WO1999019438A1 - High foaming detergent composition having non-ionic surfactant base - Google Patents

High foaming detergent composition having non-ionic surfactant base Download PDF

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Publication number
WO1999019438A1
WO1999019438A1 PCT/US1998/021788 US9821788W WO9919438A1 WO 1999019438 A1 WO1999019438 A1 WO 1999019438A1 US 9821788 W US9821788 W US 9821788W WO 9919438 A1 WO9919438 A1 WO 9919438A1
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composition
weight
average
carbon atoms
alkyl
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PCT/US1998/021788
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French (fr)
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WO1999019438A9 (en
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Steven J. Knox
Arshad Malik
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Stepan Company
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Priority to AU10896/99A priority Critical patent/AU1089699A/en
Publication of WO1999019438A1 publication Critical patent/WO1999019438A1/en
Publication of WO1999019438A9 publication Critical patent/WO1999019438A9/en

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0094High foaming compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/825Mixtures of compounds all of which are non-ionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/835Mixtures of non-ionic with cationic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/94Mixtures with anionic, cationic or non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/52Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/52Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/75Amino oxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/90Betaines

Definitions

  • This invention relates to formulations for manually washing dishes, hand soaps, and for high foaming cleaning compositions .
  • Description of the Related Art Light-duty liquid detergent formulations for kitchen surfaces are well known. Kitchen surfaces include counter tops, stove tops, dishes and any other hard surface commonly found in k tcnen environments.
  • the term "dishes” includes any utensils involved m food preparation or consumption Kitchen surfaces, particularly dishes, must be washed free of food residues, greases, proteins, starches, gums, dyes, oils and burnt organic residues .
  • anionic synthetic surfactants with or without a nomonic surfactant.
  • Many of such formulations contain a sulfonate-type anionic surfactant, for example, an alkylbenzene sulfonate or an alkane sulfonate, in conjunction with a sulfate or alkyl ether sulfate, or a nomonic surfactant, for example, an alcohol ethoxylate, an alkyl phenol ethoxylate, a mono- or diethanolamide or an amine oxide.
  • the sulfonate material generally predominates.
  • U.S. Patent No. 2,746,928 discloses that it is not possible to mix anionic surface-active agents with quaternary ammonium germicides.
  • the cationic quaternary ammonium germicide reacts with the anionic surface-active agent resulting in a reduction in germicidal and detergent activity.
  • anionic surfactants are incompatible with cationic quaternary antimicrobial surfactants and nomonic surfactants do not normally provide significant foaming capability to liquid formulations Therefore, dish washing liquids combining good foaming and antimicrobial activities are not available to the consumer.
  • anionic surfactant systems such as those found in the current light duty liquids are classified as high foamers . Conversely, nomonic surfactant systems are classified as low foamers .
  • the useful nomonic surfactants include ethoxylates that have various chain lengths not exceeding 12 carbon atoms and degrees of ethoxylation that allow the dish washing liquid to be effective on a wide range of food soils while providing excellent flash foam volume and foam stability. This system provides the consumer with effective cleaning on, but not limited to, greasy food soils, fatty food soils, and oily food soils .
  • the invention provides surfactant compositions based on nomonic surfactant components that function as cleaning compositions. Further included m the invention are disinfectant hand soaps, body washes, disinfectant or antibacterial dishwashing liquids, and conditioning shampoos. Each of these latter cleaning compositions includes at least one cationic ammonium salt. The specific cationic salts are selected depending on the ultimate use or function of the cleaning composition.
  • the invention is a microbiological active quaternary ammonium salt ingredient homogeneously incorporated into a nomonic aqueous surfactant system.
  • the formulations of the invention have excellent flash foaming and residual foaming capability although no anionic surfactants are included.
  • the invention also provides personal care compositions including a quaternary ammonium compound which is a conditioning compound.
  • the invention provides hand soap compositions comprising a nomonic surfactant base m combination with at least one cationic ammonium compound.
  • the ammonium compound may be an antibacterial compound or a conditioning agent, or both.
  • Certain hand soap formulations will include a conditioning agent and an antimicrobial compound. Similar formulations may be formulated to function as conditioning shampoos .
  • the unexpected foaming properties of the formulations of the invention are illustrated in the examples.
  • the foaming properties are due to the carefully balanced mix of nomonic surfactants.
  • the formulations tested in these examples contain preferred concentrations of ingredients.
  • the invention provides aqueous liquid cleaning compositions, the compositions being free of anionic surfactants and consisting essentially of a nomonic surfactant system and a cationic ammonium compound.
  • the invention also provides high foaming nomonic or nomomc/amphoteric systems that are excellent grease cutters.
  • the nomonic surfactant system may comprise (1) from about 0.1-50% by weight based on the weight of the composition of a linear alcohol ethoxylate having an average carbon chain length of no more than 12 carbon atoms; and (2) a surfactant member selected from the group consisting of amine oxides and betames.
  • the total concentration of active components in the composition based on the weight of the composition is at least about 5%.
  • Optional non- ionic surfactants include alkanolamides, alkyl polysaccha ⁇ des, betames, and polyhydroxy fatty acid amides. In various embodiments of the invention, these optional components may replace a portion of the alcohol ethoxylate.
  • the nomonic surfactant systems of the invention may be combined with a variety of cationic ammonium compounds, such as for example, quaternary ammonium compounds or cationic conditioning agents, to produce a cleaning composition that functions as dishwashing cleaner such as a an antimicrobial dishwashing liquid or handsoap or as a conditioning cleaner such as a conditioning shampoo.
  • dishwashing cleaner such as a an antimicrobial dishwashing liquid or handsoap
  • a conditioning cleaner such as a conditioning shampoo.
  • Formulations of the invention can be utilized as body washes and soaps, facial cleanser, bath gels, and bubble bathes .
  • the inventive formulations provide for repair of split ends .
  • disinfecting or disinfectant refers to antimicrobial and/or antibacterial activity.
  • Disinfectant, antimicrobial and antibacterial formulations of the invention are capable of reducing the rate of microbial, i.e., bacterial, reproduction, and/or killing microbial organisms .
  • the invention encompasses detergent compositions containing various combinations of linear alcohol ethoxylates and nomonic surfactants selected from amme oxides and betames. Typical compositions also include at least one cationic ammonium compound.
  • the detergent or cleaning compositions comprise a linear alcohol ethoxylate, an am e oxide, an alkyl mono- or dialkanolamide, and a cationic ammonium compound.
  • the balance of the material is water.
  • the weight ratio of linear alcohol ethoxylate to am e oxide is from about 3.1 to 1:3.
  • a particularly preferred detergent composition according to the invention is the following. a detergent formulation free from anionic surfactants consisting essentially of:
  • component (d) from about 0.5 to 20% of a cationic ammonium compound.
  • the weight ratio of component (a) to component (b) is most preferably from about 1:3 to 3:1.
  • Most preferred linear alcohol ethoxylates have about 4.5 moles of ethoxylation per mole of alcohol.
  • Most preferred alkanolamides are present at about 4-6% by weight of the composition.
  • composition of the invention is a liquid cleaning composition consisting essentially of, by weight of the composition, from about 4-7% of a C 810 alcohol ethoxylate having an average of about 9 moles of ethylene oxide, from about 12-20% of a C 810 alcohol ethoxylate having an average of about 12 moles of ethylene oxide, from about 7-13% of a fatty acid amidopropylamme oxide having an average of about 10-18 fatty acid carbon atoms, from about 1-4% of a fatty acid diethanolamide having an average of about 10-18 fatty acid carbon atoms, from about 1-4% of a fatty acid monoethanolamide having an average of about 10-18 fatty acid carbon atoms; and an antibacterial effective amount of an antibacterial quaternary ammonium compound.
  • a preferred antibacterial quaternary ammonium compound is an alkyl dimethyl benzyl ammonium chloride.
  • the balance of the composition is water.
  • Such a composition may also contain an emulsifier or thickener such as xanthan gum, as well as fragrances, etc.
  • Still another particularly preferred formulation according to the invention is an aqueous liquid cleaning composition, the compositions being free of anionic surfactants and consisting essentially of:
  • composition (d) from about 5-10% by weight of the composition of an alkylpolyglycoside.
  • Yet another composition consists essentially of:
  • Another preferred aspect of the invention is a detergent composition suitable for preparing an aqueous, liquid cleaning formulation, the detergent composition comprising, based on the total weight of active components in the composition:
  • the invention provides a detergent composition suitable for preparing an aqueous, liquid cleaning formulation, the detergent composition comprising, based on the total weight of active components m the composition: a) from about 25-60% by weight an alcohol ethoxylate having an average of 6-12 carbon atoms and containing an average of from about 4-15 moles of ethylene oxide where the concentration of alcohol ethoxylate m the composition is of the total surfactant present by weight ; b) from about 15-55% by weight of an amine oxide, a betaine or mixture thereof ; and c) 5-20% by weight of an alkanolamide having an average of from 10-16 carbon atoms; and d) up to about 20% by weight of a cationic surfactant.
  • aqueous cleaning formulation comprising from about 5% to 60% by weight of the formulation of a detergent composition, the detergent composition comprising, based on the total weight of active components m the detergent composition: (a) from about 25-60% by weight of an alcohol ethoxylate having an average of 8-10 carbon atoms an containing an average of 5-12 moles of ethylene oxide;
  • non-essential ingredients include fragrances, dyes, stabilizers, thickeners, etc.
  • Nomonic surfactants The surfactants suitable for use m the inventive compositions include the following nomonic surfactants. Alcohol ethoxylates
  • the alkyl chain of the aliphatic alcohol can either be straight or branched and generally contains from about 5 to about 22 carbon atoms.
  • the chain of ethylene oxide can contain from 2 to 30 ethylene oxide moieties per molecule of surfactant.
  • ethoxylated alcohols include the condensation product of about 6 moles of ethylene oxide with 1 mole of tridecanol, my ⁇ styl alcohol condensed with about 10 moles of ethylene oxide per mole of myristyl alcohol, the condensation product of ethylene oxide with coconut fatty alcohol wherein the coconut alcohol is a mixture of fatty alcohols with alkyl chains varying from 10 to 14 carbon atoms and wherein the condensate contains about 6 moles of ethylene oxide per mole of alcohol, and the condensation product of about 9 moles of ethylene oxide with the above-described coconut alcohol.
  • Examples of commercially available nomonic surfactants of this type include Tergitol 15-S-9 marketed by the Union Carbide Corporation, Neodol 23-7 marketed by the Shell Chemical Company and Kyro EOB marketed by the Procter & Gamble Company.
  • a preferred concentration for the alcohol ethoxylate in the composition is from about 10-70% of the total active surfactant by weight; i.e., it is from about 10-70% by weight based on the total weight of active components.
  • a more preferred range is 25-60% by weight.
  • a most preferred range is 40-60% by weight .
  • the alcohol ethoxylates have an average of 6-12 carbon atoms and contain an average of about 4-15 moles of ethylene oxide.
  • the alcohol ethoxylates have an average of 8 -CIO carbon atoms and an average of about 5-12 moles ethylene oxide.
  • the most preferred alcohol ethoxylates are selected from C 9 u alkyl ethoxylate (8EO) , C 6 10 alkyl ethoxylate (4EO) , C 810 alkyl ethoxylate (9EO) , C 810 alkyl ethoxylate (12 EO) , C alkyl ethoxylate (5 EO) , and a C u alkyl ethoxylate (7 ⁇ 0) .
  • Amide Surfactant is selected from C 9 u alkyl ethoxylate (8EO) , C 6 10 alkyl ethoxylate (4EO) , C 810 alkyl ethoxylate (9EO) , C 810 alkyl ethoxylate (12 EO) , C alkyl ethoxylate (5 EO) , and a C u alkyl ethoxylate (7 ⁇ 0) .
  • the amide type of nomonic surface active agents includes the ammonia, monoethanol and diethanolamides of fatty acids having an acyl moiety of from about 7 to about 18 carbon atoms.
  • acyl moieties are normally derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum, or by the Fischer-Tropsch process.
  • the amide surfactants useful herein may be selected from those aliphatic amides of the general formula:
  • R 4 , R 5 and R ⁇ being from about 9 to about 25.
  • Preferred amide surfactants have an average of from 10-16 carbon atoms the portion of the molecule contributed by the fatty acid. More preferably, the amide surfactants have an average of from 8-10 carbon atoms m the fatty portion. Most preferred amide surfactants are lauric (average of C 12 ) myristic (average of C 14 ) mono ethanolamide, lauric diethanolamide, lauric monoethanolamide, and lauric monoisopropanolamide .
  • a preferred concentration of the amide surfactants m the composition is 5-20% of the total active surfactant by weight. A more preferred range is 9-16% by weight.
  • Amme oxides useful m the present invention include long- cham alkyl amme oxides, i.e.. those compounds having the formula
  • R 3 (OR 4 ) x ⁇ ⁇ (R 5 ) 2
  • R 3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8 to 16 carbon atoms
  • R 4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2 carbon atoms, or mixtures thereof
  • x is from 0 to 3 , preferably 0
  • each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3 , preferably from 1 to 2 carbon atoms, or a polyethylene oxide group containing from 1 to 3 , preferably 1, ethylene oxide groups.
  • the R" groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • amme oxide surfactants m particular include C l0 -C 18 alkyl dimethyl amme oxides and C 8 -C l2 alkoxy ethyl dihydroxyethyl amme oxides.
  • Examples of such materials include dimethyloctylamme oxide, diethyldecylam e oxide, bis- (2 -hydroxyethyl) dodecylamme oxide, dimethyldodecylamme oxide, dodecylamidopropyl dimethylamme oxide and d ⁇ methyl-2- hydroxyoctadecylam e oxide.
  • Preferred are C 10 -C 18 alkyl dimethylamme oxide, and C 10 -C ⁇ a acylamido alkyl dimethylamme oxide.
  • amme oxides are C 12 14 alkyl dimethyl amme oxide, C 1218 alkyl amido propyl dimethyl amme oxide, C 1416 alkyl dimethyl amme oxide, and C 1618 alkyl dimethyl amme oxide.
  • a preferred concentration for the amme oxide, or a mixture of amme oxide and betaine, m the composition is 15-
  • the betames useful the present invention are those compounds having the formula R (R 1 ) 2 N * R 2 COO wherein R is a C 6 -C 18 hydrocarbyl group, preferably C 10 -C_ e alkyl group, each R 1 is typically alkyl, preferably methyl, and R 2 is a hydrocarbyl group, preferably a C,-C 5 alkylene group, more preferably a C x -C 2 alkylene group.
  • betames examples include coconut acylamidopropyldimethyl betaine ; hexadecyl dimethyl betame; C 12 -C 14 acylamidopropylbetaine; C 8 - C 14 acylamidohexyldiethyl betaine; 4-[C 14 -C 16 acylmethylamido- diethylammomo] -1-carboxybutane; C P -C 18 acylamidodimethyl- betaine; C 12 -C 1G acylamidopentanediethyl -betaine ; C 12 -C 16 acyl- methylamidodimethylbetame .
  • Preferred betames are C 12 -C 18 dimethylamomohexanoate and the C ⁇ -C 18 acylamidopropane (or ethane) dimethyl (or diethyl) betames.
  • sulfobetames sultaines of formula R(R t ) N+R,S0 3 -, wherein R is a C r -C 18 Hydrocarbyl group, preferably a C 10 -C 16 alkyl group, more preferably a C 12 -C alkyl group; each R is typically C 1 -C 3 alkyl, preferably methyl and R, is a C -C hydrocabyl group, preferably a C ⁇ C j alkylene or, preferably, hydroxyalkylene group.
  • Suitable sultaines are C 12 -C 14 di- hydroxyethylammomo propane sulfonate, and C 6 -C 18 dimethyl - ammomo hexane sulfonate, with C,,-C_, amido propyl ammomo-2- hydroxypropyl sultame being preferred.
  • the betaine is C12-C18 amidopropyl betame .
  • a preferred range of concentration for betames, or mixture of betaine and amme oxide, in the composition is 15- 60% of the total active surfactant by weight. A more preferred range is 20-55% by weight. A most preferred range is 22-35% by weight .
  • polyhydroxy fatty acid amides useful m the inventive detergent compositions have the formula:
  • R 1 is H, C 1 - C i hydrocarbyl, 2 -hydroxy ethyl, 2 -hydroxy propyl, or a mixture thereof, preferably C ⁇ C,, alkyl, more preferably C or C alkyl, most preferably C , alkyl (i.e., methyl) ; and R" is a C -C 31 hydrocarbyl, preferably straight - chain C -C alkyl or alkenyl, more preferably straight-chain C 9 -C 17 alkyl or alkenyl, most preferably straight-chain C ⁇ -C- ⁇ alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z preferably will be derived from a reducing sugar in a reductive ammation reaction; more preferably Z is a glycityl Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of of -CH 2 - (CHOH) n -CH 2 OH, -CH (CH 2 OH) - (CHOH) n _ CH 2 OH, - CH 2 - (CH0H) 2 (CHOR' ) -CH 2 OH, where n is an integer from 3 to 5, inclusive, and R 1 is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH 2 - (CHOH) 4 -CH 2 OH.
  • R 1 can be, for example, N-methyl, N-ethyl, N-propyl, N- lsopropyl, N-butyl, N-2 -hydroxy ethyl, or N-2 -hydroxy propyl.
  • R 2 -CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, my ⁇ stamide, capricamide, palmitamide, tallowamide, etc.
  • Z can be 1-deoxygluc ⁇ tyl , 2-deoxyfructityl , 1-deoxymalt ⁇ tyl, 1-deoxylact ⁇ tyl , 1-deoxygalact ⁇ tyl , 1- deoxymanmtyl , 1-deoxymaltotr ⁇ ot ⁇ tyl , etc.
  • Alkylpolvsaccha ⁇ des Alkylpolysaccharides such as those disclosed m U.S. Patent 4,565,647 are nomonic surfactants useful m the present invention.
  • Suitable alkylpolysaccharides include those having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccha ⁇ de, e.g., a polyglucoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
  • Any reducing saccha ⁇ de containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties.
  • the hydrophobic group is attached at the 2-, 3-, 4-, etc.
  • the mtersaccha ⁇ de bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • inventive formulations include a first nomonic surfactant member selected from the group consisting of linear alcohol ethoxylates, alkyl polysaccha ⁇ des, betames, and polyhydroxy fatty acid amides.
  • the first nomonic surfactant member is preferably a linear alcohol ethoxylate having 6-10 carbon atoms and 3 to 12 moles, more preferably 5-7 moles, of ethoxylation per mole of alcohol.
  • Other preferred alcohol ethoxylates are condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol .
  • Ethoxylated alcohols having no more than 12 carbon atoms the alkyl position are commercially avaiable and include NeodolJ 1-4; NeodolJ 1-7; NeodolJ 91-8, each of which is marketed by Shell Chemical Company.
  • compositions of the invention optionally include a second nomonic surfactant member.
  • the second member is an amme oxide m an amount of from about 1-11, more preferably 5-11, % by weight of the composition.
  • the preferred amme oxides for use as the second surfactant member may be represented by the general formula: R j R ⁇ N ⁇ 0 wherein Rj is a higher alkyl radical having from 8 to 18 carbon atoms, such as lauryl, decyl , cetyl , oleyl, stearyl, hexadecyl or an amide substituted group, such as RCONH (CH 3 ) n , wherein RCO is a long chain alkanoyl radical and n is a small whole number; R ?
  • R 3 are each lower alkyl radicals such a methyl, ethyl, propyl or a substituted lower alkyl radical such a hydroxyethyl , hydroxyethoxyethyl , hydroxy polyethoxyethyl , etc.
  • suitable tertiary amme oxides include lauryl dimethyl amide oxide, coconut dimethylamme oxide, dodecyl dimethyl amme oxide,
  • the preferred amides are C 8 -C 20 alkanol amides, monoethanolamides , diethanolamides , and lsopropanolamides .
  • a particularly preferred amide is a mixture of my ⁇ stic monoethanolamide and lauric monoethanolamide . This preferred amide is sold by Stepan Company, Northfield, Illinois as Nmol LMP. Cationic ammonium compound
  • the cationic compound is selected according to the desired end use for the formulation - typically, the cationic compound is present m amounts ranging from about 0.5 to 20% by weight of the formulation
  • the cationic ammonium compound is normally selected from the group consisting of quaternary ammonium salts and amme salts (salts of primary, secondary and tertiary amines) 1. Disinfectant formulations
  • the purpose of the quaternary ammonium disinfectants is to reduce the rate of reproduction of or kill on contact gram positive and gram negative organisms the organisms encountered in kitchen environments
  • Useful such disinfectants include BTC 8358 which is N-alkyl (50% C 14 , 40% C 2 , and 10% C 16 ) dimethyl benzyl ammonium chloride
  • BTC 8358 which is N-alkyl (50% C 14 , 40% C 2 , and 10% C 16 ) dimethyl benzyl ammonium chloride
  • Other quarternary ammonium salts may be any of the well known class of quaternary ammonium germicides characterized by the formula
  • R, Ra wherein at least one of the radicals, R , R , R 3 and R 4 (“the 'R' groups”) is a hydrophobic, aliphatic, aryl aliphatic, or aliphatic aryl radical of from 6 to 26 carbon atoms, the entire cation portion of the molecule has a molecular weight of at least 165, and the remaining R groups are hydrophobic, aliphatic, aryl aliphatic, or aliphatic aryl radical of from 6 to 26 carbon atoms
  • the hydrophobic radicals may be long-chain alkyl, long-chain alkoxy aryl, long-chain alkyl aryl, halogen- substituted long-chain alkyl aryl, long-chain alkyl phenoxy alkyl, aryl alkyl, and so forth, m nature
  • the remaining radicals on the nitrogen atom other than the hydrophobic radicals are substituents of hydrocarbon structure usually containing a total of no more than 12 carbon
  • the radical X m the above formula is any salt -forming anionic radical .
  • Suitable quaternary ammonium salts within the above description include the alkyl ammonium halides such as cetyl t ⁇ methyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl benzyl ammonium bromide, N-alkyl pyridimum halides such as N-cetyl pyridimum bromide, and the like.
  • quaternary ammonium salts include those which the molecule contains either, amide or ester linkages such a octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride.
  • Other very effective types of quaternary ammonium germicides are those which the hydrophobic radical is characterized by a substituted aromatic nucleus as in the case of lauryloxyphenyltnmethyl ammonium chloride, cetylammophenylt ⁇ methyl ammonium methosulfate, dodecylphenyl -t ⁇ methyl ammonium methosulfate, dodecylbenzltrimethyl ammonium chloride, chlorinated dodecylbenzylt ⁇ methyl ammonium chloride, and the like.
  • Preferred quaternary ammonium germicides of the above general types are the long-chain alkyl dimethylbenzyl quaternary ammonium salts, the alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium salts, the N- (acylcocoaminoformylmethyl) -pyridimum halides, the long-chain alkyl trimethyl ammonium halides, the long-chain alkyl benzyl dimethyl benzyl ammonium halides, and the long-chain alkyl benzyl diethyl ethanol ammonium halides in which the alkyl radical contains from 8-18 carbon atoms.
  • the quaternary ammonium salts useful m the invention have the general formula:
  • R_ and R 2 are straight or branched chain lower alkyl groups having from one to seven carbon atoms;
  • R 3 is a straight or branched chain higher alkyl group having from about six to sixteen carbon atoms, or a benzyl group;
  • R 4 is a straight or branched chain higher alkyl group having from about six to sixteen carbon atoms;
  • X is a halogen or a methosulfate or saccharmate ion.
  • R_ and R 2 are methyl groups; R 3 is benzyl or straight or brancfted chain alkyl having from about eight to sixteen carbon atoms; and R 4 is straight or branched chain alkyl having from about eight to sixteen carbon atoms provided that not both R, and R 4 have sixteen carbon atoms simultaneously.
  • a preferred halogen is chlorine, or a methosulfate or a saccharmate ion.
  • quaternary ammonium germicides are-, dioctyl dimethyl ammonium chloride, octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, (C 12 -C 18 ) n-alkyl dimethyl benzyl ammonium chloride, (C 12 -C 18 ) n-alkyl dimethyl ethylbenzyl ammonium chloride, (C -C 18 ) n-alkyl dimethyl benzyl ammonium saccharmate, di (C ⁇ C,) alkyl (C 6 -C 26 ) alkyl aryl ammonium salts, di (C 3 -C,) alkyl di (C 6 -C 14 ) alkyl ammonium salts, tr ⁇ (C 1 -C 7 ) alkyl (C 6 -C 26 ) alkyl ammonium salts, (C 14 -C 26 ) al
  • the quaternary ammonium salt m the present invention need not be a single entity, but may be a blend of two or more quaternary ammonium salts.
  • the more preferred quaternary salts are alkyl t ⁇ methyl ammonium compounds and alkyl dimethyl benzyl (and/or ethylbenzyl) ammonium compounds having from 10-18 carbon atoms m the long chain portion.
  • the most preferred quaternary salts are Benzalkonium (C 1216 ) chloride, alkyl (cetyl or oleyl) t ⁇ methyl ammonium chloride, or other biocidal quats such as dialkyl dimethyl quats.
  • the carbon chains should have from 6-14 carbons atoms m each of the two long chain alkyl groups .
  • Di (C 16 18 ) alkyl ammonium compounds are most preferably avoided in the compositions and formulations of the invention.
  • the amount, in weight-percent , of the quaternary ammonium salt, either as a single entity or blended, is up to about 50%, but is preferably from about 0.1%-10.0% and more preferably about 1-3%.
  • the preferred quaternary ammonium germicide is a mixture of about 34% by weight C 12 and 16% by weight C 14 n-alkyl dimethyl ethylbenzyl ammonium chloride and about 30% by weight C 14 , 15% by weight C 16 , 2.5% by weight C 12 and 2 5% by weight C l ⁇ n-alkyl dimethyl benzyl ammonium chloride.
  • the quaternary ammonium compounds can also function as cationic surfactants to produce antistatic and conditioning effects when deposited on the substrate. 2_ . Conditioning formulations
  • the invention also encompasses cleaning compositions capable of imparting a conditioning effect on a substrate such as skin or hair.
  • Such formulations include hand soaps and conditioning shampoos.
  • a variety of cationic surfactants useful as detersive surfactants and as conditioning agents are well known m the art. These materials contain ammo or quaternary ammonium hydrophilic moieties which are positively charged when dissolved m the aqueous composition of the present invention. Whether the cationic surfactant functions as a detersive surfactant or a conditioning agent, or both, will depend upon the particular compound as is well understood by those skilled the art. In general, compounds with longer chain length moieties attached to the cationic mtgogen tend to exhibit greater conditioning benefits.
  • Quaternary ammonium salts include dialkldimethyl-ammonium chlorides and t ⁇ alkyl methyl ammonium chlorides, wherein the alkyl groups have from about 12 to about 22 carbon atoms and are derived from long-chain fatty acids. These types of cationic surfactants are useful as hair conditioning agents. Examples of quaternary ammonium salts useful herein include di (coconutalkyl) dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride.
  • Stearyl dimethyl benzyl ammonium chloride and cetyl trimethyl ammonium chloride are preferred quaternary ammonium salts useful herein (Hydrogenated tallow) trimethyl ammonium chloride is a prererred quaternary ammonium salt.
  • Preferred of the conventional cationic conditioning agents are cetyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, stearyldimethyl Denzyl ammonium chloride, and (partially hydrogenated tallow) trimethylammomum chloride; these materials may also provide anti -static benefits to the present shampoo compositions.
  • Salts of primary, secondary and tertiary fatty amines are also suitable cationic surfactant materials.
  • the alkyl groups of such amines preferably have from about 12 to about 22 carbon atoms, and may be substituted or unsubstituted. Secondary and tertiary amines are preferred, tertiary amines are particularly preferred.
  • Such amines, useful herein, include stearamido propyl dimethyl amme, diethyl am o ethyl stearamide, dimethyl stearamme, dimethyl soyam e, soyamme, myristyl am e, tridecyl amme ethyl stearylam e, N-tallowpropane diamine, ethoxylated (5 moles E.O.) stearylamme, dihydroxy ethyl stearylamme, and arachidylbehenylam e .
  • Suitable amme salts include the halogen, acetate, phosphate, nitrate, citrate, lactate and alkyl sulfate salts.
  • Such salts include stearylamme hydrochlo ⁇ de, soyamme chloride, stearylamme formate, N-tallowpropane diamme dichlo ⁇ de and stearamidopropyl dimethylamme citrate.
  • Cationic amme surfactants included among those useful m the present invention are disclosed in U.S. Patent 4,275,055, Nachtigal, et al . , issued June 23, 1981, incorporated by reference herein.
  • Cationic conditioning surfactants especially useful m shampoo formulations are quaternary ammonium or ammo compounds having at least one N radical containing one or more nomonic hydrophilic moieties selected from alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, and alkylester moieties, and combinations thereof.
  • the surfactant contains at least one hydrophilic moiety within 4, preferably within 3, carbon atoms
  • hydrophilic moiety e.g., carbon atoms m a hydrophilic polyoxyalkylene (e.g., -CH 2 -CH ? -0- ) , that are adjacent to other hydrophilic moieties are not counted when determining the number of hydrophilic moieties within 4, or preferably 3, carbon atoms of the cationic nitrogen.
  • alkyl portion of any hydrophilic moiety is preferably a C 3 -C 3 alkyl.
  • Suitable hydrophile-contammg radicals include, for example, ethoxy, propoxy, polyoxyethylene, polyoxypropylene, ethylamido, propylamido, hydroxymethyl , hydroxyethyl , hydroxypropyl , methylester, ethylester, propylester, or mixtures thereof, as nomonic hydrophile moieties.
  • the ammo surfactants must be positively charged at the pH of the shampoo compositions. Generally, the pH of the shampoo compositions will be less than about 10, typically from about 3 to about 9.
  • cationic compounds suitable for use m the invention include NH 4 * , and mono-, di-, and tn-short chain alkyl ammonium salts.
  • Adiuvant materials include NH 4 * , and mono-, di-, and tn-short chain alkyl ammonium salts.
  • Various adjuvant materials may be added to these foaming aqueous detergent compositions such as small amounts of viscosity builders and conditioning agents inclusive of gums and hydroxy-propyl methyl cellulose.
  • Such ingredients can be added in an amount that does not adversely effect the foaming and cleaning characteristics of the compositions.
  • Other ingredients may include alkaline or acid buffers to aid m the adjustment and maintenance of the desired pH of the finished product such a borax, various inorganic water-soluble phosphates, sodium hydroxide, citric acid, etc.
  • Other additions include optical b ⁇ ghteners, bleaches, germicides, fungicides, bactericides, colorants, perfumes, etc. m minor amounts which do not interfere with the cleaning, foaming, conditioning, or sanitizing properties of the composition.
  • EDTA ethylenediamme tetraacetate
  • PEG polyethylene glycol
  • Other ingredients include ethylenediamme tetraacetate (EDTA) and polyethylene glycol (PEG) fatty acid esters.
  • EDTA is especically useful antibacterial cleaning compositions, particularly handsoaps, since it increases the effectiveness of the antibacterial quaternary ammonium compound, m particular against Pseudomonas Aerugmosa, a pathogenic gram-negative organism.
  • a representative PEG ester is PEG 600 distearate. This ester provides excellent viscosity enhancement the inventive surfactant systems by association with other components without causing a loss of clarity or an increase m color.
  • the detergent compositions of the invention are prepared by combining water with the alcohol ethoxylate and amme oxide surfactant members, mixing until uniform and then adding any optional components, such as, for example, amide or cationic ammonium compound, and again mixing until uniform. Heating may be employed as needed to enhance dissolution of the components.
  • Various antimicrobial cleaning formulations described herein were analyzed for detergency and foam height. Detergency and foam longevity was evaluated using the mimplate assay described below.
  • Soiled watchglasses should always be stored at room temperature [ (can be stored indefinitely) ] .
  • a test solution may be made by diluting sufficient product with [tap] water (140 ppm hardness) to a concentration of 0.048% active material. 400 ml of such a solution is employed; heating to about 130-135°F may be necessary to achieve dissolution of the product.
  • the en ⁇ point of the test is the number of mini-plates washed when further agitation of the solution fails to produce new/additional foam on the solution surface.
  • small watchglasses representing 1/3 the surface area of a large watchglass may be used as the endpomt is neared.
  • Formulations according to the invention are shown below in the following examples. In all the examples, all amounts are given in percent active by weight of the final formulation unless indicated to the contrary.
  • 1 EO refers to the average number of moles of ethylene oxide per mole of alcohol .
  • Formulation 47 can be made at 47% actives utilizing the same component ratios
  • Hand soap and conditioning shampoo formulations according to the invention are prepared essentially by the method described above for dishwashing compositions.

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Abstract

Disclosed are aqueous liquid cleaning compositions, the compositions being free of anionic surfactants and comprising: (a) linear alcohol ethoxylate; (b) amine oxide or betaine; and other, optional components, such as a cationic ammonium compound.

Description

HIGH FOAMING DETERGENT COMPOSITION HAVING NON-IONIC SURFACTANT BASE
Background of the Invention This application is a contmuation-in-part of International Application PCT/US97/06211 filed April 14, 1997, which is a continuation- m-part of U.S. Patent Application Serial No. 08/631,938, filed April 15, 1996.
Field of the Invention
This invention relates to formulations for manually washing dishes, hand soaps, and for high foaming cleaning compositions . Description of the Related Art Light-duty liquid detergent formulations for kitchen surfaces are well known. Kitchen surfaces include counter tops, stove tops, dishes and any other hard surface commonly found in k tcnen environments. The term "dishes" includes any utensils involved m food preparation or consumption Kitchen surfaces, particularly dishes, must be washed free of food residues, greases, proteins, starches, gums, dyes, oils and burnt organic residues .
Most of the consumer accepted formulations in use include anionic synthetic surfactants with or without a nomonic surfactant. Many of such formulations contain a sulfonate-type anionic surfactant, for example, an alkylbenzene sulfonate or an alkane sulfonate, in conjunction with a sulfate or alkyl ether sulfate, or a nomonic surfactant, for example, an alcohol ethoxylate, an alkyl phenol ethoxylate, a mono- or diethanolamide or an amine oxide. The sulfonate material generally predominates.
It is the anionic surfactant that provides the typical high foaming (suds) characteristics generally associated with dish washing formulations. Foam (suds) is the cleaning efficacy signal relied on by consumers. Nomonic surfactants generally do not provide good foaming characteristics.
U.S. Patent No. 2,746,928 discloses that it is not possible to mix anionic surface-active agents with quaternary ammonium germicides. The cationic quaternary ammonium germicide reacts with the anionic surface-active agent resulting in a reduction in germicidal and detergent activity.
Thus, anionic surfactants are incompatible with cationic quaternary antimicrobial surfactants and nomonic surfactants do not normally provide significant foaming capability to liquid formulations Therefore, dish washing liquids combining good foaming and antimicrobial activities are not available to the consumer.
Solutions to the problems posed by the incompatibility of cationic and anionic surfactants have focused on various non- ionic surfactant systems. While having the potential to overcome the known compatibility problems, such systems are not capable of the cleaning efficacy and foam volume demanded by consumers. Hence, there remains a critical need for cleaning compositions based on non- ionic surfactant systems that provide excellent cleaning with high foam volume.
SUMMARY OF THE INVENTION
In general, anionic surfactant systems such as those found in the current light duty liquids are classified as high foamers . Conversely, nomonic surfactant systems are classified as low foamers .
By careful selection and extensive experimentation, we have identified nomonic and nomomc/amphoteric surfactant mixtures that produce consumer acceptable foam comparable to commercial dish washing liquids that use anionic detergents. The useful nomonic surfactants include ethoxylates that have various chain lengths not exceeding 12 carbon atoms and degrees of ethoxylation that allow the dish washing liquid to be effective on a wide range of food soils while providing excellent flash foam volume and foam stability. This system provides the consumer with effective cleaning on, but not limited to, greasy food soils, fatty food soils, and oily food soils .
The invention provides surfactant compositions based on nomonic surfactant components that function as cleaning compositions. Further included m the invention are disinfectant hand soaps, body washes, disinfectant or antibacterial dishwashing liquids, and conditioning shampoos. Each of these latter cleaning compositions includes at least one cationic ammonium salt. The specific cationic salts are selected depending on the ultimate use or function of the cleaning composition.
•Certain formulations of this invention will control the presence and spread of bacteria on hard surfaces in the kitchen environment, especially dishes. In this context, the invention is a microbiological active quaternary ammonium salt ingredient homogeneously incorporated into a nomonic aqueous surfactant system. Unexpectedly, the formulations of the invention have excellent flash foaming and residual foaming capability although no anionic surfactants are included. The invention also provides personal care compositions including a quaternary ammonium compound which is a conditioning compound.
Thus, the invention provides hand soap compositions comprising a nomonic surfactant base m combination with at least one cationic ammonium compound. The ammonium compound may be an antibacterial compound or a conditioning agent, or both. Certain hand soap formulations will include a conditioning agent and an antimicrobial compound. Similar formulations may be formulated to function as conditioning shampoos .
The unexpected foaming properties of the formulations of the invention are illustrated in the examples. The foaming properties are due to the carefully balanced mix of nomonic surfactants. The formulations tested in these examples contain preferred concentrations of ingredients.
Thus, the invention provides aqueous liquid cleaning compositions, the compositions being free of anionic surfactants and consisting essentially of a nomonic surfactant system and a cationic ammonium compound.
Significantly, the invention also provides high foaming nomonic or nomomc/amphoteric systems that are excellent grease cutters.
The nomonic surfactant system may comprise (1) from about 0.1-50% by weight based on the weight of the composition of a linear alcohol ethoxylate having an average carbon chain length of no more than 12 carbon atoms; and (2) a surfactant member selected from the group consisting of amine oxides and betames. In these compositions, the total concentration of active components in the composition based on the weight of the composition is at least about 5%. Optional non- ionic surfactants include alkanolamides, alkyl polysacchaπdes, betames, and polyhydroxy fatty acid amides. In various embodiments of the invention, these optional components may replace a portion of the alcohol ethoxylate.
The nomonic surfactant systems of the invention may be combined with a variety of cationic ammonium compounds, such as for example, quaternary ammonium compounds or cationic conditioning agents, to produce a cleaning composition that functions as dishwashing cleaner such as a an antimicrobial dishwashing liquid or handsoap or as a conditioning cleaner such as a conditioning shampoo.
Formulations of the invention can be utilized as body washes and soaps, facial cleanser, bath gels, and bubble bathes .
In addition to providing styling and conditioning to the hair, the inventive formulations provide for repair of split ends .
DETAILED DESCRIPTION OF THE INVENTION
As used herein, the term disinfecting or disinfectant refers to antimicrobial and/or antibacterial activity. Disinfectant, antimicrobial and antibacterial formulations of the invention are capable of reducing the rate of microbial, i.e., bacterial, reproduction, and/or killing microbial organisms .
The invention encompasses detergent compositions containing various combinations of linear alcohol ethoxylates and nomonic surfactants selected from amme oxides and betames. Typical compositions also include at least one cationic ammonium compound. In preferred embodiments, the detergent or cleaning compositions comprise a linear alcohol ethoxylate, an am e oxide, an alkyl mono- or dialkanolamide, and a cationic ammonium compound. In such compositions, the balance of the material is water. In particularly preferred embodiments, the weight ratio of linear alcohol ethoxylate to am e oxide is from about 3.1 to 1:3.
A particularly preferred detergent composition according to the invention is the following. a detergent formulation free from anionic surfactants consisting essentially of:
(a) from about 2-23%, preferably 8-18%, by weight of a linear alcohol ethoxylate having 6-12 carbon atoms and 3-12, preferably 3 to 7 moles of ethoxylation per mole of alcohol;
(b) from about 2-23%, more preferably 4-23%, by weight of an amme oxide selected from the group consisting of (C8 16) alkyl amido ( Cτ 4) alkyl dι(C1 4) alkyl amme oxides and (C10 16) alkyl amine oxides; and optionally (c) from about 1-10%, more preferably 3-7%, by weight of (C10 16) alkyl mono- or dialkanolamides, where each alkanol portion independently has from 1-6 carbon atoms; and
(d) from about 0.5 to 20% of a cationic ammonium compound. In such compositions, the weight ratio of component (a) to component (b) is most preferably from about 1:3 to 3:1. Most preferred linear alcohol ethoxylates have about 4.5 moles of ethoxylation per mole of alcohol. Most preferred alkanolamides are present at about 4-6% by weight of the composition.
Another particularly preferred composition of the invention is a liquid cleaning composition consisting essentially of, by weight of the composition, from about 4-7% of a C810 alcohol ethoxylate having an average of about 9 moles of ethylene oxide, from about 12-20% of a C810 alcohol ethoxylate having an average of about 12 moles of ethylene oxide, from about 7-13% of a fatty acid amidopropylamme oxide having an average of about 10-18 fatty acid carbon atoms, from about 1-4% of a fatty acid diethanolamide having an average of about 10-18 fatty acid carbon atoms, from about 1-4% of a fatty acid monoethanolamide having an average of about 10-18 fatty acid carbon atoms; and an antibacterial effective amount of an antibacterial quaternary ammonium compound. A preferred antibacterial quaternary ammonium compound is an alkyl dimethyl benzyl ammonium chloride. The balance of the composition is water. Such a composition may also contain an emulsifier or thickener such as xanthan gum, as well as fragrances, etc.
Still another particularly preferred formulation according to the invention is an aqueous liquid cleaning composition, the compositions being free of anionic surfactants and consisting essentially of:
(a) from about 13-19% by weight based on the weight of the composition of a linear alcohol ethoxylate having an average carbon chain length of no more than 12 carbon atoms; and;
(b) from about 3-7% by weight of the composition of a mono- or dialkanolamide ; and
(d) from about 5-10% by weight of the composition of an alkylpolyglycoside. Yet another composition consists essentially of:
(a) from about 13-19% by weight based on the weight of the composition of a sulfobetame;
(b) from about 5-20% by weight of the composition of an amme oxide, a betaine, or mixture thereof;
(c) from about 3-7% by weight of the composition of a mono- or dialkanolamide ; and
(d) from about 3-7% by weight of the composition of an alkylpolyglycoside, the total concentration of surfactants m the composition being from about 30-35% by weight of the composition.
Another preferred aspect of the invention is a detergent composition suitable for preparing an aqueous, liquid cleaning formulation, the detergent composition comprising, based on the total weight of active components in the composition:
(a) from about 10-70% by weight of an alcohol ethoxylate having an average of 6-12 carbon atoms and an average of 4-15 moles of ethylene oxide;
(b) from about 15-60% by weight of an amme oxide, a betaine or mixture thereof;
(c) from about 5-20% by weight of an alkanolamide having an average of 10-16 carbon atoms.
In yet another preferred aspect, the invention provides a detergent composition suitable for preparing an aqueous, liquid cleaning formulation, the detergent composition comprising, based on the total weight of active components m the composition: a) from about 25-60% by weight an alcohol ethoxylate having an average of 6-12 carbon atoms and containing an average of from about 4-15 moles of ethylene oxide where the concentration of alcohol ethoxylate m the composition is of the total surfactant present by weight ; b) from about 15-55% by weight of an amine oxide, a betaine or mixture thereof ; and c) 5-20% by weight of an alkanolamide having an average of from 10-16 carbon atoms; and d) up to about 20% by weight of a cationic surfactant.
Another preferred aspect of the invention is an aqueous cleaning formulation comprising from about 5% to 60% by weight of the formulation of a detergent composition, the detergent composition comprising, based on the total weight of active components m the detergent composition: (a) from about 25-60% by weight of an alcohol ethoxylate having an average of 8-10 carbon atoms an containing an average of 5-12 moles of ethylene oxide;
(b) from about 15-55% by weight of an alkyl dimethyl amme oxide, an alkyl amido propyl dimethyl amme oxide, an alkyl amido propyl betaine, or a mixture thereof ;
(c) from about 9-16% by weight of an alkanolamide having an average of 10-16 carbon atoms, and
(d) from about 3-10% by weight of biocidal cationic surfactant.
Optional, non-essential ingredients include fragrances, dyes, stabilizers, thickeners, etc. Nomonic surfactants The surfactants suitable for use m the inventive compositions include the following nomonic surfactants. Alcohol ethoxylates
In the condensation products of aliphatic alcohols with ethylene oxide, i.e., alcohol ethoxylates, the alkyl chain of the aliphatic alcohol can either be straight or branched and generally contains from about 5 to about 22 carbon atoms. The chain of ethylene oxide can contain from 2 to 30 ethylene oxide moieties per molecule of surfactant. Examples of such ethoxylated alcohols include the condensation product of about 6 moles of ethylene oxide with 1 mole of tridecanol, myπstyl alcohol condensed with about 10 moles of ethylene oxide per mole of myristyl alcohol, the condensation product of ethylene oxide with coconut fatty alcohol wherein the coconut alcohol is a mixture of fatty alcohols with alkyl chains varying from 10 to 14 carbon atoms and wherein the condensate contains about 6 moles of ethylene oxide per mole of alcohol, and the condensation product of about 9 moles of ethylene oxide with the above-described coconut alcohol. Examples of commercially available nomonic surfactants of this type include Tergitol 15-S-9 marketed by the Union Carbide Corporation, Neodol 23-7 marketed by the Shell Chemical Company and Kyro EOB marketed by the Procter & Gamble Company.
A preferred concentration for the alcohol ethoxylate in the composition is from about 10-70% of the total active surfactant by weight; i.e., it is from about 10-70% by weight based on the total weight of active components. A more preferred range is 25-60% by weight. A most preferred range is 40-60% by weight . Generally, the alcohol ethoxylates have an average of 6-12 carbon atoms and contain an average of about 4-15 moles of ethylene oxide. Preferably, the alcohol ethoxylates have an average of 8 -CIO carbon atoms and an average of about 5-12 moles ethylene oxide. The most preferred alcohol ethoxylates are selected from C9 u alkyl ethoxylate (8EO) , C6 10 alkyl ethoxylate (4EO) , C810 alkyl ethoxylate (9EO) , C810 alkyl ethoxylate (12 EO) , C alkyl ethoxylate (5 EO) , and a Cu alkyl ethoxylate (7Ξ0) . Amide Surfactant
The amide type of nomonic surface active agents includes the ammonia, monoethanol and diethanolamides of fatty acids having an acyl moiety of from about 7 to about 18 carbon atoms. These acyl moieties are normally derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum, or by the Fischer-Tropsch process. The amide surfactants useful herein may be selected from those aliphatic amides of the general formula:
O
R4^ "R5 i° wherein R4 is hydrogen, alkyl, or alkylol and R5 and R 6l are each hydrogen, C2-C, alkyl, C2-C4 alkylol, or C -C4 alkylenes joined through an oxygen atom, the total number of carbon atoms m R4, R5 and Rβ being from about 9 to about 25. A further description and detailed examples of these amide nomonic surfactants are contained in U.S. Pat. No. 4,070,309, issued to Jacobsen on Jan. 24, 1978. That patent is hereby incorporated herein by reference.
Preferred amide surfactants have an average of from 10-16 carbon atoms the portion of the molecule contributed by the fatty acid. More preferably, the amide surfactants have an average of from 8-10 carbon atoms m the fatty portion. Most preferred amide surfactants are lauric (average of C12) myristic (average of C14) mono ethanolamide, lauric diethanolamide, lauric monoethanolamide, and lauric monoisopropanolamide .
A preferred concentration of the amide surfactants m the composition is 5-20% of the total active surfactant by weight. A more preferred range is 9-16% by weight. Amme oxide
Amme oxides useful m the present invention include long- cham alkyl amme oxides, i.e.. those compounds having the formula
0
4 R3(OR4)x^ ^(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8 to 16 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2 carbon atoms, or mixtures thereof; x is from 0 to 3 , preferably 0; and each R5 is an alkyl or hydroxyalkyl group containing from 1 to 3 , preferably from 1 to 2 carbon atoms, or a polyethylene oxide group containing from 1 to 3 , preferably 1, ethylene oxide groups. The R" groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
These amme oxide surfactants m particular include Cl0-C18 alkyl dimethyl amme oxides and C8-Cl2 alkoxy ethyl dihydroxyethyl amme oxides. Examples of such materials include dimethyloctylamme oxide, diethyldecylam e oxide, bis- (2 -hydroxyethyl) dodecylamme oxide, dimethyldodecylamme oxide, dodecylamidopropyl dimethylamme oxide and dιmethyl-2- hydroxyoctadecylam e oxide. Preferred are C10-C18 alkyl dimethylamme oxide, and C10-Cιa acylamido alkyl dimethylamme oxide.
Most preferred amme oxides are C12 14 alkyl dimethyl amme oxide, C1218 alkyl amido propyl dimethyl amme oxide, C1416 alkyl dimethyl amme oxide, and C1618 alkyl dimethyl amme oxide.
A preferred concentration for the amme oxide, or a mixture of amme oxide and betaine, m the composition is 15-
60% by weight based on the total weight of active surfactant. A more preferred concentration is from 20-55% by weight. A most preferred is 22-35% by weight. Betaine
The betames useful the present invention are those compounds having the formula R (R1) 2N*R2COO wherein R is a C6-C18 hydrocarbyl group, preferably C10-C_e alkyl group, each R1 is typically
Figure imgf000015_0001
alkyl, preferably methyl, and R2 is a
Figure imgf000015_0002
hydrocarbyl group, preferably a C,-C5 alkylene group, more preferably a Cx-C2 alkylene group. Examples of suitable betames include coconut acylamidopropyldimethyl betaine ; hexadecyl dimethyl betame; C12-C14 acylamidopropylbetaine; C8- C14 acylamidohexyldiethyl betaine; 4-[C14-C16 acylmethylamido- diethylammomo] -1-carboxybutane; C P-C18 acylamidodimethyl- betaine; C12-C1G acylamidopentanediethyl -betaine ; C12-C16 acyl- methylamidodimethylbetame . Preferred betames are C12-C18 dimethylamomohexanoate and the C ~-C18 acylamidopropane (or ethane) dimethyl (or diethyl) betames. Also included are sulfobetames (sultaines) of formula R(Rt) N+R,S03-, wherein R is a Cr-C18 Hydrocarbyl group, preferably a C10-C16 alkyl group, more preferably a C12-C alkyl group; each R is typically C1-C3 alkyl, preferably methyl and R, is a C -C hydrocabyl group, preferably a C^Cj alkylene or, preferably, hydroxyalkylene group. Examples of suitable sultaines are C12-C14 di- hydroxyethylammomo propane sulfonate, and C 6-C18 dimethyl - ammomo hexane sulfonate, with C,,-C_, amido propyl ammomo-2- hydroxypropyl sultame being preferred. In a most preferred embodiment of the invention, the betaine is C12-C18 amidopropyl betame .
A preferred range of concentration for betames, or mixture of betaine and amme oxide, in the composition is 15- 60% of the total active surfactant by weight. A more preferred range is 20-55% by weight. A most preferred range is 22-35% by weight . Polvhvdroxy fatty acid amide
The polyhydroxy fatty acid amides useful m the inventive detergent compositions have the formula:
0
R2 N I z wherein: R1 is H, C1 - Ci hydrocarbyl, 2 -hydroxy ethyl, 2 -hydroxy propyl, or a mixture thereof, preferably C^C,, alkyl, more preferably C or C alkyl, most preferably C, alkyl (i.e., methyl) ; and R" is a C -C31 hydrocarbyl, preferably straight - chain C -C alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C^-C-^ alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive ammation reaction; more preferably Z is a glycityl Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials. Z preferably will be selected from the group consisting of of -CH2- (CHOH) n-CH2OH, -CH (CH2OH) - (CHOH) n _ CH2OH, - CH2- (CH0H)2 (CHOR' ) -CH2OH, where n is an integer from 3 to 5, inclusive, and R1 is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2- (CHOH) 4-CH2OH.
R1 can be, for example, N-methyl, N-ethyl, N-propyl, N- lsopropyl, N-butyl, N-2 -hydroxy ethyl, or N-2 -hydroxy propyl. R2-CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide, myπstamide, capricamide, palmitamide, tallowamide, etc. Z can be 1-deoxyglucιtyl , 2-deoxyfructityl , 1-deoxymaltιtyl, 1-deoxylactιtyl , 1-deoxygalactιtyl , 1- deoxymanmtyl , 1-deoxymaltotrιotιtyl , etc. Alkylpolvsacchaπdes Alkylpolysaccharides such as those disclosed m U.S. Patent 4,565,647 are nomonic surfactants useful m the present invention. Suitable alkylpolysaccharides include those having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysacchaπde, e.g., a polyglucoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing sacchaπde containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside . ) The mtersacchaπde bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
As noted above, the inventive formulations include a first nomonic surfactant member selected from the group consisting of linear alcohol ethoxylates, alkyl polysacchaπdes, betames, and polyhydroxy fatty acid amides.
In preferred compositions, the first nomonic surfactant member is preferably a linear alcohol ethoxylate having 6-10 carbon atoms and 3 to 12 moles, more preferably 5-7 moles, of ethoxylation per mole of alcohol. Other preferred alcohol ethoxylates are condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol . Ethoxylated alcohols having no more than 12 carbon atoms the alkyl position are commercially avaiable and include NeodolJ 1-4; NeodolJ 1-7; NeodolJ 91-8, each of which is marketed by Shell Chemical Company.
The compositions of the invention optionally include a second nomonic surfactant member. In preferred compositions, the second member is an amme oxide m an amount of from about 1-11, more preferably 5-11, % by weight of the composition.
The preferred amme oxides for use as the second surfactant member may be represented by the general formula: RjR^Nδ 0 wherein Rj is a higher alkyl radical having from 8 to 18 carbon atoms, such as lauryl, decyl , cetyl , oleyl, stearyl, hexadecyl or an amide substituted group, such as RCONH (CH3) n, wherein RCO is a long chain alkanoyl radical and n is a small whole number; R? and R3 are each lower alkyl radicals such a methyl, ethyl, propyl or a substituted lower alkyl radical such a hydroxyethyl , hydroxyethoxyethyl , hydroxy polyethoxyethyl , etc. Examples of suitable tertiary amme oxides include lauryl dimethyl amide oxide, coconut dimethylamme oxide, dodecyl dimethyl amme oxide,
0 ?H= S ?H> coco C—N—(CH2)3 N—*~0 tallow C—N—(CH2)3 N—*-0
I ° I 1 '
H CH3 H CH3 and the like.
The preferred amides are C8-C20 alkanol amides, monoethanolamides , diethanolamides , and lsopropanolamides . A particularly preferred amide is a mixture of myπstic monoethanolamide and lauric monoethanolamide . This preferred amide is sold by Stepan Company, Northfield, Illinois as Nmol LMP. Cationic ammonium compound
The cationic compound is selected according to the desired end use for the formulation - typically, the cationic compound is present m amounts ranging from about 0.5 to 20% by weight of the formulation The cationic ammonium compound is normally selected from the group consisting of quaternary ammonium salts and amme salts (salts of primary, secondary and tertiary amines) 1. Disinfectant formulations
In the antimicrobial or disinfectant formulations, the purpose of the quaternary ammonium disinfectants is to reduce the rate of reproduction of or kill on contact gram positive and gram negative organisms the organisms encountered in kitchen environments Useful such disinfectants include BTC 8358 which is N-alkyl (50% C14, 40% C2, and 10% C16) dimethyl benzyl ammonium chloride Other quarternary ammonium salts may be any of the well known class of quaternary ammonium germicides characterized by the formula
R-i R2
N X / \
R, Ra wherein at least one of the radicals, R , R , R3 and R4 ("the 'R' groups") is a hydrophobic, aliphatic, aryl aliphatic, or aliphatic aryl radical of from 6 to 26 carbon atoms, the entire cation portion of the molecule has a molecular weight of at least 165, and the remaining R groups are hydrophobic, aliphatic, aryl aliphatic, or aliphatic aryl radical of from 6 to 26 carbon atoms The hydrophobic radicals may be long-chain alkyl, long-chain alkoxy aryl, long-chain alkyl aryl, halogen- substituted long-chain alkyl aryl, long-chain alkyl phenoxy alkyl, aryl alkyl, and so forth, m nature The remaining radicals on the nitrogen atom other than the hydrophobic radicals are substituents of hydrocarbon structure usually containing a total of no more than 12 carbon atoms. The radical X m the above formula is any salt -forming anionic radical . Suitable quaternary ammonium salts within the above description include the alkyl ammonium halides such as cetyl tπmethyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl benzyl ammonium bromide, N-alkyl pyridimum halides such as N-cetyl pyridimum bromide, and the like. Other suitable types of quaternary ammonium salts include those which the molecule contains either, amide or ester linkages such a octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride. N- (laurylcocoammoformylmethyl) - pyridimum chloride, and so forth Other very effective types of quaternary ammonium germicides are those which the hydrophobic radical is characterized by a substituted aromatic nucleus as in the case of lauryloxyphenyltnmethyl ammonium chloride, cetylammophenyltπmethyl ammonium methosulfate, dodecylphenyl -tπmethyl ammonium methosulfate, dodecylbenzltrimethyl ammonium chloride, chlorinated dodecylbenzyltπmethyl ammonium chloride, and the like.
Preferred quaternary ammonium germicides of the above general types are the long-chain alkyl dimethylbenzyl quaternary ammonium salts, the alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium salts, the N- (acylcocoaminoformylmethyl) -pyridimum halides, the long-chain alkyl trimethyl ammonium halides, the long-chain alkyl benzyl dimethyl benzyl ammonium halides, and the long-chain alkyl benzyl diethyl ethanol ammonium halides in which the alkyl radical contains from 8-18 carbon atoms.
The quaternary ammonium salts useful m the invention have the general formula:
- 1! R2-N-R3 X" R4 wherein R_ and R2 are straight or branched chain lower alkyl groups having from one to seven carbon atoms; R3 is a straight or branched chain higher alkyl group having from about six to sixteen carbon atoms, or a benzyl group; R4 is a straight or branched chain higher alkyl group having from about six to sixteen carbon atoms; and X is a halogen or a methosulfate or saccharmate ion.
In preferred quaternary ammonium salts, R_ and R2 are methyl groups; R3 is benzyl or straight or brancfted chain alkyl having from about eight to sixteen carbon atoms; and R4 is straight or branched chain alkyl having from about eight to sixteen carbon atoms provided that not both R, and R4 have sixteen carbon atoms simultaneously. A preferred halogen is chlorine, or a methosulfate or a saccharmate ion.
Illustrative of suitable quaternary ammonium germicides are-, dioctyl dimethyl ammonium chloride, octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, (C12-C18) n-alkyl dimethyl benzyl ammonium chloride, (C12-C18) n-alkyl dimethyl ethylbenzyl ammonium chloride, (C -C18) n-alkyl dimethyl benzyl ammonium saccharmate, di (C^C,) alkyl (C6-C26) alkyl aryl ammonium salts, di (C3-C,) alkyl di (C6-C14) alkyl ammonium salts, trι(C1-C7) alkyl (C6-C26) alkyl ammonium salts, (C14-C26) alkyl di (Cj-C,) alkyl aryl ammonium salts , and (C14- Cl6) alkyl tn (Cx-C7) alkyl aryl ammonium salts. This is not an exhaustive list and other quaternary ammonium salts having germicidal activity will suffice. The quaternary ammonium salt m the present invention need not be a single entity, but may be a blend of two or more quaternary ammonium salts. The more preferred quaternary salts are alkyl tπmethyl ammonium compounds and alkyl dimethyl benzyl (and/or ethylbenzyl) ammonium compounds having from 10-18 carbon atoms m the long chain portion. The most preferred quaternary salts are Benzalkonium (C1216) chloride, alkyl (cetyl or oleyl) tπmethyl ammonium chloride, or other biocidal quats such as dialkyl dimethyl quats.
Where the cationic surfactant is a dialkyl dimethyl ammonium compound, the carbon chains should have from 6-14 carbons atoms m each of the two long chain alkyl groups . Di (C16 18) alkyl ammonium compounds are most preferably avoided in the compositions and formulations of the invention.
The amount, in weight-percent , of the quaternary ammonium salt, either as a single entity or blended, is up to about 50%, but is preferably from about 0.1%-10.0% and more preferably about 1-3%. The preferred quaternary ammonium germicide is a mixture of about 34% by weight C12 and 16% by weight C14 n-alkyl dimethyl ethylbenzyl ammonium chloride and about 30% by weight C14, 15% by weight C16, 2.5% by weight C12 and 2 5% by weight C n-alkyl dimethyl benzyl ammonium chloride.
The quaternary ammonium compounds can also function as cationic surfactants to produce antistatic and conditioning effects when deposited on the substrate. 2_ . Conditioning formulations
The invention also encompasses cleaning compositions capable of imparting a conditioning effect on a substrate such as skin or hair. Such formulations include hand soaps and conditioning shampoos. A variety of cationic surfactants useful as detersive surfactants and as conditioning agents are well known m the art. These materials contain ammo or quaternary ammonium hydrophilic moieties which are positively charged when dissolved m the aqueous composition of the present invention. Whether the cationic surfactant functions as a detersive surfactant or a conditioning agent, or both, will depend upon the particular compound as is well understood by those skilled the art. In general, compounds with longer chain length moieties attached to the cationic mtgogen tend to exhibit greater conditioning benefits. Cationic surfactants among those useful herein are disclosed the following documents, all incorporated by reference herein: M.C. Publishing Co., McCutcheon ' s, Detergents & Ewulsifiers, (North American edition 1993); Schwartz et al . , Surface Active Agents, Their Chemistry and Technology, New York; Interscience Publishers, 1949; U.S. Patent 3,155,591, Hilfer, issued November 3, 1964; U.S. Patent 3,929,678, Laughlm et al . , issued December 30, 1975; U.S. Patent 3,959,461, Bailey et al . , issued May 25, 1976; and U.S. Patent 4,387,090, Bolich, Jr., issued June 7, 1983.
Quaternary ammonium salts include dialkldimethyl-ammonium chlorides and tπalkyl methyl ammonium chlorides, wherein the alkyl groups have from about 12 to about 22 carbon atoms and are derived from long-chain fatty acids. These types of cationic surfactants are useful as hair conditioning agents. Examples of quaternary ammonium salts useful herein include di (coconutalkyl) dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride. Stearyl dimethyl benzyl ammonium chloride and cetyl trimethyl ammonium chloride are preferred quaternary ammonium salts useful herein (Hydrogenated tallow) trimethyl ammonium chloride is a prererred quaternary ammonium salt. Preferred of the conventional cationic conditioning agents are cetyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, stearyldimethyl Denzyl ammonium chloride, and (partially hydrogenated tallow) trimethylammomum chloride; these materials may also provide anti -static benefits to the present shampoo compositions. Salts of primary, secondary and tertiary fatty amines are also suitable cationic surfactant materials. The alkyl groups of such amines preferably have from about 12 to about 22 carbon atoms, and may be substituted or unsubstituted. Secondary and tertiary amines are preferred, tertiary amines are particularly preferred. Such amines, useful herein, include stearamido propyl dimethyl amme, diethyl am o ethyl stearamide, dimethyl stearamme, dimethyl soyam e, soyamme, myristyl am e, tridecyl amme ethyl stearylam e, N-tallowpropane diamine, ethoxylated (5 moles E.O.) stearylamme, dihydroxy ethyl stearylamme, and arachidylbehenylam e . Suitable amme salts include the halogen, acetate, phosphate, nitrate, citrate, lactate and alkyl sulfate salts. Such salts include stearylamme hydrochloπde, soyamme chloride, stearylamme formate, N-tallowpropane diamme dichloπde and stearamidopropyl dimethylamme citrate. Cationic amme surfactants included among those useful m the present invention are disclosed in U.S. Patent 4,275,055, Nachtigal, et al . , issued June 23, 1981, incorporated by reference herein. Cationic conditioning surfactants especially useful m shampoo formulations are quaternary ammonium or ammo compounds having at least one N radical containing one or more nomonic hydrophilic moieties selected from alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, and alkylester moieties, and combinations thereof. The surfactant contains at least one hydrophilic moiety within 4, preferably within 3, carbon atoms
(inclusive) of the quaternary nitrogen or cationic ammo nitrogen. Additionally, carbon atoms that are part of a hydrophilic moiety, e.g., carbon atoms m a hydrophilic polyoxyalkylene (e.g., -CH2-CH?-0- ) , that are adjacent to other hydrophilic moieties are not counted when determining the number of hydrophilic moieties within 4, or preferably 3, carbon atoms of the cationic nitrogen. In general, the alkyl portion of any hydrophilic moiety is preferably a C3-C3 alkyl. Suitable hydrophile-contammg radicals include, for example, ethoxy, propoxy, polyoxyethylene, polyoxypropylene, ethylamido, propylamido, hydroxymethyl , hydroxyethyl , hydroxypropyl , methylester, ethylester, propylester, or mixtures thereof, as nomonic hydrophile moieties. The ammo surfactants must be positively charged at the pH of the shampoo compositions. Generally, the pH of the shampoo compositions will be less than about 10, typically from about 3 to about 9.
Other cationic compounds suitable for use m the invention include NH4 *, and mono-, di-, and tn-short chain alkyl ammonium salts. Adiuvant materials
Various adjuvant materials may be added to these foaming aqueous detergent compositions such as small amounts of viscosity builders and conditioning agents inclusive of gums and hydroxy-propyl methyl cellulose. Such ingredients can be added in an amount that does not adversely effect the foaming and cleaning characteristics of the compositions. Other ingredients may include alkaline or acid buffers to aid m the adjustment and maintenance of the desired pH of the finished product such a borax, various inorganic water-soluble phosphates, sodium hydroxide, citric acid, etc. Other additions include optical bπghteners, bleaches, germicides, fungicides, bactericides, colorants, perfumes, etc. m minor amounts which do not interfere with the cleaning, foaming, conditioning, or sanitizing properties of the composition.
Other ingredients include ethylenediamme tetraacetate (EDTA) and polyethylene glycol (PEG) fatty acid esters. EDTA is especically useful antibacterial cleaning compositions, particularly handsoaps, since it increases the effectiveness of the antibacterial quaternary ammonium compound, m particular against Pseudomonas Aerugmosa, a pathogenic gram-negative organism. A representative PEG ester is PEG 600 distearate. This ester provides excellent viscosity enhancement the inventive surfactant systems by association with other components without causing a loss of clarity or an increase m color.
All documents, e.g., patents and journal articles, cited above or below are hereby incorporated by reference m their entirety.
In the examples, all amounts are stated in percent by weight of active material unless indicated otherwise.
One skilled m the art will recognize that modifications may be made m the present invention without deviating from the spirit or scope of the invention. The invention is illustrated further by the following examples which are not to be construed as limiting the invention or scope of the specific procedures or compositions described herein. The detergent compositions of the invention are prepared by combining water with the alcohol ethoxylate and amme oxide surfactant members, mixing until uniform and then adding any optional components, such as, for example, amide or cationic ammonium compound, and again mixing until uniform. Heating may be employed as needed to enhance dissolution of the components. Various antimicrobial cleaning formulations described herein were analyzed for detergency and foam height. Detergency and foam longevity was evaluated using the mimplate assay described below. Foam height was evaluated according to the Ross Miles Foam Height test as described by J. Ross and J.D. Miles m Oil and Soap, 1_8; 99 (1941) at 0.032% active concentration using water of 140 ppm hardness at 25°C. Ross- Miles test results are displayed in cm.
Foam longevity and Detergency Evaluation The capability of various formulations for cleaning and degreasmg was determined by the Mini-Plate Test, as follows: Preparation of Soil Material
1. Melt shortening (Crisco, approx. 100 g) m a beaker at 160°F. 2. Add a small amount (not much needed for deep color) of red dye to melted Crisco and stir until dissolved.
3. Calibrate syringe to deliver 0.36 g of Crisco soil on each plate .
4. Apply 0.36 g of Crisco oil to each of the watchglasses (One large watchglass is equivalent to three mini-plates) . 5. When all of the larger watchglasses have been soiled, recalibrate syringe to deliver 0.12 g of Crisco soil to each plate. 6. Apply 0.12 g of Crisco soil to each of the smaller watchglasses .
7. Allow soiled watchglasses to harden at room temperature overnight before using.
8. Soiled watchglasses should always be stored at room temperature [ (can be stored indefinitely) ] .
Procedure for Analyzing Test Formulations
1. A test solution may be made by diluting sufficient product with [tap] water (140 ppm hardness) to a concentration of 0.048% active material. 400 ml of such a solution is employed; heating to about 130-135°F may be necessary to achieve dissolution of the product.
3. The solution in placed in a Pyrex dish and then agitated with a paintbrush to generate foam, and the temperature of the solution adjusted to 120 F
4. At this point, large watchglasses (which represent three plates each) are washed, one every 45 seconds, by removing a thin layer of soil at a time from the surface of the plate with the paintbrush, then agitating the paintbrush m the solution to remove the adhering soil (which consequently breaks down the foam) .
5. The enάpoint of the test is the number of mini-plates washed when further agitation of the solution fails to produce new/additional foam on the solution surface. In certain tests, small watchglasses representing 1/3 the surface area of a large watchglass may be used as the endpomt is neared.
Formulations according to the invention are shown below in the following examples. In all the examples, all amounts are given in percent active by weight of the final formulation unless indicated to the contrary.
Figure imgf000029_0001
1 EO refers to the average number of moles of ethylene oxide per mole of alcohol .
Figure imgf000030_0001
- 2!
Figure imgf000031_0001
Figure imgf000032_0001
Formulation 47 can be made at 47% actives utilizing the same component ratios
Broad Spectrum Antimicrobial Hand Soap Formulation
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
♦Comparative example
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
FORMULATION NO.
Figure imgf000042_0001
Figure imgf000043_0001
*Comparative example
Hand Soap and Conditioning Shampoo Formulations
Hand soap and conditioning shampoo formulations according to the invention are prepared essentially by the method described above for dishwashing compositions.
Figure imgf000044_0001
Figure imgf000045_0001
From the foregoing, it will be appreciated that although specific embodiments of the invention have been described herein for purposes of illustration, various modifications may be made without deviating from the spirit or scope of the invention.

Claims

What is claimed is:
1. An aqueous liquid cleaning composition, the composition being free of anionic surfactants and comprising a nomonic surfactant system consisting essentially of: (a) from about 0.1-50% by weight based on the weight of the composition of a linear alcohol ethoxylate having an average carbon chain length of no more than 12 carbon atoms ; and
(b) a surfactant member selected from the group consisting of amme oxides, betames, and mixtures thereof, the total concentration of active components m the composition based on the weight of the composition is at least about 5%.
2. A composition according to claim 1, further including a surfactant selected from the group consisting of alkanolamides, alkyl polysaccharides , betames, cationic ammonium compounds, polyhydroxy fatty acid amides, and mixtures thereof .
3. A composition according to Claim 2, comprising from about 0 5-20% by weight of the composition of a cationic ammonium compound .
4. A composition according to claim 2, wherein the amount of linear alcohol ethoxylate is from about 8-18% by weight of the composition.
5. A composition according to claim 4, wherein the amount of linear alcohol ethoxylate is from about 9-17% by weight of the composition.
6. A composition according to claim 4, wherein the amount of the amme oxide m the composition is from about 3-23% by weight of the composition.
7. A composition according to claim 1, wherein the amount of linear alcohol ethoxylate has from 6-11 carbon atoms m the alkyl portion and from about 4-8 moles of ethoxylation per mole of alcohol .
8. A composition according to claim 1, wherein the amounts of linear alcohol ethoxylate and amme oxide m the composition are respectively, by weight of the composition, from about 9-18%, and 3-23%.
9. An aqueous liquid cleaning composition, the composition being free of anionic surfactants and consisting essentially of: a) from about 2-23% Py weight based on the weight of the composition of a linear alcohol ethoxylate having an average carbon chain length of no more than 12 carbon atoms ; (b) from about 2-23% bv weight based on the weight of the composition of a surfactant member selected from the group consisting of amme oxides, betames, and mixtures thereof ; and
(c) a cationic ammonium compound, the total concentration of active components in the composition based on the weight of the composition is at least about 5%.
10. A composition according to Claim 9, wherein the cationic ammonium compound is a quaternary ammonium disinfecting compound .
11. A composition according to Claim 10, wherein the linear alcohol ethoxylate has a minimum of 6 carbon atoms and 3 to 12 moles of ethoxylation per mole of alcohol.
12. A composition according to claim 11, wherein the amount of linear alcohol ethoxylate is from about 8-18% by weight of the composition.
13. A composition according to claim 12, wherein the amount of linear alcohol ethoxylate is from about 9-17% by weight of the composition.
14. A composition according to claim 13, wherein the amount of the amme oxide m the composition is from about 3-23% by weight of the composition.
15. A composition according to claim 14, wherein the amounts of linear alcohol ethoxylate and amme oxide m the composition are respectively, by weight of the composition, from about 9-18%, and 3-23%.
16. A method for preparing a cleaning composition comprising :
(a) preparing a surfactant system consisting essentially of: d) from about 0.1-50% by weight based on the weight of the composition of a linear alcohol ethoxylate having an average carbon chain length of no more than 12 carbon atoms ; and
(n) a surfactant member selected from the group consisting of amme oxides, betames, and mixtures thereof; and
(b) combining the surfactant system with a cationic ammonium compound such that the total concentration of active components m the composition based on the weight of the composition is at least about 5%.
17. An aqueous liquid cleaning composition, the composition being free of anionic surfactants and comprising a nomonic surfactant system consisting essentially of: (a) from about 13-19% by weight based on the weight of the composition of a linear alcohol ethoxylate having an average carbon chain length of no more than 12 carbon atoms; and;
(b) from about 3-7% by weight of the composition of a mono- or dialkanolamide ; and
(c) from about 5-10% by weight of the composition of an alkylpolyglycoside .
18. An aqueous liquid cleaning composition, the composition being free of anionic surfactants and comprising a nomonic surfactant system consisting essentially of:
(a) from about 13-19% by weight based on the weight of the composition of a sulfobeta e;
(b) from about 5-20% by weight of the composition of an amme oxide, a betaine, or mixture thereof;
(c) from about 3-7% by weight of the composition of a mono- or dialkanolamide or mixtures thereof; and
(d) from about 3-7% by weight of the composition of an alkylpolyglycoside, the total concentration of surfactants m the composition being from about 30-35% by weight of the composition.
19. A composition according to claim 17, further comprising a cationic ammonium compound.
20. A composition according to claim 18, further comprising a cationic ammonium compound.
21. A composition according to claim 19, where the amounts of cationic ammonium compound is from about 0.5 to 20% by weight of the composition.
22. A composition according to claim 20, where the amounts of cationic ammonium compound is from about 0.5 to 20% by weight of the composition.
23. A composition according to Claim 1, wherein the amount of linear alcohol ethoxylate is from about 5-40% by weight based on the weight of the composition.
24. A composition according to Claim 1, wherein the amount of linear alcohol ethoxylate is from about 5-12% by weight based on the weight of the composition.
25. An aqueous liquid cleaning composition consisting essentially of, by weight of the composition, from about 4-7% of a Cb 10 alcohol ethoxylate having an average of about 9 moles of ethylene oxide, from about 12-20% of a C8 10 alcohol ethoxylate having an average of about 12 moles of ethylene oxide, from about 7-13% of a fatty acid amidopropylamme oxide having an average of about 10-18 fatty acid carbon atoms, from about 1-4% of a fatty acid diethanolamide having an average of about 10-18 fatty acid carbon atoms, from about 1-4% of a fatty acid monoethanolamide having an average of about 10-18 fatty acid carbon atoms; and an antibacterial effective amount of an antibacterial quaternary ammonium compound.
26. A composition according to claim 25, wherein the antibacterial quaternary ammonium compound is an C8-C18 alkyl dimethyl benzyl ammonium chloride.
27. An aqueous liquid cleaning composition, the composition being free of anionic surfactants and comprising a nomonic surfactant system consisting essentially of: (a) from about 1-5% by weight based on the weight of the composition of a linear alcohol ethoxylate having an average carbon chain length of from about 8 to 12 carbon atoms and from about 5-12 moles of ethoxylation per mole of alcohol;
(b) from about 3-10% by weight of the composition of a betaine ;
(c) from about 1-3% by weight of the composition of a mono- or dialkanolamide; and (d) from about 1-5% by weight of the composition of an quaternary ammonium compound.
28. An aqueous liquid cleaning composition, the composition being free of anionic surfactants and comprising a nomonic surfactant system consisting essentially of:
(a) from about 0.1-10% by weight based on the weight of the composition of a linear alcohol ethoxylate having an average carbon chain length of no more than about 12 carbon atoms and from about 4-12 moles of ethoxylation per mole of alcohol;
(b) from about 0.05-25% by weight of the composition of a betaine ;
(c) from about 0.1-5% by weight of the composition of a mono- or dialkanolamide; (d) from about 0.05 to 15% by weight of a amme oxide, the combined amount of betaine and amme oxide being from about 0.1 to 30% by weight of the composition; and
(d) from about 0.1-5% by weight of the composition of an quaternary ammonium compound, the total concentration of surfactants the composition no more than about 25% by weight of the composition.
29. A detergent composition suitable for preparing an aqueous, liquid cleaning formulation, the detergent composition comprising, based on the total weight of active components in the composition:
(a) from about 10-70% by weight of an alcohol ethoxylate having an average of 6-12 carbon atoms and an average of 4-15 moles of ethylene oxide;
(b) from about 15-60% by weight of an amme oxide, a betaine or mixture thereof;
(c) from about 5-20% by weight of an alkanolamide having an average of 10-16 carbon atoms.
30. A detergent composition according to claim 29, further comprising up to about 50% by weight of a cationic surfactant.
31. An aqueous liquid composition comprising from about 3- 10% by weight of the detergent composition of claim 29.
32 A detergent composition according to claim 29, where component (b) is an amme oxide which is an alkyldimethyl amme oxide having an average of from 10-18 carbon atoms m the alkyl portion.
33. A detergent composition according to claim 29, where component (b) is an amme oxide which is an alkyl amido propyl dimethyl amme oxide having an average of from 12-18 carbon atoms m the alkyl portion.
34. A detergent composition according to claim 29, where the component (b) is a betaine which is alkyl amido propyl betaine having an average of 10-18 carbon atoms the alkyl portion.
35. A detergent composition according to claim 30, wherein the cationic surfactant is a biocidal quaternary ammonium compound . 36. A detergent composition according to claim 29, further comprising an alkyl trimethyl ammonium conditioning compound.
5 37. A detergent composition according to claim 29, wherein component (b) is a combination of an amine oxide and an alkyl polyglucoside, or a betaine and an alkyl polyglucoside .
0 38. A detergent composition suitable for preparing an aqueous, liquid cleaning formulation, the detergent composition comprising, based on the total weight of active components in the composition: a) from about 25-60% by weight an alcohol ethoxylate 5 having an average of 6-12 carbon atoms and containing an average of from about 4-15 moles of ethylene oxide where the concentration of alcohol ethoxylate in the composition is of the total surfactant present by weight ; 0 b) from about 15-55% by weight of an amine oxide, a betaine or mixture thereof ,- and c) 5-20% by weight of an alkanolamide having an average of from 10-16 carbon atoms; and d) up to about 20% by weight of a cationic surfactant. 5
39. A detergent composition according to claim 38, wherein the amount of component (b) is from about 20-35% by weight.
40. A detergent composition according to claim 39, wherein 0 the cationic surfactant is from about 3-10% by weight.
42. A detergent composition according to claim 39, wherein the alcohol ethoxylate has an average of from 8-10 carbon atoms and contains an average of 5-12 moles of ethylene oxide. 5
43. A detergent composition according to claim 39, wherein the amount of the alkanolamide in the composition is from about 9-16% by weight.
44. A detergent composition according to claim 39, wherein the amount of the alcohol ethoxylate is from about 25-60% by weight .
45. A detergent composition according to claim 39, wherein the amount of the alcohol ethoxylate is from about 40-60% by weight .
46. An aqueous cleaning formulation comprising from about 5% to 60% by weight of the formulation of a detergent composition, the detergent composition comprising, based on the total weight of active components in the detergent composition: (a) from about 25-60% by weight of an alcohol ethoxylate having an average of 8-12 carbon atoms an containing an average of 5-12 moles of ethylene oxide;
(b) from about 15-55% by weight of an alkyl dimethyl amine oxide, an alkyl amido propyl dimethyl amine oxide, an alkyl amido propyl betaine, or a mixture thereof;
(c) from about 9-16% by weight of an alkanolamide having an average of 10-16 carbon atoms; and
(d) from about 3-10% by weight of biocidal cationic surfactant .
47. A formulation according to claim 46, wherein the amine oxides have an average of 10-18 carbon atoms in the alkyl group.
48. A formulation according to claim 47, wherein the component (b) is from about 20-35% by weight of the detergent composition.
49. A formulation according to claim 47, wherein the component (b) is an alkyl amido propyl betaine having an average of from 12-18 carbon atoms in the alkyl portion.
50. A composition according to claim 25, wherein the antibacterial quaternary ammonium compound is a di (C6-C14) alkyl dimethyl ammonium chloride .
PCT/US1998/021788 1997-10-15 1998-10-15 High foaming detergent composition having non-ionic surfactant base WO1999019438A1 (en)

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EP1077250B1 (en) * 1999-08-16 2005-01-26 Agroserve Limited Aqueous cleaning formulations
WO2001053442A3 (en) * 2000-01-24 2001-12-20 Colgate Palmolive Co Antimicrobial cleaning composition containing a cationic surfactant
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US8080269B2 (en) 2003-03-05 2011-12-20 Byocoat Enterprises, Inc. Antimicrobial solutions and process related thereto
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WO2005105964A3 (en) * 2004-04-29 2006-01-19 Basf Ag Synergistic surfactant mixtures with higher dynamic properties and lower cmc
EP1931209A1 (en) * 2005-09-03 2008-06-18 Byocoat Enterprises, Inc. Antimicrobial solutions and process related thereto
EP1931209A4 (en) * 2005-09-03 2011-01-19 Byocoat Entpr Inc Antimicrobial solutions and process related thereto
AU2005336108B2 (en) * 2005-09-03 2012-01-12 Byocoat Enterprises, Inc. Antimicrobial solutions and process related thereto
EP1975224A1 (en) * 2007-03-30 2008-10-01 Johnson & Johnson Consumer France SAS Mild, foaming cleansing composition
WO2009023010A1 (en) * 2007-08-14 2009-02-19 Shaklee Corporation Cleaning composition
WO2012175942A2 (en) 2011-06-20 2012-12-27 Reckitt & Colman (Overseas) Limited Foaming topical antimicrobial cleaning compositions
EP2862563A1 (en) 2011-06-20 2015-04-22 Reckitt & Colman (Overseas) Limited Foaming topical antimicrobial cleaning compositions
EP2857362A4 (en) * 2012-07-31 2015-12-30 Orientnano Co Ltd Microbial flora activator, anti-filamentous fungi agent comprising said microbial flora activator as active ingredient, and method for treating waste water containing oil, fat, etc. using said microbial flora activator
EP3184618A1 (en) 2015-12-22 2017-06-28 The Procter & Gamble Company Antimicrobial hard surface cleaning compositions providing improved grease removal
WO2017112448A1 (en) * 2015-12-22 2017-06-29 The Procter & Gamble Company Antimicrobial hard surface cleaning compositions providing improved grease removal
US10323214B2 (en) 2015-12-22 2019-06-18 The Procter & Gamble Company Antimicrobial hard surface cleaning compositions providing improved grease removal
US10597610B2 (en) 2015-12-22 2020-03-24 The Procter & Gamble Company Antimicrobial hard surface cleaner comprising a thickening copolymer
US11427787B2 (en) 2018-12-20 2022-08-30 Ecolab Usa Inc. Surfactant blend for removal of fatty soils
EP4126379A4 (en) * 2020-04-01 2024-05-22 Energizer Auto, Inc. Hydrophobic finish car wash compositions and methods of use thereof

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