to the doctors and she prescribed me with omeparzole for "acid reflux" that didn't make a blind bit of difference, I had bad but bare able stomach pains10 replies 0 votes
Side effects of omeprazole...
Went to doctors last night for constant indigestion, the acid in the throat and all that, general diagnosis of acid reflux, prescribed 20mg omeprazole every took first one this morning, and was fine with it, until about 10 minutes later when i'd arrived at school. Began feeling extremely hot,...1 reply 0 votes
Does any one have an experience any side after taking omeprazole ?
Chest pain for 8 years
What are some natural ways to reduce reflux?
omeprazole bad effects eyes heart
partner taking omperazole ,,
Oesophageal stricture
Omeprazole side effects
Have been on Omeprazole for some time now for hiatus hernia and stomach acid. I took 20 mg twice a day which settled my stomach, but then I noticed some leg aching and this got better when I went down to 20 mg once a day. For the last few months I've been getting increasing puffiness of my ankles,...10 replies 0 votes
Omneprazole - does taking a high dose now and again have any serious effects?
I have severe dyspepsia, and have done for about 15 years ( i am 36). The doctor (after 2 endoscopies) diagnosed non dysf ulceritous. I take omprezole when I get stomach pain, but usually have to take 2 or 3 20mg tablets to get any relief. Does anyone know if osteoporosis would still be a risk0 replies 0 votes
Can omeprozole make acid reflux worse?
I have been on omeprozole for 2 months for acid reflux and I have got worse in that time - I'm sure it must be the tablets that are making it worse. My doctor's advice was to increase the dose from 20mg to 40mg. No thanks. Has anyone else had this happen to them? I'm waiting for an endoscopy so I13 replies 0 votes
I HAVE BEEN TAKING OMEPRAZOLE FOR ABOUT 2 MONTHS AS I HAVE GASTROESOPHAGEAL REFLUX DISEASE (GERD) I HAD AN ENDOSCOPY WHICH SAID IT WAS GRADE B. FOR THE LAST 2 WEEKS MY HAIR HAS BEEN FALLING OUT QUITE A LOT AND SOMETIMES IT COMES OUT IN CLUMPS. THE DOCTOR SAID ITS NOT ALOPECIA, OR A FUNGAL2 replies 0 votes
Hair loss in patches
Hair growth
Hair loss
Hi, I've been taking Omerprozrole since April, I have been loosing my hair and now I've got a few bald bits and my hair is gone very thin, has ayone else experienced this problem34 replies 3 votes
Just took my first dose
I am 26 years old and have been suffering from nausea and occasional vommiting for the last 3 months. It was really bad at first and caused me to take several trips to the ER, where they prescribed me Ondansetron for nausea. During my most recent trip to the ER I informed the doctor that I was a1 reply 0 votes
I've refused treatment for h. Pylori and am taking only acid blocker
i couldn't take omeprazole as I felt it affected my moods. This is working good for my GERD along with trying to keep to an alkaline diet. I'm too afraid of the side effects of the triple therapy of antibiotics and acid blockers. I feel I'm taking my life in my hands at 75 but im not in any6 replies 0 votes
omeprazole made me feel like a zombie!
I started taking this drug about 10 days ago as I had never heard of it, and went to the doctor with bad indigestion. I don't like taking medications but I was in pain and thought what harm could it do. Anyway I started getting really strange feelings like I was in a bit of a dream, and getting19 replies 0 votes
I've stopped taking Omeprazole at last after almost 10 years
After camera investigation 10 years ago finding the valve at top of my stomach dosnt close properly i was put on Omeprazole, now 10 years later and several side effects like smell tastes mouth ulcers chapped and split lips ive found a new wonder drug and convinced my GP to prescribe on repeat prescription,...1 reply 1 vote
Omeprazol 40mg twice a day
losec tablets
ive taken losec for 18 years 20mg twice aday 3 weeks ago i had to have a camera down my throat a week later i started with chest stomach pain so doctor put me on 40mg for a few days as any one else had a prob after having a camera its over a week now and doesnt seem to be getting any better1 reply 0 votes
change of dose question
Hello all, So I went to my gi doc today and he wants to be more agressive with my treatment and take me to 40mg from 10mg (which he said is the baby dose LOL) I'm kind of nervous about it. Does anyone else take that much? Is that the adult dose? I had no side effects on the 10mg and I'm nervous to9 replies 0 votes
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UAE: Biggest climber in visa index
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MIDEAST STOCKS-Markets to rise on stronger global environment
Abu Dhabi's ADWEA in talks with banks for $350 mln project bond
Emirates hints at no Dubai Airshow orders, pushes decision on A350/787 to next year
UAE minister says plans to boost oil output capacity on track
MIDEAST STOCKS-Saudi, Egypt markets barely move in early trade
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MIDEAST STOCKS-UAE markets narrowly mixed in thin, early trade
There is a silver lining, Recession fears drive world markets starkly downward, Dubai beach sex case: Jailed Britons vow to appeal, Raw sewage threat to booming Dubai, In global crisis, oil insulates Gulf, Middle East jubilant over Wall St woes
October 18, 2008 3:17 by kippreport
The Daily Telegraph reports that Michelle Palmers and Vince Acor vow to appeal the verdict.
The Financial Times explains why some people in the Middle East are rejoicing over the global financial crisis.
Newsweek claims the crisis isn't all bad news.
Recession fears have prompted some markets to plummet even further, reports Time.
Oil producing countries in the Gulf are relatively insulated, claims the Christian Science Monitor.
Party with the stars
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text: More from SI Report: Dodgers release pitcher Freddy Garcia Report: Dodgers release pitcher Freddy Garcia Marshawn Lynch sports gold cleats for Super Bowl Marshawn Lynch sports gold cleats for Super Bowl Louisville vs. FIU: Game time, live stream, TV coverage Louisville vs. FIU: Game time, live stream, TV coverage Pittsburgh-area high school football player dies after... Pittsburgh-area high school football player dies after... Close Tweet0 Share0 Comment0 Share0 Share0 Stumble It0 Print0 More SI Wire Report: Cubs shortstop Starlin Castro has $3.6 million seized in legal dispute by Scooby Axson Email Posted: Thu Dec. 19, 2013 Cubs shortstop Starlin Castro had a career-low in batting average last season. ( Jonathan Daniel/Getty Images)Chicago Cubs shortstop Starlin Castro had $3.6 million seized from his bank accounts for refusing to pay three percent of his contract to a baseball school in the Dominican Republic, according to a report in the Chicago Tribune.Castro's father, Diogenis Castros, reportedly signed the agreement with the school Mi Futuro Biliguer when Starlin was 15.Castro signed a seven-year, $60 million contract extension with the team in 2012. He paid part of his original $45,000 signing bonus to the school, according to the report, but did not expect to continue paying the school throughout his career.Castro, 23, hit .245 with 10 home runs and 44 RBI in 161 games for the Cubs last season.VERDUCCI: Five first-timers deserve to make Hall of Fame but only three willMore from the Chicago Tribune:Castro's coach at the school, Manuel Nunez, was planning to sue Castro for "breach of trust and securities distraction," according to a report, trying to force Castro to give him 3 percent of his contract. A source said Castro's attorney plans to file a countersuit against Nunez and claims the contract is baseless, saying the father could not sign away his son's future earnings Promoted Stories Comments


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I received the ring this morning IT IS GORGEOUS... thank you thank you.
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Thanks for all you help in getting me and my wedding set they are very beautiful and my wife to be just loves them. I loved how you took my order and got...
Tri-Color Hand Braided Wedding Band TC-159
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An experimental electronic concept album about a space explorer becoming one with time. Features chiptune, ambient, and other genres. Read more
Funding Unsuccessful
This project's funding goal was not reached on January 13, 2013.
An experimental electronic concept album about a space explorer becoming one with time. Features chiptune, ambient, and other genres.
Scott Baumann
Project by
Scott Baumann
First created | 6 backed
About this project
I'm raising funds to release an electronic album with a varied sense of genre. It is a sic-fi concept album about a space traveler who is on a mission to investigate the moons of Unara, a gas giant in a fictional future-universe.
The story will take you through time & space on an adventure that will be riveting and inquisitive all at once.
The digital edition will have all of the songs in your choice of mp3 or FLAC and will include the art that comes with the special edition.
The normal edition will be a 4-panel digipack and feature a 4 panel insert with 2 panoramas by SumikoOneeSan. (This will include a free digital version).
The special edition will feature a 16 page insert with art for each track by SumikoOneeSan, and will include a DinosaurDevice t-shirt.
Risks and challenges
There are a few risks and challenges that come with this project, the primary risk being, how quickly the art and package replication are complete.
I have been working with Sumiko to ensure the art is complete by the end of the kickstarter date.
In addition, the replication of the physical cd's could take longer than I expected. I'm dealing with that by moving the expected mail-out date to February.
If a set-back occurs, I can deal with that by having someone help me with the mailing process, to ensure that the rewards get to all the backers in time.
Along with that, delays in shipment could occur if I get an overwhelming amount of backers over $10 dollars, just because I'm going to do all of the mail-outs myself.Learn about accountability on Kickstarter
Although the music is finished, I wanted to have the ability to release the album physically.
Despite most music distribution being digital these days, a physical product makes for a more quality release, and will really speak for itself as far as the product is concerned.
Long story short, why not both?
Select this reward
Pledge $5 or more
About $5 USD
14 backers
A digital copy of the album complete with unique track art and story for each track.
16 pages of original digital art by SumikoOneeSan
Available in MP3, FLAC, and AAC.
This reward comes with any pledge over $5.LessEstimated delivery:Manage your pledge
Select this reward
Pledge $10 or more
About $10 USD
6 backers
A physical copy of the album in a 4 panel digipack, with a 4 panel insert with panoramic art by SumikoOneeSan. Includes the liner notes that have the Mission Logs.Less
Select this reward
Pledge $20 or more
About $20 USD
2 backers
A physical copy of the album in a 4 panel digipack, with a 4 panel insert with panoramic art by SumikoOneeSan. Includes the liner notes that have the Mission Logs.
Includes a Dinosaur Device t-shirt in s,m,l,xl.Less
Select this reward
Pledge $35 or more
About $35 USD
4 backers Limited (21 left of 25)
A special edition of the album featuring a 16 page art insert, with the liner note mission logs for each track.
Includes a Dinosaur Device t-shirt in s,m,l,xlLess
All gone!
Pledge $50 or more
About $50 USD
10 backers All gone!
A copy of the special edition, along with a t-shirt.
Includes your name in the special thanks of the album.Less
Funding period
- (60 days)


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The Buckeye Show
Tuesday 3/12/13
Posted by Alicia Barnhart March 12, 2013High Contrast Version
Congrats to Craft and Thomas!
Here's tonight's rundown:
Buckeyes getting primed for Big Ten Tourney
Was Thad Matta shafted for Big Ten Coach of the Year?
and an Iowa wrestler trashes his Big Ten medal.
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Sir Charles Holroyd(1861-1917), Painter and Director of the National Gallery
Sitter in 5 portraits
Artist of 3 portraits
Sir Charles Holroyd initially studied engineering at Leeds, then from 1880 to 1884 moved to London to study art at the Slade School under Legros. He began exhibiting etchings at the Society of Painter-Etchers and became a Fellow of the society in 1885. Holroyd exhibited at the Royal Academy from 1885 until 1895, mainly religious and historical subjects and portraits. Later he confined himself primarily to landscape painting and etching. He was the first Keeper of the Tate Gallery (1897-1906) and served as Director of the National Gallery (1906-16).
by Sir Charles Holroyd
pencil, 1904
by Sir Charles Holroyd
bronze medal, circa 1905
On display in Room 26 at the National Portrait Gallery
by Sir Charles Holroyd
etching, exhibited 1905
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Tags: stimulating, brunette, honey, pigtails, anally, smashed, two, studs
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Stimulating brunette honey with pigtails getting anally smashed by two studs


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Fixed-Price - Est. Budget: $200 - Posted
I want an Expert to create Training Tutorials on Node.js The tutorials must be in text format and must pass copyscape. Screenshots and visuals, to aid learning will be a plus. If you think you are the right candidate , please answer the following questions in your bid 1) What is your Node.js Experience ? 2) Give me sample of any Node.js Tutorial you may have created earlier? 3) What other sub-topics will you cover for the different course topics mentioned in the course attachment in the project description? This is important to define scope of work and avoid disputes later. Suggestions and recommendation in course outline from writers point of view will be considered
Skills: AngularJS Data mining Ember.js Node.js


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Tags: misty, ass, moves, little, booty, shake
Submited: 6 years old
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EZ Flow's new World of Riches Mirror Finish Gels provide a wealth of color at your fingertips. The color gels have a luster effect like metal while retaining a nice mirrored quality. Colors include Gold Fleck, Bronzer, Blush Gold, Platinum, Red Metal, and Liquid Copper.
For more information, visit EZ Flow.
Celebrity Face Off Contest 2015: Paying Homage to a Musical Muse14 photos
Nail Looks From NYFW S/S2016234 photos
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What's the cause of the pinkish-red oval area on the pad of my client's toes?
Am I losing my touch applying acrylics?
Should I have a TV in my salon?
Is perfectionism on the job a blessing or a curse?
What's the best way to recruit techs for a new salon?
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