1997-06-09 Assigned to ECOLOAB INC. reassignment ECOLOAB INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BESSE, MICHAEL E., HEI, KIMBERLY L. PERSON, HEI, ROBERT D.P., KLOS, TERRY J., LOKKESMOE, KEITH D., TARARA, JAMES J.
A touchless car wash composition, that can be made from a concentrate and diluted to use concentration using commonly available service water can comprise an ether amine or diamine in particular a fatty ether amine or diamine. The novel compositions are typically free of hydrocarbon solvents and silicone materials that are common in prior art compositions. The compositions are used in touchless car wash processes in which the materials are sprayed in the form of an aqueous dilute solution to remove soil from the vehicle surface. The aqueous compositions are self removing and very small amounts of the aqueous solutions remain to create water spotting on cleaned vehicle surfaces. The novel compositions of the invention can also contain a variety of other ingredients in a fully formulated system. Such ingredients include rapid dewatering of painted surfaces, improved cleanliness of glass and painted surfaces. A substantial reduction of water spotting and concentrates stability. When used in systems using the direct contact between a brush, the friction between the brush and the vehicle surface is substantially reduced.
This invention relates to aqueous compositions that can be used in washing, rinsing or dewatering of vehicle surfaces. Such surfaces can be made of glass, rubber, painted surfaces, steel and aluminum wheels, plastic panels, thermoplastic/fabric or thermoplastic/fiber composite panels, plastic lenses and a variety of glass or metal composites and plastic trim pieces. The compositions of the invention are typically sprayed or wiped onto a vehicle surface for the purpose of removing a variety of soils common in the transportation, railway, airport, highway, etc. environment. Such soils are derived from fuels, lubricants, hydraulic and other functional fluids, dirt and grime, vehicle exhaust components, residue from prior cleaners, waxes, etc. Preferably, the compositions of the invention are used in either brushed, fabric contact or touchless systems. Such touchless systems involve a simple spray-on of the aqueous systems followed by an aqueous rinse leaving a clean vehicle surface, the surface comprising little or no residual cleaning composition or rinse.
Soiled vehicle surfaces have been cleaned for many years using a variety of compositions and methods. Such compositions can be as simple as solutions of organic dish soaps or common all-purpose utility cleaners. In commercial or industrial vehicle cleaning such as semi-automatic and completely automatic car washes, a variety of cleaning materials have been used in a cleaning system that can often contain a pre-rinse or pre-cleaning step, a cleaning step followed by a combination of one or more steps using waxes, rinses, anti-rust agents, mechanical dryers, etc. Such vehicle cleaning operations can be embodied in a retail cleaning operations designed for cleaning vehicles by personal owners or by car wash personnel. Such cleaning stations can also include stations operated by car rental agencies, retail car dealerships, automobile fleet operators, bus sheds, train depots, airplane maintenance buildings, etc.
One class of commonly available automotive cleaning materials contain a variety of anionic surfactants that is used in conjunction with compatible nonionic surfactants, sequestrants, waxes and other ingredients.
Hydrocarbon wax compositions, applied after the aforementioned cleaning step, promote a shiny finish and are blended to promote removal of water from the vehicle surfaces. Such waxes also often contain a wax with anionic or nonionic surfactants, anti-rust agents and other components that form a fully functional system that can dewater automobiles leaving a dry shiny finish.
A second class of waxing composition is commonly available including a typical formulation containing surfactants, solvents and a silicone wax-like material that forms a shiny surface. Silicones are well known, very hydrophobic materials that when used in vehicle waxing compositions with other components such as nonionic detergents, anti-rust agents, etc. to form a shiny, dry vehicle surface.
One common theme in the prior art cleaning compositions is an anionic material (typically a sulfonate or sulfate surfactant), while the prior art waxing compositions require hydrocarbon or silicone wax materials.
Amine compounds have also been commonly formulated in hydrocarbon containing and silicone containing wax compositions and compositions that contain both hydrocarbons and silicants. For example, Chestochowski et al., U.S. Pat. No. 3,440,063 teaches fatty amine-organic acid salts in car wash formulations. Baker et al., U.S. Pat. No. 3,592,669 discloses a hydrocarbon wax composition containing a fatty alkyl amine in a transparent film forming composition. Cifuentes et al., U.S. Pat. No. 5,258,063 discloses a gloss improving foam for use on vehicle surfaces. The film combines waxes with an alkyl cyclohexyl amine. Herring, GB 1,349,447 discloses a car polish composition comprising a paraffin wax combined with an alkyl diamine. Lastly, ABE, WO 92-22632 discloses a water repellent car window washing composition using a fatty amine acetate salt in combination with a hydrocarbon solvent and silicone wax in a complex formula containing a fluorocarbon active material. Fatty alkyl amines typically have the formula R-NH2 wherein R is a hydrocarbon group that can have 1-3 unsaturated bonds but contain 6-24 straight chain carbon atoms.
Eriksson, WO 92-08823 discloses cleaning and degreasing agent containing an ethoxylated alkyl amine. Eriksson, EP 43360 teaches a metal corrosion protector comprising an ethoxylated amine composition. Lemin et al., GB 2,036,783 discloses a water repellent foam using a cationic dewatering agent comprising an ethoxylated amine that can also use an optional anti-static agent. Fatty ethanol amine amide compounds have been disclosed in, for example, in Bayless, U.S. Pat. No. 5,330,673 for use in adhesives and cleaners. Further, JP 06-145603 teaches a dewatering film form using triethanolamine and a hydrocarbon wax or silicone wax. JP 05-156289 teaches a vehicle cleaner containing short chain water soluble amines. Lastly, JP 03-024200 teaches a detergent for soil removal on vehicles using a short chain aqueous or nonaqueous amine.
Fox, U.S. Pat. No. 4,284,435 teach a car wash composition using an ethoxylated quaternary amine composition. Karalis et al., U.S. Pat. No. 4,864,060 teaches a car wash composition combining a quaternary ammonium compound and an amine oxide material. Betty, Jr. et al., U.S. Pat. No. 3,756,835 teaches an auto polish that combine a quaternary ammonium compound and an ethoxylated amine and a petroleum mineral oil. Tarr, U.S. Pat. No. 5,221,329 teaches a water repellent material used as a coating for aircraft comprising a quaternary ammonium compound and a saline compound. JP 03-262763 and JP 58-076477 disclose car wash compositions and anti-spotting coating compositions that can contain quaternary amine materials in combination with additives such as waxes, cationic surfactants, etc.
These prior art vehicle cleaning materials have had some success in the marketplace. However, the marketplace continually searches for materials having improved properties. Properties that can always use improvement include the gloss of the cleaned vehicle surface, the rate and amount of dewatering, water spotting on glass or painted surfaces, concentrate stability, solution clarity and overall ease of preparing aqueous dilutions from the aqueous concentrate materials. The marketplace has continually searched for improvements in aqueous systems containing organic cleaner materials that can have improved soil removal, improved gloss in the final vehicle surface, reduced spotting and improved dewatering. Lastly, the environmental compatibility of the hydrocarbon and silicone wax-like materials has been questioned in recent years. A substantial need exists to develop vehicle cleaners and rinses that can clean and shine with minimal aqueous residue in touchless or cloth or brush systems.
The ether amine and diamine compositions of the invention are typically formulated in liquid or solid aqueous concentrate materials in which the ether amine or diamine is combined with other compatible cleaning agents in a compatible aqueous concentrate that can be diluted with service water to form a material that can be readily applied (i.e.) sprayed onto a vehicle surface for the purpose of cleaning the vehicle surface leaving the vehicle with a shiny, glossy finish and with a minimum of water spotting or streaking. The amine is made compatable in the compositions of the invention using a stabilizing agent comprising a neutralizing acid or a nonionic surfactant. The stabilizing agent produces single phase ether amine compositions which can be clear solutions. A listing of the typical amine compounds used in the current art are shown in Table 11 (pages 38-39). In contrast to the prior art, anionic surfactants such as sulfates or sulfonates are not preferred and compositions of the invention are substantially free of amine reacting anionic materials. Such acid anionic materials like alkyl benzene sulfonates, alpha olefin sulfonates, and alcohol sulfates are believed to react with, neutralize and reduce the activity of the fatty amines of the invention.
For the purpose of this patent application, the term "vehicle" is intended to mean any transportation conveyance including automobiles, trucks, sport utility vehicles, buses, golf carts, motorcycles, monorails, diesel locomotives, passenger coaches, small single engine private airplanes, corporate jet aircraft, commercial airline equipment, etc. The term "touchless cleaning system" is directed to processes in which the cleaning materials are directly contacted with a vehicle surface comprising a painted surface, a thermal plastic composite surface, a glass surface, a rubber surface, or surfaces containing common automobile trim units for soil removal with a spray or flood with no added mechanical action used in soil removal. A "dewatering agent" promotes rapid and substantially complete drainage of aqueous residue on a vehicle surface. In use, an aqueous cleaner composition can be permitted to remain in contact with such surfaces for a relatively short period of time (less than 5 minutes) to promote soil removal. The aqueous systems are typically removed from the vehicle surface using an aqueous rinse followed by a dewatering agent. The term "hydrocarbon free wax" is intended to convey the concept that the materials of the invention do not contain a substantial proportion of any hydrocarbon that can participate in either soil removal, dewatering or providing a shiny coating to a vehicle painted surface. The term "silicone-free" is intended to convey the concept that the compositions of the invention are substantially free of silicone materials at concentrations typically available for the purpose of promoting a shiny surface, dewatering, water removal or spot or streak prevention. Trivial amounts of wax or silicone can be added within the scope of the invention. The term "anti-soiling" is intended to convey the concept that the materials of this invention aid in eliminating or repelling hard-surface water spots caused by soluble solids in rinse waters.
______________________________________         Wt %      Preferred Wt %______________________________________CARWASHAlkyl ether amine           1-55        2-8Nonionic Surfactant           1-55        5-15Amine oxide     0-25        5-15Sequestrant     1-10        5-10Base or Acid    Adj to desired pHWater           BalanceDRYING AGENTNEUTRAL AGENT (SOLUTION PHASE)Alkyl ether amine           1-55        5-15Nonionic Surfactant           0-20 can be used                       1-7           0.1-20 is usefulAcid            To desired pH or           solution clarityWater and/or    BalancesolventNON-NEUTRALIZED AGENT (EMULSIFIED.sup.1 PHASE)Alkyl ether amine           1-50        5-15Nonionic (or blended           1-20        3-10nonionic) SurfactantWater and/or solvent           BalanceWASH AND DRY CAR WASH FORMULAAlkyl ether amine           0.1-50      2-10Nonionic Surfactant           1-20        5-15Fatty amine ethoxylate           0-20        1-10Alkyl dimethyl amine-oxide           0.1-20      5-15Sequestrant     0.5-20      5-10Solvent (glycol ether)           1-15        2-10Base (pH adjustment)           0.1-5       1-3Silicate (aluminum           0.1-5       0.5-3protection)Solidification agent           Optional    0.1-30.sup.2Water           Balance     Balance______________________________________ .sup.1 Amine in water, dispersed amine in continuous aqueous phase. .sup.2 Solidification agent is used only if solid formulation is needed.
In general, the formulations can be liquid or solid and can contain the fatty ether amine compositions of the invention in combination with a variety of other materials useful in the manufacture of vehicle cleaning and dewatering agents including nonionic surfactants, amine oxide surfactants, sequestrants, acidic materials, basic materials, solvents, and a variety of other useful materials such as dyes, fragrances, thickening agents, foaming surfactants and others. Conventional hardeneing or solidification agents can be used including urea, PEG materials, nonionics, etc.
Preferred amines include tetradecyloxypropyl-1,3-diaminopropane; a C12-14 alkyl oxypropyl-1,3-diaminopropane; a C12-15 alkyloxypropyl amine and other similar materials that can be obtained in the market place under the tradename of TOMAH® DA19, DA18, DA17, DA1618, DA14, PA19, PA17, PA16, PA14, PA1214, etc.
Nonionic surfactants useful in cleaning compositions, include those having a polyalkylene oxide polymer as a portion of the surfactant molecule. Such nonionic surfactants include, for example, chlorine-, benzyl-, methyl-, ethyl-, propyl-, butyl- and other like alkyl-capped polyethylene glycol ethers of fatty alcohols; polyalkylene oxide free nonionics such as alkyl polyglycosides; sorbitan and sucrose esters and their ethoxylates; alkoxylated ethylene diamine; alcohol alkoxylates such as alcohol ethoxylate propoxylates, alcohol propoxylates, alcohol propoxylate ethoxylate propoxylates, alcohol ethoxylate butoxylates, and the like; dodecyl, octyl or nonylphenol ethoxylates, polyoxyethylene glycol ethers and the like; carboxylic acid esters such as glycerol esters, polyoxyethylene esters, ethoxylated and glycol esters of fatty acids, and the like; carboxylic amides such as diethanolamine condensates, monoalkanolamine condensates, polyoxyethylene fatty acid amides, and the like; and polyalkylene oxide block copolymers including an ethylene oxide/propylene oxide block copolymer such as those commercially available under the trademark PLURONIC™ (BASF-Wyandotte), and the like; and other like nonionic compounds. Silicone containing nonionic surfactants such as the ABIL B8852 or Silwet 7602 can also be used. The following materials are particularly preferred: fatty amines (coco, tallow, etc. amines) ethoxylated with 2 to 18 moles of ethylene oxide (EO), substituted amines of the formula: R1 --O--R2 --NH--R2 --NH2, or ethoxylated species thereof, wherein R1 is a fatty group, each R2 is independently a C1-6 alkylene; a poloxamine, an (EO)x (PO)y --NH--R2 --NH2, wherein R2 is a C1-6 alkylene group; C9-14 alcohol ethoxylated with 3 to 10 moles of ethylene oxide (EO), coco alcohol ethoxylated with 3 to 10 moles EO, stearyl alcohol ethoxylated with 5 to 10 moles EO, mixed C12 -C15 alcohol ethoxylated with 3 to 10 moles EO, mixed secondary C11 -C15 alcohol ethoxylated with 3 to 10 moles EO, mixed C9 -C11 linear alcohol ethoxylated with 3 to 10 moles EO and the like. It is preferred that the nonionic have from 8 to 12 carbon atoms in the alkyl group. When this preferred alkyl group is used the most preferred nonionic is the mixed C9 -C11 alcohol ethoxylated with 3-7 moles EO.
An important nonionic surfactant can comprise an amine oxide. Such materials are made by oxidizing a t-alkyl amine to an amine oxide. Preferred amine oxides are typically C6-28 alkyl dimethylamine oxides. Representative examples of such amine oxides are lauryl dimethylamine oxide, dodecyl dimethylamine oxide, tetradecyl dimethylamine oxide, cetyl dimethylamine oxide, stearyl dimethylamine oxide, dodecyl diethylamine oxide, bis(2-hydroxypropyl)tetradecylamine oxide, etc.
Typical aqueous compositions combined with service water can contain the sequestrant to reduce the undesirable effects of typically di- and trivalent metal cations. Such cations can reduce the effect of a variety of the organic components of the formulations of the invention and can promote water spotting. Suitable chelating agents include both inorganic and organic chelating agents. Inorganic silicates, carbonates, phosphates, and borates are examples. Organic chelating agents include trisodium nitrilotriacetate, trisodium hydroxyethylethylenediamine triacetate, tetrasodium ethylenediamine tetraacetate, polyacrylic acid sodium salts and other sequestering or chelating agents well known in the industry.
The compositions of the invention can contain an acidic or basic material that can act to neutralize either a basic or acidic pH, respectively. Such basic materials include amines, sodium hydroxide, sodium silicate materials, etc. These materials can act as an alkaline builder, soil disbursement and buffering agent. The preferred silicate materials also act as an aluminum protectant that can reduce the impact of the chemicals of the invention on exposed aluminum surfaces. The alkaline builder material should be present in amounts sufficient to obtain a pH approximately neutral (i.e., about 6 to 10, preferably 6-9). A variety of typically weak or mild acids can be used to neutralize and solubilize the basic compositions to a variety of pH's. Such acids include acetic acid, hydroxyacetic acid, phosphoric acid, citric acid, and other typical acids used in the manufacture of cleaning compositions.
The formulations of the invention can contain a solvent material. The preferred chemistry requires no solvent. Preferred solvents comprise alcohols, glycols, glycol ether materials. Such materials tend to have aliphatic moieties containing 2 to 6 carbon atoms. Examples of such materials include ethanol, propanol, isopropanol, butanol, 2-butanol, 2-methyl-2-propanol, butoxy diglycol, ethoxy diglycol, polypropylene glycol, ethylene glycol methyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether, dipropylene glycol n-butyl ether, butoxy ethanol, phenoxy ethanol, methoxy propanol, propylene glycol, n-butyl ether, tripropylene glycol, n-butyl ether, propylene glycol, hexylene glycol and other similar oxygenated solvents.
A series of "touchless" car washes were made, with and without an alkyl-ether diamine to test for detergency and dewatering effects. The test was done using a 1 wt % dilution of the footnoted formulas. The material was applied by (i) a low-pressure spray application of 100 ml of the diluted test solution to a 16 ft2 side panel on a white 1994 Dodge Caravan, (ii) allowing a 30 second wait time, and (iii) finally a high (600 psi) pressure water rinse using approximately 0.5 gallon of well water.
Table 1 illustrates the improved painted surface dewatering effects when using the fatty ether amine, while also yielding good detergency. The panels were evaluated with a gloss meter for gloss, and visually for dewatering. The % gloss reading is a relative reference scale of black equals 0% and white equals 100% with cleaning enhancement indicated by an increased value; i.e., usually soiled surfaces are in the range of about 50-70% gloss while cleaned surfaces being about 90-110% gloss. Mirrored surfaces can be greater than 100%.
TABLE 1______________________________________Touchless Car Formula Tests Using An AlkylEther Diamine               Vehicle Surface                           Painted Surface               Final Gloss 50% DewateringRun # Detergent Formulas.sup.3               Reading.sup.4                           Rate (min:sec).sup.5______________________________________1     alkyl-ether-diamino               98%         0:09 formula D.sup.62     alkyl-ether-diamine               101%        0:05 formula C.sup.73     alkyl-ether-diamine               .sup. 91%.sup.9                           0:15 formula B.sup.84     conventional (non-               96%         .sup. 2:26.sup.11 amine) formula.sup.10______________________________________ .sup.3 The footnoted detergent concentrates were made as listed, but used as 1.0 wt % dilutions. .sup.4 Gloss increase measured with a handheld gloss meter; measuring the surface gloss after cleaning in 5 areas of the vehicles driver side surface (an avg. of 6 gloss measurements per area). The final gloss readings were after 5 minutes of drying. .sup.5 Dewatering rate = visual evaluation time for 50% of the water to drain from the surface. .sup.6 Formula D = 2.7% cocoamine 15 mole ethoxylate (Varonic K215), 14% Na HEDTA (Versonol 120), 3.0% C.sub.12-14 linear alkyloxypropyl-1,3-diamino propane (Tomah DA1618), 3.2% C.sub.12 alkyl dimethyl amine oxide, 10.0% nonionic surfactants, 0.25% NaOH, and the remainder as water. .sup.7 Formula C = 3.0% Varonic K215, 14% Versonol 120, 5.0% Tomah DA1618 4.0% amine oxide, 10.0% Dowanol glycols, 0.25% NaOH, and the remainder as water. .sup.8 Formula B = 3.5% Varonic K215, 14% Versonol 120, 5.0% Tomah DA1618 3.2% amine oxide, 11.0% nonionic surfactants, 2.5% Dowanol glycols, 0.25% NaOH, and the remainder as water. .sup.9 Incomplete cleaning was noted with this formula. .sup.10 Conventional formula = 4.5% potassium pyrophosphate TKPP, 9.25% LAS linear alkane sulfonate acid, 2.24% alphaolefin sulfonate (AOS), 8% Dowanol glycols, 1.13% NaOH, and the remainder as fragrance/water. .sup.11 The water actually began to dry before dewatering so the time indicated is for 50% removal by either route.
A "touchless" car washes was made, with and without a fatty alkyl-ether monoamine to test for detergency and even better dewatering effects vs. Example 1. The test was done using a 1 wt % dilution of the footnoted formulas, (i) a low-pressure spray application of 100 ml of the diluted test solution was made to a 16 ft2 side panel on a white 1994 Dodge Caravan, (ii) then allowing a 30 second wait time, and (iii) finally a high (600 psi) pressure water rinse using approximately 0.5 gallon of well water.
Table 2 illustrates the improved dewatering effects when using the amine vs. a conventional detergent. Better results for the primary vs. ether diamine are also shown. The panels were evaluated with a gloss meter for gloss, and visually for dewatering. The relative % gloss values shows both amine formulas (runs 1 and 2) to yield gloss values greater than the conventional formula (run 3); and that the amine can impart a "shine" to the surface that enhances the surface gloss to >100% values.
TABLE 2______________________________________Touchless Car Formula Tests Using Alkyl EtherDiamines and Monoamines             Alkyl    Vehicle  50% Detergent   Ether    Surface Final                               DewateringRun # Formulas.sup.1             Amine    Gloss Reading.sup.2                               Rate (min:sec).sup.3______________________________________1     fatty alkyl-ether             Tomah    111%     0:11 diamine     DA-1618 formula D.sup.42     fatty alkyl-ether             Tomah    110%     0:03 monoamine   PA-19 formula D.sup.53     conventional             none      96%     >3.00.sup.7 (non-amine) formula.sup.6______________________________________ .sup.1 The footnoted detergent concentrates were made as listed, but used as 1.0 wt % dilutions. .sup.2 Gloss increase measured with a handheld gloss meter; measuring the surface gloss after cleaning in 3 areas of the vehicles driver side surface (an avg. of 6 gloss measurements per area). The gloss readings were after 5 min. of drying time. .sup.3 Dewatering rate = visual evaluation time for 50% of the water to drain from the surface. .sup.4 Formula D diamine = 2.7% Varonic K215, 14% Versonol 120, 3.0% Toma DA1618, 3.2% amine oxide, 10.0% nonionic surfactants, 0.25% NaOH, and the remainder as water. .sup.5 Formula D monoamine = 2.7% Varonic K215, 14% Versonol 120, 3.0% C.sub.12-14 oxypropylamine (Tomah PA19), 3.2% amine oxide, 10.0% nonionic surfactant, 0.25% NaOH, and the remainder as water. .sup.6 Conventional formula = 4.5% TKPP, 9.25% LAS acid, 2.24% AOS, 8% Dowanol glycols, 1.13% NaOH, and the remainder as fragrance/water. .sup.7 The water actually began to dry before dewatering so the time indicated is for 50% removal by either route.
Mechanical-brush vehicle washes were made with and without a fatty ether amine to test for enhanced gloss, water removal, and spotting. Table 3 illustrates the improved effects when using the fatty ether amine. The vehicle surfaces were evaluated with a gloss meter for gloss, and visually for dewatering and spotting. A dewatering improvement of the amine formulas vs. the conventional formulas was determined using the gravimetrically determined water weight remaining on the vehicle side surface after a 30 second drain time. Then 100%×(1 - wt on amine treated surface )=dewatering wt on conventional surface improvement.
TABLE 3__________________________________________________________________________Mechanical Brush Formula Tests.sup.1__________________________________________________________________________                                Residual Water                                Removal Amine               Vehicle Surface  vs.               Gloss Increase   Conventional (%Run                 (vs. soiled                       50% Dewatering                                dewatering                                         Water Spot#  Test Vehicle     Detergent Formula               state).sup.2                       Rate.sup.3 (minisec)                                improvement)                                         Rating.sup.4__________________________________________________________________________1  Truck 1     alkyl-ether-               57%     0:04     83%      1.5     diamine formula 1.sup.52  Truck 1     Conventional 1               49%     1:58     --       3     (amine free).sup.6__________________________________________________________________________                                Residual Water                                Removal Amine               Vehicle Surface  vs.               Gloss Increase   Conventional (%Run                 (vs. soiled                       50% Dewatering                                dewatering                                         Water Spot#  Test Vehicle     Detergent Formula               state).sup.12                       Rate.sup.13 (minisec)                                improvement)                                         Rating.sup.14__________________________________________________________________________3  Truck 2     alkyl-ether-               31%     0:08     87%      2     diamine formula 1.sup.54  Truck 2     Conventional 1               18%     3:17     --       4     (amine free).sup.65  Truck 3     alkyl-ether-               33%     0:04     86%      1.5     diamine formula 1.sup.56  Truck 3     Conventional 1               28%     2:05     --       4     (amine free).sup.67  car 1  alkyl-ether-               125%    0:06     75%      ND     diamine formula 2.sup.78  car 1  Conventional 2               101%    3:00     --       ND     (amine free).sup.8__________________________________________________________________________ .sup.1 Two wash formulas were tested on: 1) industrial linen distribution vehicles (10' high, 20' long, 8' width), or ii) a 1989 blue Ford Taurus wagon, using mechanical scrub brushes. Mechanical brush washings were mad using 1.3 vol % dilutions of the concentrated formulas, with and without amine additives, and the surfaces tested for enhanced gloss, water removal, and visual spotting. .sup.2 Gloss increase measured with a handheld gloss meter; measuring the surface gloss before and after cleaning in 4 quarters of the truck side surfaces (avg. of 3 measurements per area). Gloss % increase = gloss (before # - after #)/before #) × 100%. .sup.3 Dewatering rate = visual evaluation time for 50% of the water to drain from the surface. .sup.4 1 = no too few water spots, small diameter, easily removed by wiping. 2 = a few water spots, medium in size, easily removed by wiping. 3 = a few too many water spots, large in size, difficult to remove by wiping. 4 = many water spots, large insize, difficult to remove, dirty looking. ND = no data .sup.5 Amine formula 1 = 2% Varonic K215, 7% EDTA, 3% Tomah DA1618, 3.2% amine oxide, 10% nonionic surfactants, 10% Dowanol glycols, 0.25% NaOH, and the remainder as water. .sup.6 Conventional formula 2 = 4.5% TKPP, 9.25% LAS acid, 2.24% AOS, 8% Dowanol glycols, 1.13% NaOH, and the remainder as fragrance/water. .sup.12 Gloss increase measured with a handheld gloss meter; measuring th surface gloss before and after cleaning in 4 quarters of the truck side surfaces (avg. of 3 measurements per area). Gloss % increase = gloss ((before # - after #)/before #) × 100%. .sup.13 Dewatering rate = Visual evaluation time for 50% of the water to drain from the surface. .sup.14 1 = no too few water spots, small diameter, easily removed by wiping. 2 = a few water spots, medium in size, easily removed by wiping. 3 = a few too many water spots, large in size, difficult to remove by wiping. 4 = many water spots, large insize, difficult to remove, dirty looking. ND -- no data .sup.7 Amine formula 2 = 2% Tomah DA19, 14.0% Versene 100, 2.4% amine oxide, 10% ethoxylated nonionic surfactants, 10% Dowanol DPNP/DPM, and th remainder as water. .sup.8 Conventional formula 2 = 14.0% Versene 100, 2.4% amine oxide, 10% ethoxylated nonionic surfactants, 10% Dowanol DPN:/DPM, and the remainder as water.
To determine the water repellency of the fatty ether amine materials on tile-glass surfaces, aqueous 0.03 wt %-active solutions were made (at various pH's), the solutions applied over the tile-glass surface, and rinsed with city water till the water quickly ran off (˜5 seconds rinse). The tile was then dried overnight and was re-rinsed with 100 mls of soft water and, after 10 seconds of drain time, the residual surface water was determined gravimetrically. The data of Table 4 shows the dewatering effect of the various amines. Water removal of >90% for all the amine containing test formulas (runs 1-11) was observed relative to the non-amine test controls (runs 1-2). Also, the current invention examples show substantial improvement of the prior art commercial formulas (runs 12-20).
TABLE 4______________________________________Water Repellency.sup.1                                 Water                          Residual                                 Removal                 Test So- Water  (% vs.Run # Amine Compound  lution pH.sup.2                          (grams)                                 control).sup.3______________________________________1     control (no amine).sup.4                 2.8      4.03   --2     control (no amine).sup.4                 10.8     5.62   --Composition of the Invention3     C.sub.12-15 linear ether diamine.sup.5                 2.6      0.12   97%4     C.sub.12-15 linear ether diamine.sup.5                 10.6     0.23   96%5     C.sub.12-15 linear ether                 2.3      0.08   98% monoamine.sup.66     C.sub.12-15 linear ether                 10.7     0.16   97% monoamine.sup.67     car wash I.sup.7 + PA-19                 11.3     0.18   97%8     car wash II + PA-19.sup.6                 11.3     0.15   97%9     car wash II.sup.8 + DA-19.sup.5                 11.2     0.21   96%10    car wash II.sup.8 + DA-1618.sup.9                 11.1     0.26   95%11    acid cleaner I.sup.10 + DA-19.sup.5                 2.7      0.06   99%Prior Art12    BELIEVE.sup.11  10.4     4.92   12%13    ZIP WAX CAR WASH -                 8.7      5.03   10% SHINE.sup.1214    SUDDEN SHINE CLEAN                 7.0      5.61   <1% & SHINE.sup.1315    ethoxylated alkyl amine I.sup.14                 3.0      3.98    1%16    ethoxylated alkyl amine II.sup.15                 10.0     5.87    0%17    alkyl dimethyl benzyl                 2.7      3.69    8% quat.sup.1618    alkyl dimethyl benzyl                 9.2      5.43    3% quat.sup.1619    alkyl amine acetate.sup.17                 4.7      0.55   87%20    alkyl amine/diamine                 9.8      0.38   78% mixture.sup.18______________________________________ .sup.1 The test amines or ammonium formulas were made up as 3 wt % amine in the test solutions. The commercial products (lines 17, 18, 19) were no prediluted. Each formula was tested using 12" × 12" glass squares which were treated with 1.5 vol % aqueous dilutions of the aforementioned solutions, at various pH's, then rinsed under well water for 5 seconds, and finally drained for 5 seconds. The residual surface water was determined gravimetrically. .sup.2 The pH was adjusted with glycolic or acetic acids. .sup.3 Water removal was calculated using 100 × (1 - residual water test sample/residual water control); where the residual water control use was control sample line1 for test solutions at pH's <7.0 and control sample line2 for pH's >7.0. .sup.4 Well water neutralized with glycolic acid or NaOH; i.e., no amines or ammonium compounds present. .sup.5 Tomah DA19. .sup.6 Tomah PA19. .sup.7 Car wash I = 3% ethoxylated amine, 7% EDTA, 3% Tomah PA19, 3% amin oxide, 10% nonionic surfactant, 2% silicate, 1% NaOH, and the remainder a fragrance/water. .sup.8 Car wash II = 6% monoethanol amine MEA, 5% EDTA, 8% betaine surfactant, 20% glycol solvents, 6% LAS, 3% amines, remainder as fragrance/water. .sup.9 Tomah DA1618. .sup.10 Acid cleaner I = 7% sulfamic acid, 7.5% citric acid, 12% amine oxide, 9% glycol solvents, 10% phosphoric acid, remainder as fragrance/dye/water. .sup.11 BELIEVE is an industrial car wash detergent for high pressure washing, from S. C. Johnson Co., Rascine, WI. .sup.12 ZIP WAX is a commercial car wash detergent, from Turtle Wax, Inc. Chicago, IL. .sup.13 SUDDEN SHINE is a consumer car shine and windshield dewatering aid, from Plastone Co., Bedford Park, IL. .sup.14 Prior art using ethoxylated alkylamines; JP 63048398, Ger. Offen DE 4,412,380, GB 2036783 using Exxon ET5. .sup.15 Prior art as in ref. 14, but using Varonic K215. .sup.16 Prior art using quats like WO 9222632, US 4,284,435, JP 58076477 using 0372 from Ecolab. .sup.17 Prior art like WO 9222632, US 3440063 using Armene OL. .sup.18 Prior art like US 3440063 using an amine mixture = 2:1:0.5 of Duomene OL:Duomene CD:Armene OL.
The dewatering fatty alkyl ether amines of the invention can also impart a lubricious component to the polymeric brush heads used in mechanical transportation washers. This friction reduction is deemed important for minimizing scratching and wear in mechanical car wash systems employing polymeric bristle brushes to enhance auto soil removal. Recognizing a near logarithmic scale for the relative coefficient of friction (COF), the results show the remarkable improvement in lubricity of this patent (lines 1-5) vs. the prior art (lines 6-7). The COF's below 1.00 are indicative of minimal drag, while those of the prior art above 1.00 impart considerable wear to hard surfaces, and those above ˜1.3 COF indicate extreme wear.
TABLE 5______________________________________Lubricity of Polymeric Washing Brush Surfaces.sup.1                           Relative    Friction Wash          Coefficient ofTest #   Formula      Test Amine                           Friction.sup.2______________________________________1        car wash     DA-1618   0.90    formula 1.sup.32        car wash     DA-1618   0.99    formula 2.sup.43        car wash     DA-1618   0.97    formula 3.sup.54        car wash     DA-18     0.95    formula 4.sup.66        BELIEVE CAR  benzyl quat                           1.33    WASH.sup.87        ZIP WAX CAR  none      1.22    WASH.sup.9______________________________________ .sup.1 Samples for lubricity measure were diluted to 0.1% (unless otherwise stated) with distilled water containing 200 ppm NaHCO.sub.3, an streamed along the perimeter of a polished stainless steel plate measurin 20.5 cm in diameter. The plate was connected to an electric motor, and rotated at an even rate when switched on. A polyester disk weighing 238 g was attached to a load cell and placed on the plate in the area wetted by the lubricant solution. When the electric motor was switched on, the disk glided freely on the plate. The drag between the polyester surface and th stainless steel plate was detected by the load cell, and transferred to a chart recorder. To assure consistency of the test method, the drag from a standard reference anionic wash detergent solution was measured before an after each trial run, and the value obtained therefrom arbitrarily assigned a coefficient of friction of 1.00. Each trial run was referenced to the fatty acid lubricant trials, thus the results are reported as a relative coefficient of friction vs. this standard. .sup.2 Control car wash concentrate for lubricity COF reference: 2.0% hydrotrope, 4.0% SXS, 10.0% EDTA, 8.0% nonionic surfactant, 13.5% TEA, 10.0% anionic surfactants, and the remainder soft water. .sup.3 7.0% glycols, 9.0% amine, 4.0% neutralizing acid, 2% linear nonionic surfactant, and the remainder as soft water. .sup.4 7.0% glycols, 9.0% amine, 4.0% neutralizing acid, 2% secondary nonionic surfactant, and the remainder as soft water. .sup.5 7.0% glycols, 9.0% amine, 4.0% neutralizing acid, 1% secondary nonionic surfactant, and the remainder as soft water. .sup.6 7.0% glycols, 6.0% amine, 4.0% neutralizing acid, 10% secondary nonionic surfactant, and the remainder as soft water. .sup.8 BELIEVE is an industrial car wash detergent for high pressure washing, from S. C. Johnson Co., Rascine, WI. .sup.9 ZIP WAX is a commercial car wash detergent, from Turth Wax, Inc., Chicago, IL.
A test was performed to determine the ability of coatings of the fatty amines of the invention to repel or minimize ever present, and unsightly, water spots in detergent products (like windshield dewatering aids). Because this soil, on a windshield, is one of the more visual for a consumer, any control would be quite beneficial. Tables 6 and 7 list evaluations for various amines, 2 control samples, and 4 examples of competitive art for hard water scale formation. The test was conducted by applying the amine coating to a glassy-ceramic titled surface, except for the control samples, then followed by 15 well water rinses, with 30-minute drying between rinses. The tiles were visually evaluated at the end of the 15 cycles on a scale of 1-4 (see reference #2 in Table 6).
The current results show that the longer chain (>C12) alkyl-ether amines function extremely well as hard-surface water spot inhibitors while the prior art is less effective, and sometimes comparable to no treatment at all.
TABLE 6______________________________________Anti-Scaling Properties of Amine CoatingsUsing Well Water                           Final Well    Amine Anti-  Test Solution                           Water SpotRun #    Sealant      pH.sup.1  Rating.sup.2______________________________________Compositions of the Invention1        C.sub.12-15 linear                 2.6       1    ether diamine.sup.32        C.sub.12-15 linear                 6.0       1    ether diamine.sup.33        C.sub.12-15 linear                 10.5      1    ether diamine.sup.34        C.sub.12-14 linear                 2.2       1    ether diamine.sup.45        C.sub.12-14 linear                 8.8       1    ether diamine.sup.46        branched     3.0       2    isotridecyl    ether diamine.sup.57        branched     8.0       2    isotridecyl    ether diamine.sup.58        C.sub.8-10 linear                 8.4       3    ether monoamine.sup.69        C.sub.8-10 linear                 3.2       4    ether monoamine.sup.6Prior Art10       prior art.sup.7 ;                 8.0       2    ethoxylated    alkyl amine.sup.811       prior art.sup.9 ;                 2.7       4    benzyl quat.sup.1012       prior art.sup.9 ;                 7.4       4    benzyl quat.sup.1013       none (control                 3.1       4    A).sup.1114       none (control                 8.6       4    B).sup.11______________________________________ .sup.1 pH adjusted with glycolic acid. .sup.2 1 = no to few water spots, small diameter, easily removed by wiping. 2 = a few water spots, medium in size, easily removed by wiping. 3 = a few to many water spots, large in size, difficult to remove by wiping. 4 = many water spots, large in size, difficult to remove, dirty looking. .sup.3 Tomah DA19. .sup.4 Tomah DA1618. .sup.5 Tomah DA17. .sup.6 Tomah PA1214. .sup.9 current art using quats; JP 58076477. .sup.10 Ecolab Q372 quat. .sup.11 Control = a tile cleaned with Chlorox cleanser, rinsed five times and dried.
Example 6 was repeated but now using formulated detergent cleaners instead of dewatering aids. Similar control of water spotting can be achieved.
TABLE 7______________________________________Anti-Spotting Properties of Amine Coatings inFormulated Cleaners                           Final Well WaterRun #  Cleaning Product               Test Solution pH                           Spot Rating.sup.1______________________________________1      acid cleaner.sup.2               2.6         4  (no amine)2      acid cleaner.sup.2               3.0         1  (with ether  amine).sup.33      neutral cleaner.sup.4               7.1         4  (no amine)4      neutral cleaner.sup.4               6.7         1  (with ether  amine).sup.35      alkaline     10.3        4  cleaner.sup.5 (no  amine)6      alkaline     10.3        2  cleaner.sup.5 (with  ether amine).sup.3______________________________________ .sup.1 Concentrated cleaners used at recommended 2oz/gal. dilution. .sup.2 Acid Cleaner = 7% sulfamic acid, 7.5% citric acid, 12% amine oxide 9% glycol solvents, 10% phosphoric acid, remainder as fragrance/dye/water .sup.3 Amine = Tomah DA19. .sup.4 neutral cleaner: 6.8% acetic acid, 9.6% KOH, 10.0% linear alcohol ethoxylate, 10.0% hexylene glycol, remainder water. Additional KOH used for neutralization when no amine present. .sup.5 Alkaline Cleaner = 6% MEA, 5% EDTA, 8% betaine surfactant, 20% glycol solvents, 6% LAS, remainder as fragrance/water.
Detergent samples were prepared fatty alkyl ether amines of the invention, and the prior art as taught by Chestochowski2 and Fasterding2, with alcohol or glycol-type solvents added at various levels to fulfill the prior art's requirement for a stabilizing hydrotrope. Samples were warmed to 49° C. and stirred continuously for 30 minutes, after which time formula stability was assessed visually. The results, shown in Table 8, demonstrate an advantage to the incorporation of the highly soluble linear alkyl ether amines or diamines, insofar as a hydrotrope is not required for concentrate stability. This is a departure from the prior art as described by the cited references; i.e., the use of alkyl ether amines and diamines allows for minimizing or eliminating co-solvents and hydrotropes, while the formulas of the prior art require substantial hydrotrope coupling.
TABLE 8______________________________________Concentrate Stability with Hydrotropesat Various Levels                               Concentrate   Base Formula               Hydrotrope                         %     Stability______________________________________current alkyl ether --        0.0   OKinvention.sup.1   diamineprior art.sup.2   alkyl diamine               --        0.0   undissolved                               solids.sup.3current alkyl ether propylene 2.5   OKinvention.sup.1   diamine     glycolprior art.sup.2   alkyl diamine               propylene 2.5   undissolved               glycol          solidscurrent alkyl ether propylene 5.0   OKinvention.sup.1   diamine     glycolprior art.sup.2   alkyl diamine               propylene 5.0   undissolved               glycol          solidscurrent alkyl ether hexylene  2.5   OKinvention.sup.1   diamine     glycolprior art.sup.2   alkyl diamine               hexylene  2.5   undissolved               glycol          solidscurrent alkyl ether hexylene  5.0   OKinvention.sup.1   diamine     glycolprior art.sup.2   alkyl diamine               hexylene  5.0   OK               glycolcurrent alkyl ether isopropanol                         2.5   OKinvention.sup.1   diamineprior art.sup.2   alkyl diamine               isopropanol                         2.5   undissolved                               solidscurrent alkyl ether isopropanol                         5.0   OKinvention.sup.1   diamineprior art.sup.2   alkyl diamine               isopropanol                         5.0   OK______________________________________ .sup.1 Proposed art incorporating linear alkyl ether diamines, formulated as follows: designated hydrotrope with 2.5% acetic acid, 10.0% C.sub.12-1 alkyloxypropyl1,3-diamino propane, 10.0% nonionic surfactant, and the remainder soft water. .sup.2 Prior art as per DD 91104, US 3440063, and DE 3439440 formulated with designated hydrotropes and 2.5% acetic acid, 6.6% NOleyl-1,3-diamino propane, 3.4% Ncoco-1,3-diamino propane, 10% nonionic surfactant, and the remainder soft water. .sup.3 Undissolved solids in the liquid material are not desirable, singl phase liquids are preferred.
Samples representing the proposed invention and the prior art set forth in the footnotes of Table 9 were formulated according to the compositions in Table 9 below. One percent solutions were prepared using the challenge water diluent (below), and the solution pH adjusted to 5-10 with dilute acetic acid or KOH. Clouding behavior was determined after 15 minutes. Surprisingly, the superior solubility of the proposed arts linear alkyl ether (di)amines as evidenced by the aforementioned concentrate stability, is buttressed by a tolerance for anions which is unsurpassed by the current fatty amine technology. The alkyl ether (di)amines allow for an extended pH range for formulation, and selection of the appropriate alkyl ether amine raw material allows for a formulation pH range not available with the prior art amines.
A test of clouding behavior of detergent solutions as per Weber6 was done. A 500 ppm Na2 SO4 and 500 ppm NaCl softened water preparation was made. This anion-laden water was used as the detergent diluent.
TABLE 9__________________________________________________________________________Solution Clarity at pH 5-10 in Anion-Laden Soft WaterCompositions           1% Solution Clarity in Challenge.sup.1 Water                  pH.sup.2Test   Formula     Amine Type % 5   6   7   8   10  11__________________________________________________________________________Proposed Art1  detergent I.sup.3     tetradecyloxypropyl-                8 clear                      clear                          clear                              clear                                  cloudy                                      --     1,3-diamino propane2  detergent     C.sub.12-14 alkyloxypropyl-                8 clear                      clear                          clear                              clear                                  cloudy                                      --   II.sup.3     1,3 diamino propane3  detergent     C.sub.12-14 alkyloxypropane                6 clear                      clear                          clear                              clear                                  cloudy                                      --   III.sup.3     1,3 diamino propane4  detergent     C.sub.12-15 alkyl-                3 --  --  --  --  --  clear   IV.sup.4     oxypropylamine5  detergent     C.sub.12-14 alkyloxypropyl-                3 --  --  --  --  --  clear   IV.sup.4     1,3 diamino propanePrior Art6  prior art     cocoamine  3 --  --  --  --  --  cloudy   I.sup.4,5,67  prior art     oleylamine 3 --  --  --  --  --  cloudy   I.sup.4,5,69  prior art     N-oleyl-1,3-diamino                8 hazy/                      hazy/                          cloudy                              cloudy                                  cloudy                                      --   III.sup.3,5,6     propane      opaque                      opaque10 prior II.sup.3,5,6     N-oleyl/cocoa-1,3-                4/4                  clear                      clear                          clear                              cloudy                                  cloudy                                      --     diamino propane11 prior art     N-oleyl/cocoa-1,3-                4/4                  clear                      clear                          clear                              cloudy                                  cloudy                                      --   III.sup.3,5,6     diamino propane12 prior art     N-oleyl/coco-1,3-                4/2                  cloudy                      clear                          clear                              cloudy                                  cloudy                                      --   III.sup.3,5,6     diamino propane__________________________________________________________________________ .sup.1 Challenge water prepared by adding 500 ppm Na.sub.2 SO.sub.4 and 500 ppm NaCl to softened water. .sup.2 1% detergent solutions adjusted to pH 5, 6, 7, 8, 9 or 10 with dilute acetic acid or dilute KOH. .sup.3 Composition of formulas: 8.0% total amines, 10.0% hydrotrope, 1.8% acetic acid, 10.0% nonionic surfactant, and 70.2% water. .sup.4 Composition of formula: 3.0% amine, 7.0% EDTA, 12.7% alcohol and alkylamine nonionic surfactants, 2.5% builder, 3.2% amine oxide. .sup.5 Prior art as taught by DD 91104, US 3440063, and DE 3439440. .sup.6 Prior art examples presented in US 5441654, and US 5062978.
Windshield dewatering samples representing the proposed invention and the prior art were tested for consumer safety by pouring 1 gram of the formula concentrate on a watch glass slide and heating with a propane flame. The results of Table 10 show a subjective rating of the products, and demonstrate the aqueous fatty alkyl ether amines to be much safer for general use over the prior art. The current invention samples (test 1-3) went to dryness, while all the prior art examples (4-7) supported rapid to instantaneous combustion.
TABLE 10______________________________________Flammability of Window Dewatering Aids.sup.1Test #    Wash Formula   Flammability______________________________________Current Art1         car dewatering flash point >180° F.     formula 3.sup.22         car dewatering flash point >180° F.     formula 4.sup.23         car dewatering flash point >180° F.     formula 5.sup.2Prior Art4         SUDDEN SHINE.sup.3                    flammable5         RAIN-X.sup.4   very flammable6         prior art I.sup.5                    very flammable7         prior art II.sup.6                    flammable______________________________________ .sup.1 Samples representing the proposed invention and the prior art were tested for consumer safety by pouring 1 gram of the formula concentrate o a watch glass slide and heating with a propane flame. The results show a subjective rating of the products. .sup.2 Same test samples as noted in Table 5. .sup.3 SUDDEN SHINE is a commercial auto dewatering aid from Plastone Co. Chicago, IL. .sup.4 RAINX is a commercial auto windshield dewatering aid, from .sub.----, Phoenix, AZ. .sup.5 prior art as taught in DD 91104. .sup.6 prior art as taught in DE 3439440.
The following formulation was manufactured into a solid block car wash formulation that could be dispensed by spraying the solid composition with water in a dispenser creating a concentrate solution that can be then conveyed to a use locus in a vehicle cleaning station. The formulation is made by introducing ingredients 1 through 4 in a heated stirred tank of appropriate size. After the material is heated and mixed to a temperature of about 75° C., ingredients 5 and 6 are added and mixed until uniform. In the uniform mixture, item 7 is added and mixed until uniform. After equilibration is achieved, powdered ingredients 8 and 9 are slowly added to avoid caking or lumping. The composition is stirred until uniform and charged in 8 pound portions to polyethylene bottles which can then be cooled and solidified. The bottles are ideal for capping, distribution and use at a vehicle cleaning station. The solid formulation achieves results similar to the liquid formulation set forth above.
wherein the aqueous concentrate composition is substantially free of a hydrocarbon wax and a polydimethyl siloxane.
2. The composition of claim 1 wherein the nonionic comprises a C6-24 alcohol ethoxylate, a fatty amine ethoxylate, a fatty ether amine ethoxylate, an alkylphenol ethoxylate or mixtures thereof.
3. The composition of claim 1 wherein the fatty alkyl ether amine comprises a C10-20 alkyl oxyalkyl-1,3-diaminopropane.
4. The composition of claim 1 wherein the fatty alkyl ether amine comprises a C10-20 alkyl oxyalkylamine.
5. The composition of claim 1 consisting essentially of about 1-20 wt % of the fatty alkyl ether amine composition, about 0.1 to about 20 wt % of nonionic surfactant, about 0.01 to about 10 wt % of sufficient acid or base material to obtain a substantially neutral pH and water.
6. The composition of claim 1 comprising about 0.1 to 20 wt % of the fatty alkyl ether amine composition, about 0.1 to 10 wt % of a nonionic surfactant composition or blend thereof and water.
7. The composition of claim 1 wherein the composition comprises an emulsion.
wherein the composition is substantially free of a hydrocarbon wax and is also substantially free of a polydimethyl siloxane.
9. The composition of claim 8 wherein the alkyl ether amine comprises a C10-20 alkyl oxypropyl-1,3-diaminopropane.
10. The composition of claim 8 wherein the alkyl ether amine comprises a C10-20 alkyloxypropylamine.
11. The composition of claim 8 wherein the sequestering agent comprises an organic chelant.
12. The composition of claim 8 wherein the sequestering agent comprises a condensed phosphate.
13. The composition of claim 8 wherein the sequestering agent comprises ethylene diamine tetraacetic acid, trisodium hydroxyethylene diamine triacetate or salts thereof.
14. The composition of claim 8 wherein the nonionic surfactant comprises an EO/PO block copolymer, an alkylphenol ethoxylate, a linear alcohol ethoxylate a fatty amine ethoxylate or fatty ether amine ethoxylate or mixtures thereof.
15. The composition of claim 10 wherein the composition additionally comprises an ethoxylate amine of the formula R--N(A) (B) where A is (EO)x and B is (EO)y or H; wherein EO represents ethyleneoxide, x represents a number from about 1 to 50 and R represents the fatty alkyl group, a fatty alkyl ether group or fatty alkyl ether group having 6-24 carbon atoms.
16. The composition of claim 10 wherein the aqueous concentrate composition has a pH of about 6-13.
wherein the aqueous composition and rinse is substantially free of a hydrocarbon and a polydimethyl siloxane material.
18. The method of claim 17 wherein the rinse is applied at high pressure.
19. The method of claim 17 wherein the high pressure comprises greater than about 100 pounds per square inch.
20. The method of claim 17 wherein the alkyletheramine comprises a C10-20 alkyloxypropyl-1,3-diaminopropane.
21. The method of claim 17 wherein the alkyletheramine comprises a C10-20 alkyloxypropylamine.
22. The method of claim 17 wherein the nonionic surfactant comprises a linear alcohol ethoxylate, an alkyl phenol ethoxylate, an EO/PO block copolymer fatty amine ethoxylate, fatty ether amine ethoxylate or mixtures thereof.
wherein the aqueous cleaner composition is substantially free of a hydrocarbon and is substantially free of a polydimethyl siloxane composition.
24. The method of claim 23 wherein the rinse is applied at high pressure.
25. The method of claim 23 wherein the high pressure comprises greater than about 100 pounds per square inch.
26. The method of claim 23 wherein the alkyletheramine comprises a C10-20 alkyloxypropyl-1,3-diaminopropane.
27. The method of claim 23 wherein the alkyletheramine comprises a C10-20 alkyloxypropylamine.
28. The method of claim 23 wherein the nonionic surfactant comprises a linear alcohol ethoxylate, an alkyl phenol ethoxylate, an EO/PO block copolymer fatty amine ethoxylate, fatty ether amine ethoxylate or mixtures thereof.
wherein the aqueous composition is substantially free of a hydrocarbon and is substantially free of a polydimethyl siloxane composition.
30. The method of claim 29 wherein the rinse is applied at high pressure.
31. The method of claim 29 wherein the high pressure comprises greater than about 100 pounds per square inch.
32. The method of claim 29 wherein the alkyletheramine comprises a C10-20 alkyloxypropyl-1,3-diaminopropane.
33. The method of claim 29 wherein the alkyletheramine comprises a C10-20 alkyloxypropylamine.
34. The method of claim 29 wherein the nonionic surfactant comprises a linear alcohol ethoxylate, an alkyl phenol ethoxylate, an EO/PO block copolymer fatty amine ethoxylate, fatty ether amine ethoxylate or mixtures thereof.
36. The composition of claim 35 wherein the solidification agent is urea.
37. The composition of claim 35 wherein the nonionic comprises a C6-24 alcohol ethoxylate, a fatty amine ethoxylate, a fatty ether amine ethoxylate, an alkylphenol ethoxylate or mixtures thereof.
38. The composition of claim 35 wherein the fatty alkyl ether amine comprises a C10-20 alkyl oxyalkyl-1,3-diaminopropane.
39. The composition of claim 35 wherein the fatty alkyl ether amine comprises a C10-20 alkyl oxyalkylamine.
40. The composition of claim 35 consisting essentially of about 1-20 wt % of the fatty alkyl ether amine composition, about 0.1 to about 20 wt % of nonionic surfactant, about 0.01 to about 10 wt % of sufficient acid or base material to obtain a substantially neutral pH and water.
41. The composition of claim 35 comprising about 0.1 to 20 wt % of the fatty alkyl ether amine composition, about 0.1 to 10 wt % of a nonionic surfactant composition or blend thereof and water.
42. The composition of claim 35 additionally comprising a sequestrant.
43. The composition of claim 35 additionally comprising a silicate.
44. The composition of claim 35 additionally comprising an amine oxide.
MX9801498A MX9801498A (en) 1997-02-25 1998-02-24 Vehicle cleaning and drying compositions.
ITTO980141 IT1302062B1 (en) 1997-02-25 1998-02-24 Compounds for cleaning and drying vehicles.
AR003210A1 (en) * 1995-08-07 1998-07-08 Procter & Gamble detergent compositions for clothes washing comprising a detersive surfactant selected amine and especially perfumes.


2.75.010 Supervision, management and control of public library – Functions of library board.
2.75.020 Right of library board to accept and use gifts, bequests, etc.
2.75.030 Supervision of public library program.
2.75.040 Established – Use by public.
2.75.050 Contribution of books and periodicals accepted.
2.75.060 Special assessment for library as part of costs in civil actions.
*Charter reference – Authority of council to grant aid to public library, § 11(11).
State law reference – Local libraries, Code of Virginia, § 42.1-33 et seq.
The general supervision, management and control of the city’s public library is hereby transferred to the city manager, with the library board being retained in an advisory capacity to the librarian. The library board shall serve in an advisory capacity to the librarian on the development and revision of policies, the selection of reading and recorded materials, evaluation of priorities which should be given to different library materials and programs and the encouragement of optimum utilization of the library programs by the citizens of the city. (Code 1964, § 2-46; Code 1985, § 15-1; Amended during the 2003 reformat).
Cross reference – Time limit for parking at public library, SCC 10.25.090.
The library board shall have the right to accept donations, gifts, demises and bequests of money, tangible and intangible personal property and real estate and to use such, or the income therefrom, for the benefit of the public library. (Code 1964, § 2-47; Code 1985, § 15-2).
The library director, who shall be appointed by and report to the city manager, shall supervise the city’s public library program. (Code 1964, § 17-8.1; Code 1985, § 15-3; Ord. 1-14-8).
*State law reference – Law libraries, Code of Virginia, §§ 42.1-60 – 42.1-71.
A law library is hereby established under the name of “Staunton-Augusta Law Library” and the same shall be open for the use of the public under such rules and regulations as may be established by the judge of the circuit court of Augusta County, by order, from time to time; provided, however, that the use of the books owned by the Supreme Court of Virginia shall conform to such rules and regulations as the Supreme Court of Virginia may prescribe, from time to time, for the use of such library and the times it shall be kept opened. (Ord. 9-9-82, § 2; Code 1985, § 15-14).
The contribution of the Augusta County Bar Association of all the law books and law periodicals owned by such association and located within the Supreme Court of Virginia Law Library on the third floor of the Masonic Building is hereby accepted. (Ord. 9-9-82, § 1; Code 1985, § 15-15).
(1) There is hereby assessed as part of the costs incident to each civil action filed in the circuit court of the city and the general district court of the city the sum of $2.00. Such assessment shall be collected by the clerk of the court in which the action is filed and remitted to the treasurer of the city and held by such treasurer in a separate fund, subject to disbursements by the judge of the circuit court of Augusta County for the acquisition of law books and law periodicals and other lawful disbursements for the use and maintenance of the law library established by this article.
(2) The assessment provided for in this section shall be in addition to all other costs prescribed by law, but shall not apply to any action in which the commonwealth or any political subdivision thereof or the federal government is a party and in which costs are assessed against the commonwealth, any such political subdivision or the federal government. (Ord. 9-9-82, § 3; Code 1985, § 15-16).
State law reference – Authority for above section, Code of Virginia, § 42.1-70.


Every child deserves and is entitled to receive financial support from his or her parents. With the help of a San Jose child support lawyer, support may be ordered when parents are obtaining a divorce, legal separation, or annulment. Child support is also available in a paternity action, when a child was born to parents who were not married at the time the child was born, or in a domestic violence case where one parent is seeking a restraining order from the Court.
Child support may be ordered by the Court until the supported child turns 18, and is not a full-time high school student, turns 19, marries or registers in a domestic partnership, emancipates, or passes away, whichever occurs first. There are special cases when support may be ordered for a longer period of time, such as when the child has a disability and that child is not self-supporting. Parents may also agree to a support order that is longer in duration than the limit set by law.
The right to child support has not been assigned to the county pursuant to Welf. & Inst.C. §11477 and no public assistance application is pending. See Family Code §4065(a)(5).
In order to modify a child support order, a change of circumstances is generally required. A change of circumstances may include: 1) a change in timeshare; 2) a change in either party’s income; or 3) a change in other variables that would warrant a modification of support.
However, if parties have entered into a below guideline stipulated agreement regarding child support, no change of circumstances need to be demonstrated in order to modify the child support order to the guideline level. See Family Code §4065(d).
Additionally, under no circumstances may a parent waive their right to child support. Child support is for the benefit of the children. Accordingly, child support is always modifiable.
Childcare Costs: related to employment or reasonably necessary education or training for employment. See Family Code §4062(a)(1).
Uninsured Health Costs: reasonable uninsured health care costs for the children. See Family Code §4062(a)(2).
Educational or Other Special Needs: costs related to a child’s education or special needs. See Family Code §4062(b)(1).
Visitation Travel Expenses: expenses related to travel for visitation. See Family Code §4062(b)(2).
While additional support is generally shared on a 50-50 allocation, deviation from this allocation may be ordered upon an affirmative request. If a different allocation is requested, the Court will calculate support first and then add-ons may be allocated based proportionately on the parties’ adjusted net disposable income. See §4061(b)(2).
Re: New-Mate Income: Generally, there is a statutory bar to looking at a new-mate’s income for support purposes. However, it might be possible in an extraordinary case where not doing so would result in extreme hardship to the child. Marriage of Wood, 37 CA4th at 1071.
Upon re-marriage or entering into a new relationship, parents often question whether their new spouse or new-mate’s income will be considered for child support purposes. Under Family Code §4057.5, the Court generally does not include the new spouse or new mate’s income. It is only in cases where excluding this income would lead to extreme and severe hardship to a child that the Court may decide that the new income should be considered. If this preliminary determination is made, the Court then must also determine if considering the new-mate’s income would lead to a severe hardship to a child supported by the obligator or the new-mate.
If you would like to consult with a support lawyer about whether new-mate income should be considered in your support case, contact Aeschleman Law for a consultation.
Whether you or the other parent are seeking a child support order for the first time or seeking to modify a prior child support order, the San Jose child support attorneys at Aeschleman Law can assist you in calculating the guideline support that is appropriate in your case. We will negotiate with the other parent, and if negotiations fail, we will zealously advocate for you in Court to obtain an order that protects your child’s rights to financial support as well as your right to have support properly calculated. If you are the supporting parent and you believe that you are being asked to pay more than you can afford or than what your child requires, the family law attorneys at Aeschleman Law can analyze your financial circumstances to determine whether your support order should be lowered, and if it is appropriate, will advocate that you are not ordered to pay more than what is required by law.
Aeschleman Law can also assist you if you have an existing support order and the other parent is not complying with that order. We will advise you in how to enforce your support order and to collect any past due support payments.


text:
The cooperation concept, which in its content can be regarded as an economic phenomenon, the essence of which is the economic relationships between partners in terms of cooperation in order to achieve the common goal of lower specific costs of resources on the basis of mutual benefit for all participants, has become a powerful component and a promising direction. economic development of many countries of the world.
The activity of cooperative enterprises takes place in a certain institutional environment, which is defined as a set of fundamental social, political, legal, and economic rules within the framework of human behavior. It is the institutional approach to the cooperation development that is currently at the center of attention of contemporary researchers and needs a detailed analysis. Therefore, the purpose of the article is to study the main institutional imperatives of the development of cooperative relations of business entities in modern conditions.
In the article, based on theoretical-methodical analysis and structurally functional approach, the system-forming socio-economic institutes of cooperation are defined. It is determined that among the socio-economic institutions of co-operation, institutions of cost, efficiency, co-operative ideology occupy a significant place. The institution of expenditures is described in detail, defined types of transaction costs (information search, negotiation, measurement, specification and protection of property rights, opportunistic behavior, politicization) and their characteristics in the context of cooperation. The institute of cooperative ideology and its influence on expenses of cooperative association are investigated. It is proved that the main advantage and motive of cooperation is the desire to obtain an additional (synergetic) effect from the interaction of participants. The synergistic effect may be due to the fact that the combined use of several mutually agreed strategies is more beneficial than the isolated implementation of someone and comes as a result of the self-organization of complex systems. The following main elements of the cooperative system of interaction are defined: enterprise integrator, suppliers of material resources, competitors, intermediaries, consumers, etc. The synergy effect in the cooperative is substantiated.
cooperation; socio-economic institutions; transaction costs; cooperative ideology; synergy effect.
Minakov, I. A. (2007). Kooperaciya i agropromyshlennaya integraciya v APK [Cooperation and agro-industrial integration in the agro-industrial complex]. Moscow: Kolos S [in Russian].
United Nations (2010, February 11). General Assembly. Resolution adopted by the General Assembly 64/136 «Cooperatives in social development». Retrieved from www.copac.coop/publications/un/a64r136e.pdf.
Böök, S. Å., Prickett, M., & Treacy, M. (eds.) (1992, October). Cooperative values in a changing world: report to the ICA Congress, Tokyo. Geneva: The International Cooperative Alliance.
Laidlaw, A. (1980, October). Cooperatives in the year 2000. The 27th Congress of the International Cooperative Alliance, Moscow.
Watkins, W. P. (1986). Cooperative Principles Today and Tommorow. UK: Holyoake Books.
Review of International Cooperation (1995). The International Cooperative Alliance Statement on Cooperative Identity. ICA Review, 88, 1.
Veblen, T. (1965). The Theory of the Leisure Class: An Economic Study of Institutions. New Brunswick (USA), London (U. K.): Transaction Publishers.
Coase, R. H. (1937, 1952). The Nature of the Firm. Econometrica, 4, reprinted in American Economic Association. Readings in Price Theory. Chicago: Irwin, 331—351.
North, D. C. (1990). Institutions, institutional change and economic performance. Cambridge.
Vilyamson, O. E. (2001). Ekonomichni instytutsii kapitalizmu: firmy, marketynh, ukladannia kontraktiv [Economic institutions of capitalism: companies, marketing, contracts]. Kyiv, ArtEk [in Ukrainian].
North, D. (1986). The New Institutional Economics. Journal of Institutional and Theoretical Economics, 142, 230—237.
Ushkarenko, U. V. (2009). Vykorystannia instytutsiinoho pidkhodu pry stvorenni kooperatyvu [Using the institutional approach to creating a cooperative]. Tavriiskyi naukovyi visnyk : zb. nauk. prats KhDAU — Tavriysky Scientific Bulletin: Sb. sciences works of KSIAU, 65. Kherson: Ajlant [in Ukrainian].
Naumenkova, S. V. (2014). Forecasting of capitalization of banking institutions in Ukraine. Financial and credit activity: problems of theory and practice, 17, 57—64.
Shastitko, A. E. (1998). Neoinstitucional'naya ekonomicheskaya teoriya [Neo-institutional economic theory]. Moscow: TEIS [in Russian].
Ushkarenko, Yu. V. (2009). Silskohospodarska kooperatsiia v evoliutsiinomu vymiri [Agricultural co-operation in the evolutionary dimension]. Kherson: Ajlant [in Ukrainian].
Williamson, O. E. (1979). Transaction-cost economics — governance of contractual relations. Journal Of Law & Economics, 22 (2), 233—261.
Haken, H. (1983). Synergetics, An Introduction. Berlin: Springer.
Минаков И. А. Кооперация и агропромышленная интеграция в АПК / И. А. Минаков. — Москва : Колос С, 2007. — 264 с.
United Nations. General Assembly. Resolution adopted by the General Assembly 64/136 «Cooperatives in social development»: 11 February 2010 [Electronic resource]. — Available at : www.copac.coop/publications/un/a64r136e.pdf.
Böök S. Å. Cooperative values in a changing world : report to the ICA Congress, Tokyo, October 1992 / edited by Margaret Prickett and Mary Treacy. – Geneva : The International Co-operative Alliance, 1992. — 252 p.
Laidlaw A. Cooperatives in the year 2000 : a paper prepared for the 27th Congress of the International Cooperative Alliance / A. Laidlaw. — Moscow, 1980. — 98 p.
Watkins W. P. Cooperative Principles Today and Tommorow / W. Р. Watkins. — Manchester, UK : Holyoake Books, 1986. — 169 p.
Review of International Cooperation. The International Cooperative Alliance Statement on Cooperative Identity // ICA Review. — 1995. — Vol. 88. — № 1.
Veblen T. The Theory of the Leisure Class: An Economic Study of Institutions / T. Veblen. — New Brunswick (USA), London (U. K.) : Transaction Publishers, 1965. — 261 p.
Coase R. H. The Nature of the Firm / R.H. Coase // Econometrica. — 1937. — № 4 ; Reprinted in American Economic Association. Readings in Price Theory. — Chicago : Irwin, 1952. — P. 331—351.
North D. C. Institutions, institutional change and economic performance / D. C. North. — Cambridge, 1990. — 195 p.
Вільямсон О. Е. Економічні інституції капіталізму: фірми, маркетинг, укладання контрактів / О. Е. Вільямсон. — Київ : АртЕк, 2001. — 472 с.
North D. The New Institutional Economics / D. North // Journal of Institutional and Theoretical Economics. — 1986. — Vol. 142. — P. 230—237.
Ушкаренко Ю. В. Використання інституційного підходу при створенні кооперативу / Ю. В. Ушкаренко // Таврійський науковий вісник : зб. наук. праць ХДАУ. — Херсон : Айлант, 2009. — Вип. 65. — С. 170—175.
Naumenkova S. V. Forecasting of capitalization of banking institutions in Ukraine / S. V. Naumenkova, I. V. Domanetskyi // Financial and credit activity: problems of theory and practice. — 2014. — № 17. — Р. 57—64.
Шаститко А. Е. Неоинституциональная экономическая теория / А. Е. Шаститко. — Москва : ТЕИС, 1998. — 169 с.
Ушкаренко Ю. В. Сільськогосподарська кооперація в еволюційному вимірі : монографія / Ю. В. Ушкаренко. — Херсон : Айлант, 2009. — 404 с.
Williamson O. E. Transaction-cost economics — governance of contractual relations / O. E. Williamson // Journal of Law & Economics. — 1979. — Vol. 22 (2). — Р. 233—261.
Haken H. Synergetics, An Introduction / H. Haken. — 3rd. ed. — Springer, 1983. — 242 р.

matches: V. V. V. V. V. V.


Who Is Getting Your Tip Money? It Is Time to Put Limits on Tip-Pooling.
Please see the attached letter, which I drafted to send today to the California Supreme Court on behalf of the California Employment Lawyers' Association.
This is a letter under Rule 8.500(g) of the 2009 California Rules of Court in support of the petition for review by the Plaintiff/Appellant in Lu v. Hawaiian Gardens Casino, Inc. (2009) 170 Cal.App.4th 466, 88 Cal.Rptr.3d 345, California Court of Appeal, Second District, Division 3, No. B194209 (hereafter, Lu). This letter, on behalf of the California Employment Lawyers Association (CELA), seeks to have this Court define the scope of permissible tip pooling. The Court of Appeal’s decision in Lu is just one of several recent decisions by Courts of Appeal attempting to define the parameters of permissible tip pooling without Supreme Court guidance. Though this Court has discussed Cal. Lab. Code §351, the basis for the instant dispute (see Industrial Welfare Com. v. Superior Court (1980) 27 Cal.3d 690, 166 Cal.Rptr. 331, and Henning v. Industrial Welfare Com. (1988) 46 Cal.3d 1262, 252 Cal.Rptr. 278), this Court has never weighed in on the extent to which employers may appropriate money given by customers to service employees as gratuities and distribute it to other non-supervisory employees.
California Courts of Appeal have long followed Leighton v. Old Heidelberg, Ltd. (1990) 219 Cal.App.3d 1062, 268 Cal.Rptr. 647 (decided closely on the heels of Henning), which ruled that enforced tip pooling between servers and bussers at a restaurant is permissible under §351. Leighton emphasized that the regulation states that a gratuity is “hereby declared to be the sole property of the employee or employees to whom it was paid, given, or left for.” (Ital. added to emphasize the plural.) However, recent decisions have begun to extend the tip pooling concept beyond merely multiple service employees assisting a single customer at a restaurant table. Lu stretches the tip pool to sharing tips between a casino dealer (who directly received the tip from the customer for his/her service) and chip runners, hostesses, poker tournament and poker rotation coordinators, customer services representatives or “floormen,” and concierges. Lu, 170 Cal.App.4th at 471. CELA believes that the better-reasoned view is that tip pooling can only be proper, under the plain language of §351, between non-supervisory employees for whom the gratuities in question were “paid, given, or left for.” Under §351, tip income must not be used by an employer to subsidize the wages of other non-supervisory employees who were not responsible for the service which caused the customer to provide a gratuity.
The undersigned writes on behalf of CELA, a “person” within the meaning of Rule 8.500(g), seeking to support the petition for review. CELA is a statewide non-profit organization dedicated to protecting workers’ rights. CELA’s member attorneys represent employees in all types of employment cases in state and federal courts and before administrative agencies, including employment discrimination, wrongful discharge, wage and hour, and unemployment insurance matters. In each of these substantive areas of law, CELA’s members and their clients challenge employers who fail to adhere to California and federal employment laws. CELA frequently appears as amicus curiae in matters before this Court, including, e.g., recent appearances in Murphy v. Kenneth Cole Productions, Inc. (2007) 40 Cal.4th 1094, 56 Cal.Rptr.3d 880, Gentry v. Superior Court (2007) 42 Cal.4th 443, 64 Cal.Rptr.3d 773, and Edwards v. Arthur Andersen LLP (2008) 44 Cal.4th 937, 81 Cal.Rptr.3d 282.
CELA’s members have an abiding interest in the scope of permissible tip pools, directly at issue in this case. In particular, CELA seeks to ensure that the concept of tip pooling is not abused so as to undermine employees’ property interest in their gratuities, guaranteed by Labor Code §351, and that the State’s wage and hour laws are “liberally construed with an eye to promoting [worker] protection,” as this Court required in Henning, 42 Cal.3rd at 1269 (citing Industrial Welfare Com’n, 27 Cal.3d at 700-703). CELA hopes that this Court will not permit an interpretation, like that applied in Lu, which results or could result in tips given directly to millions of California non-supervisory workers being misappropriated to defray employers’ labor costs with respect to other workers.
In Henning, 46 Cal.3d at 1279-1281, and Industrial Welfare Com’n, 27 Cal.3d at 729-731, the Court applied §351 to eliminate the practice of tip crediting, which had been used to pay service employees receiving gratuities less than the minimum wage, or a lower minimum wage than non-tipped employees. Part of the rationale for these decisions eliminating tip crediting and the two-tiered minimum wage was that “a lower minimum (which in itself is to provide an adequate) wage is only possible because tips are used to subsidize it” (see Henning, 46 Cal.3d at 1278, citing Industrial Welfare Com’n) – and employers should not be able to use tips (the property of the employees who received them) to subsidize otherwise inadequate wages. This Court discussed the legislative history behind §351, noting that the section, in its current form, was designed to prevent employers from “obtain[ing] the benefit (as, in effect, the payment of wages) of tips and other gratuities received by their employees,” and “from taking any tip given by a patron to his employee.” Henning, 46 Cal.3d at 1279.
"We dare say that the average diner has little or no idea and does not really care who benefits from the gratuity he leaves, as long as the employer does not pocket it, because he rewards for good service no matter which one of the employees directly servicing the table renders it. This, and the near impossibility of being able to determine the intent of departed diners in leaving a tip, in our view, account for the Legislature's use of the term 'employees' in declaring that 'every such gratuity is hereby declared to be the sole property of the employee or employees to whom it was paid, given, or left for.' (Lab.Code, § 351, italics added.) It is clear that the Legislature intended by this section to cover just such a situation." Leighton, 219 Cal.App.3d at 1069.
However, the Lu court disingenuously extends this language to the present situation. CELA hopes this Court will recognize the difference between leaving a gratuity in a tip cup at a coffee shop counter or on a table at a restaurant, where it may be pooled between all the non-supervisory employees providing the service the customers received, and a tip given directly to (for example) a casino dealer working at a table alone, apparently to recognize him/her. In the latter situation, there is no need to divine the customer’s intentions – he/she is tipping the dealer. There is no reason to believe that the customer intended also to recognize chip runners, or hostesses (who are separately tipped), etc. This is not a scenario in which rejection of tip pooling would create counter-productive incentives for employees and workplace strife, as in Leighton, 219 Cal.App.3d at 1070. There, the rejection of tip pooling between servers and bussers might lead to tips being commandeered by the first person to grab them off the table, and infighting as a result. Id. Here, the dealer need not fight for the tips he/she is given or swipe them before other employees notice – the tips are given to or left for him/her directly, and no one else.
The casino simply wants to subsidize the wages of its chip runners and others who do not receive tips by giving them part of the tips earned by dealers. According to Henning, this is against the legislative intent of §351, because it is taking money out of the dealers’ hands and using it to keep down the employers’ labor costs. While CELA would certainly condone an effort to ensure greater pay for chip runners and other non-tipped employees, and they will need to receive greater wages to attract their labor, if they are not receiving portions of dealers’ gratuities, their pay should not come out of the pockets of the tipped employees – but from the casinos.
The plain language of the statute is that the gratuities become the property of the non-supervisory employees for whom they are left. “Every gratuity is hereby declared to be the sole property of the employee or employees to whom it was paid, given, or left for.” Cal. Lab. Code §351. Courts do not need to get into case-by-case findings regarding customers’ intent, which, as Leighton explained, can be vague. But it is safe to hold that, where tips are left in a tip cup or at a restaurant table, they are the property of all non-supervisors involved in providing the customer with good service – whereas, when tips are handed to a casino dealer or left at a casino table where a dealer is still sitting and where he/she is the only person working, the tips are the sole property of that dealer.
For the foregoing reasons, CELA hopes this Court will not permit courts to follow Lu, allowing the spreading to non-tipped employees of gratuities earned by and owned by particular employees, designed only to avoid payment of competitive wages in the labor market. Please grant the petition for review.
 See also, e.g., Budrow v. Dave & Buster’s of California, Inc. (2009) 171 Cal.App.4th 875, 90 Cal.Rptr.3d 239; Etheridge v. Reins International California, Inc. (2009) 172 Cal.App.4th 908, 91 Cal.Rptr.3d 816.
 All courts agree that supervisory employees must be strictly excluded from tip pools, and CELA does not challenge the portion of Lu addressing this issue. See Cal.Lab. 350(a) and (d); Lu, 170 Cal.App.4th at 485-486 (citing Jameson v. Five Feet Restaurant (2003) 107 Cal.App.4th 138, 141-143, 131 Cal.Rptr.2d 771).
 See Etheridge, 172 Cal.App.4th 908, discussing Henning and Industrial Welfare Commission (“Even though an employer can no longer use tip sharing to subsidize minimum wages of non-tipped employees, it is possible that an employer could use tip sharing to subsidize market wages of non-tipped employees, resulting in the same evil. Thus, when considering tip pooling, it is important to make certain that the employer is not using the tip pool as a de facto tip credit against market wages.”) (emph. in original). See generally id., 172 Cal.App.4th 908 (Klein, P.J., concurring and dissenting) (“The majority opinion here eviscerates section 351 's guarantee that a gratuity belongs to the employee or employees for whom it was left. The majority opinion authorizes the employer to confiscate a portion of the gratuities left for servers and to redistribute those monies to other employees, so as to subsidize the wages of non-tipped employees, in accordance with the employer's self-interest and priorities. For these reasons, the propriety and parameters of employer-mandated tip pooling warrant the prompt attention of the California Supreme Court or the Legislature.”) (emph. in original).
The sanctity of the attorney-client relationship is a fundamental pillar of our legal system, recognized throughout the public and private sector. “[T]he attorney-client privilege is the oldest privilege recognized for confidential communications at common law and is intended ‘to encourage full and frank communications between attorneys and their clients and thereby promote broader public interests in the observance of law and the administration of justice.’” Grimes v. Dept. of Navy, 99 M.S.P.R. 7, 11 (2005) (quoting Upjohn Co. v. United States, 449 U.S. 383, 389, 101 S.Ct. 677, 66 L.Ed.2d 584 (1981)). “The attorney-client privilege protects confidential disclosures made by a client to an attorney in order to obtain legal advice,...as well as an attorney's advice in response to such disclosures.” United States v. Chen, 99 F.3d 1495, 1501 (9th Cir. 1996) (quotation omitted), cert. denied, 520 U.S. 1167, 117 S.Ct. 1429, 137 L.Ed.2d 538 (1997). The attorney-client privilege falls into the class of absolute privileges. Swidler & Berlin v. United States, 524 U.S. 399, 409, 118 S.Ct. 2081, 141 L.Ed.2d 379 (1998). If you are engaged in an attorney-client relationship with counsel at the time of particular communications, then an absolute privilege should apply to those communications.
However, what if you learn that your employer, either intentionally or inadvertently, has come into possession of attorney-client emails sent through a work email account? First, if you learn that attorney-client communications or attorney work product documents are in the employer’s possession, you should immediately seek return of such communications. You should advise the employer that you consider the documents to be attorney-client privileged communications (and possibly attorney work product privileged as well). You should be clear that it is not your intention to waive any attorney-client, work product, or other privileges that apply to these documents.
You can also remind your employer that, under Fed.R.Civ.P. 26(b)(5)(B), after being notified of an inadvertent disclosure of privileged information, “a party must promptly return, sequester, or destroy the specified information and any copies it has; must not use or disclose the information until the claim is resolved; must take reasonable steps to retrieve the information if the party disclosed it before being notified; and may promptly present the information to the court under seal for a determination of the claim.” “Once a party claims the attorney-client privilege, the communication sought to be suppressed is presumed confidential.” La Jolla Cove Motel and Hotel Apartments, Inc., v. Superior Court, 121 Cal.App.4th 773, 791 (2004) (citing Cal.Evid.Code, § 917).
Generally, you can put your employer on notice that the ethical canons of the legal profession preclude the employer from searching intentionally to discover privileged information in an employee’s email account, knowing that such information is subject to an asserted or very likely attorney-client or work-product privilege. Such would include all communications between an employee and his/her employment lawyer. The American Bar Association’s Standing Committee on Ethics and Professional Responsibility, “Formal Opinion 92-368: Inadvertent Disclosure of Confidential Materials (1992),” makes clear that counsel should not seek to review information it has reason to believe was inadvertently disclosed.
If the employer is trying to hold against you something you discussed with your employment attorney on a company email system, you should also remind the employer that privileged communications do not lose their privileged character because they are communicated electronically. See California's Evidence Code § 917(b). See also, e.g., 18 U.S.C. § 2517(4) (wiretap law recognizing that electronic communications may have privileged character); Kintera, Inc. v. Convio, Inc., 219 F.R.D. 503, 514 (S.D. Cal. 2003) (applying attorney-client privilege to email communications). However, attorney-client privilege can be waived, and if the privilege is waived, then those communications may be fair game for employers to use.
The “sacred” attorney-client privilege can be waived “implicitly” only under rare, defined circumstances (see Bittaker v. Woodford, 331 F.3d 715, 718-721 (9th Cir. 2003)), such as (for example) in a legal malpractice action, where the attorney-client communications are directly placed at issue in the litigation. On the other hand, an “express waiver occurs when a party discloses privileged information to a third party who is not bound by the privilege, or otherwise shows disregard for the privilege by making the information public.” Id. at 719. By communicating to the employer seeking return of disclosed information immediately after learning of its disclosure, you convey a strong desire to maintain the privilege. On the other hand, if you forward your attorney’s email to someone else not involved in the attorney-client relationship, you have likely implicitly waived the privilege as to that particular communication.
It is the present policy of Bryan Schwartz Law (www.BryanSchwartzLaw.com) to communicate as little as possible, or not at all, with clients on their work email, because, at the very least, it creates a headache in subsequent litigation when an employer inadvertently discovers attorney-client communications and tries to use them in the case. However, I believe strongly that privileges between employees and their attorneys – not to mention, prisoners emailing their attorneys, and other attorney-client email relationships – would be of little value if, by disclaimer, “Big Brother” could simply deem all communications via particular media as non-confidential, such that privilege would be waived inherently and broadly. Many employees in the workforce do not have private email apart from their work email accounts, and thus would not be able to email their attorneys at all. Perhaps all work email (not only that of the employer against whom a party is litigating) – by virtue of the fact that a non-attorney administrator can access it – would be unprivileged, including all emails sent by attorneys to clients from the attorneys’ own law firms’ email accounts. By this rule, all of the emails between the employer and the employer’s own attorneys regarding your case would also be unprivileged, because privilege was waived when they utilized the company’s email system. Perhaps all email sent via Gmail, Yahoo, Comcast, SBC, and Hotmail would also be unprivileged, since there are no doubt skilled individuals who can access our emails sent via these services as well.
In sum, while the danger of inadvertent disclosure during discovery makes attorney-client communications by work email not a “best practice,” it does not mean that all attorneys and all clients who communicate via a work email have waived their sacred rights. In practice, many or most employers tolerate usage of work email for some personal uses. If the employer demonstrated a widespread enforcement of a “no personal use” policy, such that you and individuals known to you were being routinely counseled and disciplined for using their email to send greetings to spouses or friends, or, if the employer’s email system generally prevented outside emails all together, then perhaps you would be on clear notice that your emails were being monitored and would have a reasonable belief they were non-confidential. However, just because we are aware in the abstract that someone (like a forensic software examiner or technology specialist) could figure out how to probe our email accounts, is not the same as knowing that each of our emails is being actively monitored. By way of contrast, when one calls a credit card company, the phone system indicates on every call that you are “being monitored and recorded for quality and training purposes” – which might defeat an expectation of privacy/confidentiality. See also Cal. Evid. Code. §917(b). In many cases, there is no indication that employees know that each of their emails are being individually monitored. An employee of an employer with hundreds or thousands of employees worldwide need not assume that every communication he/she has with anyone about anything is being read by individuals who are not the intended recipients of the communication.
Even if you could ever have reasonably expected the employer to learn that you did exchange some emails with your attorney while at work (i.e., the identities of your addressees), you would have no reason to believe that the employer at the direction of legal counsel would overtly violate legal ethical obligations by seeking to review the substance of communications known to be between a client and his/her counsel.
Your communications with counsel via work email arguably maintain their privileged character, and should not be employed by the employer against you.
 It is no doubt possible for technologically-gifted individuals to listen to attorney-client communications via telephone, too, and yet courts have found that individuals have a reasonable expectation of privacy in their phone conversations. Quon v. Arch Wireless Operating Co., Inc., 529 F.3d 892, 904 (9th Cir. 2008) (citing Katz v. United States, 389 U.S. 347, 353, 88 S.Ct. 507, 19 L.Ed.2d 576 (1967) (“One who occupies [a phone booth], shuts the door behind him, and pays the toll that permits him to place a call is surely entitled to assume that the words he utters into the mouthpiece will not be broadcast to the world. To read the Constitution more narrowly is to ignore the vital role that the public telephone has come to play in private communication.”). Before Katz, courts had found that communications by United States mail could also be entitled to confidentiality/an expectation of privacy. Quon, 529 F.3d at 905 (citing United States v. Jacobsen, 466 U.S. 109, 114, 104 S.Ct. 1652, 80 L.Ed.2d 85 (1984)). Email (and text message) plays a role today like the phone booth and the U.S. mail have played in the past, and the content of messages transmitted via these media can have a reasonable expectation of privacy and confidentiality. Quon, 529 F.3d at 905-906 (citing United States v. Forrester, 512 F.3d 500, 510 (9th Cir. 2008)).
 Without having statistical or expert data on point, my experience suggests that virtually every client, co-worker, and friend whose work email permits sending to and receiving from outside parties does have personal communications from time to time on this email system, which he or she does not expect to be read by non-addressees at the employer.