WO1999019438A1 - High foaming detergent composition having non-ionic surfactant base - Google Patents
High foaming detergent composition having non-ionic surfactant base Download PDFInfo
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- 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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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0094—High foaming compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/835—Mixtures of non-ionic with cationic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/525—Carboxylic 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/75—Amino oxides
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
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
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AU10896/99A AU1089699A (en) | 1997-10-15 | 1998-10-15 | High foaming detergent composition having non-ionic surfactant base |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US94367597A | 1997-10-15 | 1997-10-15 | |
US08/943,675 | 1997-10-15 |
Publications (2)
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WO1999019438A1 true WO1999019438A1 (en) | 1999-04-22 |
WO1999019438A9 WO1999019438A9 (en) | 1999-09-30 |
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PCT/US1998/021788 WO1999019438A1 (en) | 1997-10-15 | 1998-10-15 | High foaming detergent composition having non-ionic surfactant base |
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WO (1) | WO1999019438A1 (en) |
Cited By (17)
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---|---|---|---|---|
WO2001053442A2 (en) * | 2000-01-24 | 2001-07-26 | Colgate-Palmolive Company | Antimicrobial cleaning composition containing a cationic surfactant |
WO2002076207A1 (en) * | 2001-03-27 | 2002-10-03 | The Dial Corporation | Antibacterial compositions |
EP1284135A2 (en) * | 2001-08-16 | 2003-02-19 | Johnson & Johnson Consumer Companies, Inc. | Mild cleansing composition having stable foam |
WO2004009754A1 (en) * | 2002-07-24 | 2004-01-29 | Reckitt Benckiser Inc | Acidic hard surface cleaners |
EP1077250B1 (en) * | 1999-08-16 | 2005-01-26 | Agroserve Limited | Aqueous cleaning formulations |
WO2005105964A2 (en) * | 2004-04-29 | 2005-11-10 | Basf Aktiengesellschaft | Synergistic surfactant mixtures with higher dynamic properties and lower cmc |
US6998372B2 (en) | 2001-08-16 | 2006-02-14 | J&J Consumer Companies, Inc. | Moisturizing detergent compositions |
EP1931209A1 (en) * | 2005-09-03 | 2008-06-18 | 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 |
US8075936B2 (en) | 2003-03-05 | 2011-12-13 | Byocoat Enterprises, Inc. | Antimicrobial solutions and process related thereto |
WO2012175942A2 (en) | 2011-06-20 | 2012-12-27 | 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 |
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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- 1998-10-15 WO PCT/US1998/021788 patent/WO1999019438A1/en active Application Filing
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Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
WO2001053442A2 (en) * | 2000-01-24 | 2001-07-26 | Colgate-Palmolive Company | Antimicrobial cleaning composition containing a cationic surfactant |
WO2002076207A1 (en) * | 2001-03-27 | 2002-10-03 | The Dial Corporation | Antibacterial compositions |
US6616922B2 (en) * | 2001-03-27 | 2003-09-09 | The Dial Corporation | Antibacterial compositions |
US6998372B2 (en) | 2001-08-16 | 2006-02-14 | J&J Consumer Companies, Inc. | Moisturizing detergent compositions |
EP1284135A2 (en) * | 2001-08-16 | 2003-02-19 | Johnson & Johnson Consumer Companies, Inc. | Mild cleansing composition having stable foam |
EP1284135A3 (en) * | 2001-08-16 | 2003-10-08 | Johnson & Johnson Consumer Companies, Inc. | Mild cleansing composition having stable foam |
AU2003281521B2 (en) * | 2002-07-24 | 2009-05-21 | Reckitt Benckiser Llc | Acidic hard surface cleaners |
WO2004009754A1 (en) * | 2002-07-24 | 2004-01-29 | Reckitt Benckiser Inc | Acidic hard surface cleaners |
US8586115B2 (en) | 2003-03-05 | 2013-11-19 | Byocoat Enterprises, Inc. | Antimicrobial solutions and process related thereto |
US8075936B2 (en) | 2003-03-05 | 2011-12-13 | Byocoat Enterprises, Inc. | Antimicrobial solutions and process related thereto |
US8080269B2 (en) | 2003-03-05 | 2011-12-20 | Byocoat Enterprises, Inc. | Antimicrobial solutions and process related thereto |
WO2005105964A2 (en) * | 2004-04-29 | 2005-11-10 | Basf Aktiengesellschaft | Synergistic surfactant mixtures with higher dynamic properties and lower cmc |
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 |
Also Published As
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WO1999019438A9 (en) | 1999-09-30 |
AU1089699A (en) | 1999-05-03 |
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