WO2005078063A2 - Improved liquid detergent composition for use with a foam-generating dispenser - Google Patents

Improved liquid detergent composition for use with a foam-generating dispenser Download PDF

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Publication number
WO2005078063A2
WO2005078063A2 PCT/US2005/004220 US2005004220W WO2005078063A2 WO 2005078063 A2 WO2005078063 A2 WO 2005078063A2 US 2005004220 W US2005004220 W US 2005004220W WO 2005078063 A2 WO2005078063 A2 WO 2005078063A2
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composition
viscosity
alkyl
liquid detergent
detergent composition
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English (en)
French (fr)
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WO2005078063A3 (en
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Howard David Hutton, Iii
Bernard Frans De Ryck
Peter Robert Foley
Kevin George Goodall
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to JP2005518099A priority Critical patent/JP2006521417A/ja
Priority to EP05713269A priority patent/EP1761625A2/en
Publication of WO2005078063A2 publication Critical patent/WO2005078063A2/en
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Publication of WO2005078063A3 publication Critical patent/WO2005078063A3/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
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017Multi-phase liquid compositions
    • C11D17/0021Aqueous microemulsions
    • 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
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • 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
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • 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
    • C11D3/16Organic compounds
    • C11D3/18Hydrocarbons
    • 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
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2006Monohydric alcohols
    • C11D3/2037Terpenes
    • 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
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2041Dihydric alcohols
    • C11D3/2062Terpene
    • 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
    • C11D3/43Solvents

Definitions

  • the present invention relates to liquid detergent compositions. Specifically, the present invention relates to liquid detergent compositions which are to be used with a foam-generating dispenser.
  • Liquid detergent compositions are well-known for use in cleaning items such as laundry, dishes, hard surfaces, hair, human and other types of skin, etc. Such compositions typically include a surfactant, and a solvent, and posses a viscosities which can range from extremely thin, such as dilute alcohol-based cleaning compositions to paste and gel-type cleaning compositions.
  • the present invention relates to a liquid detergent composition for use with a foam-generating dispenser which contains from about 10% to about 90% of a surfactant, from about 10% to about 70% of a solvent, and the balance adjunct detergent ingredients.
  • the liquid detergent composition has a viscosity at 5 °C of less than about 0.15 Pa*s, a viscosity-temperature slope of more than about -0.008 Pa*s/°C and also has a flash point of at least about 40 °C. It has now been found that such a liquid detergent composition may more easily generate foam at a variety of typical use conditions, while concurrently remaining safe for use in areas adjacent to an open flame, such as a kitchen sink, and/or a kitchen countertop. Such compositions therefore balance both concerns and more consistently, readily and easily generate foam from a foam-generating dispenser than compositions which do not have the discussed viscosity-temperature slope and flash point profiles.
  • alkyl means a hydrocarbyl moiety which is straight or branched, saturated or unsaturated. Unless otherwise specified, alkyl moieties are preferably saturated or unsaturated with double bonds, preferably with one or two double bonds. Included in the term “alkyl” is the alkyl portion of acyl groups. As used herein, the term “comprising” means that other steps, ingredients, elements, etc. which do not affect the end result can be added.
  • microemulsion means a oil-in-water emulsion which has the ability to emulsify oil into non-visible droplets. Such non-visible droplets typically have maximum diameter of less than about 100 angstroms (A), preferably less than 50 A as measured by methods known in the art, such as ISO 7027 which measures turbidity at a wavelength of 880 nm. Turbidity measuring equipment is easily available from, for example, Omega Engineering, Inc., Stamford, Connecticut, U.S.A.
  • protomicroemulsion means a composition which may be diluted with water to form a microemulsion.
  • liquid crystal composition means a composition which is in a liquid crystal state or form, and may be clear or lactescent. Liquid crystal compositions are further defined in, for example, U.S. Patent No. 5,523,013 to Durbut, et. al., published on June 4, 1996.
  • the liquid detergent composition herein contains from about 10% to about 90% of a surfactant, from about 10% to about 70% of a solvent, and the balance adjunct detergent ingredients. More importantly, the composition has a viscosity at 5 °C of less than about 0.15 Pa*s, a viscosity-temperature slope of less than about -0.008 Pa*s/°C, and a flash point of at least about 40 °C.
  • Such a composition may be in the form of a solution, a liquid crystal composition, a microemulsion, and/or a protomicroemulsion as desired.
  • the liquid detergent composition is typically intended as a hard surface cleaning composition, a hand or automatic machine dishwashing composition, a scouring composition, and/or a laundry and fabric care composition, preferably a hard surface cleaning composition, a hand dishwashing composition, and/or a scouring composition, more preferably a hard surface cleaning composition and/or a hand dishwashing composition, and even more preferably a hand dishwashing composition.
  • Such a composition is especially for use in combination with a foam-generating dispenser, preferably a non-aerosol and non-trigger-type foam-generating dispenser, such as are known in the art of body washes, shaving, and/or personal toiletries.
  • a foam-generating dispenser preferably a non-aerosol and non-trigger-type foam-generating dispenser, such as are known in the art of body washes, shaving, and/or personal toiletries.
  • foam-generating mechanisms of such dispensers specifically provide excellent results when used in combination with the compositions herein.
  • the surfactants useful herein include anionic surfactants, amphoteric surfactants, cationic surfactants, zwitterionic surfactants, as well as nonionic surfactants, preferably a combination of anionic and nonionic surfactants are employed herein.
  • Surfactants as described herein include those having about 10 or more carbon atoms in the longest alkyl chain and/or alkaryl group. Such surfactants are present at from about 10% to about 90%, preferably from about 15% to about 75%, and more preferably from about 20% to about 60% by weight of the liquid detergent composition.
  • the anionic surfactant useful herein includes water-soluble salts or acids of the formula ROSO 3 M, wherein R preferably is a Cw-Qjo linear or branched hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 2 o alkyl component, more preferably a C ⁇ o-C ⁇ 4 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation or ammonium or substituted ammonium, but preferably sodium and/or potassium.
  • R preferably is a Cw-Qjo linear or branched hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 2 o alkyl component, more preferably a C ⁇ o-C ⁇ 4 alkyl or hydroxyalkyl
  • M is H or a cation, e.g., an alkali metal cation or ammonium or substituted ammonium, but
  • Suitable anionic surfactants for use herein are water-soluble salts or acids of the formula RO(A) m SO M wherein R is an unsubstituted linear or branched C ⁇ 0 -C2o alkyl or hydroxyalkyl group having a C 10 -C2 0 alkyl component, preferably a C 12 -C20 alkyl or hydroxyalkyl, more preferably C] 2 -C ⁇ 4 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 5, more preferably between about 0.5 and about 2, and M is H or a cation which can be, for example, a metal cation, ammonium or substituted-ammonium cation.
  • R is an unsubstituted linear or branched C ⁇ 0 -C2o alkyl or hydroxyalkyl group having a C 10 -C2 0 alkyl component, preferably a C 12
  • Alkyl ethoxylated sulfates (abbreviated herein as C ⁇ _ ⁇ E m S, where X-Y represents the alkyl group chain length, and where m is the same as described above) as well as alkyl propoxylated sulfates are thus preferred herein.
  • Exemplary surfactants are C ⁇ 0 -C ⁇ 4 alkyl polyethoxylate (1.0) sulfate, C ⁇ o-C 14 polyethoxylate (1.0) sulfate, C 10 -C ⁇ 4 alkyl polyethoxylate (2.25) sulfate, C ⁇ 0 -C ⁇ 4 polyethoxylate (2.25) sulfate, C 10 -C ⁇ 4 alkyl polyethoxylate (3.0) sulfate, C ⁇ o-C ⁇ 4 polyethoxylate (3.0) sulfate, and C ⁇ 0 -C ⁇ 4 alkyl polyethoxylate (4.0) sulfate, C IO -CJ S polyethoxylate (4.0) sulfate.
  • the anionic surfactant is a mixture of alkoxylated, preferably ethoxylated and non-alkoxylated sulfate surfactants.
  • the preferred average degree of alkoxylation is from about 0.4 to about 0.8.
  • alkyl sulphonates and alkyl aryl sulphonates including water-soluble salts or acids of the formula RSO3M wherein R is a C 10 -C 20 linear or branched, saturated or unsaturated alkyl or aryl group, preferably a C10-C 20 alkyl or aryl group and more preferably a C ⁇ 0 -Cj 4 alkyl or aryl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, dieth
  • the carbon chain of the anionic surfactant comprises one or more alkyl, preferably C ⁇ alkyl, branching units.
  • the average percentage branching of the anionic surfactant is greater than about 30%, more preferably from about 35% to about 80% and most preferably from about 40% to about 60%, by weight of the anionic surfactant.
  • Such average percentage of branching can be achieved by formulating the composition with one or more anionic surfactants all of which are preferably greater than about 30% branched, more preferably from about 35% to about 80% and most preferably from about 40% to about 60%.
  • the composition may comprise a combination of branched anionic surfactant and linear anionic surfactants such that on average the percentage of branching of the total anionic surfactant combination is greater than about 30%, more preferably from about 35% to about 80% and most preferably from about 40% to about 60%.
  • the amphoteric surfactant herein is a surfactant whose charge changes according to the pH of the composition, and is preferably selected from the various amine oxide surfactants.
  • Amine oxides are semi-polar surfactants and include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
  • R 3 where Rj is a C JO - I4 alkyl and R 2 and R 3 are methyl or ethyl, and those described in U.S. Pat. No. 4,316,824 to Pancheri, granted on February 23, 1982; U.S. Pat. No. 5,075,501 to Borland and Smith, granted on December 24, 1991; and U.S. Pat. No. 5,071,594 to Borland and Smith, granted on December 10, 1991.
  • Preferred amine oxide surfactants have the formula: R 3
  • R 3 is an alkyl, a hydroxyalkyl, an alkyl phenyl group or a mixture thereof containing from about 10 to about 22 carbon atoms
  • R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof
  • x is from 0 to about 3
  • each R 5 is an alkyl or a hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
  • the R 5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • Preferred amine oxide surfactants include the Cio- s alkyl dimethyl amine oxides and the C 10 -C 1 2 alkoxy ethyl dihydroxy ethyl amine oxides. Also suitable are amine oxides such as propyl amine oxides, represented by the formula:
  • R 1 is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from about 10 to about 18 carbon atoms
  • R 2 and R 3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2- hydroxypropyl, or 3-hydroxypropyl and n is from 0 to about 10.
  • a further suitable species of amine oxide semi-polar surface active agents comprise compounds and mixtures of compounds having the formula: R 2 R 1 (C 2 H 4 O) n -N— --> ⁇ O R 3
  • Rj is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from about 10 to about 18 carbon atoms
  • R 2 and R 3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2- hydroxypropyl, or 3-hydroxypropyl and n is from 0 to about 10.
  • amphoteric surfactant useful in the present invention includes amido propyl betaines and derivatives of aliphatic or heterocyclic secondary and ternary amines in which the aliphatic moiety can be straight chain, or branched and wherein one of the aliphatic substituents contains from about 8 to about 24 carbon atoms and at least one aliphatic substituent contains an anionic water- solubilizing group.
  • suitable amphoteric surfactants are disclosed in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch).
  • Cationic surfactants useful herein include quaternary ammonium salts having at least one C10-C1 4 alkyl chain, charge-balanced with an anion, such as chloride.
  • Preferred cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula: [R 2 (OR 3 ) v ] [R 4 (OR 3 ) y ] 2 R 5 N + ⁇ - wherein R 2 is an alkyl or alkyl benzyl group having from about 10 to about 18 carbon atoms in the alkyl chain, each R 3 is selected from the group consisting of-CH 2 CH 2 -, CH 2 CH(CH 3 )-, -CH 3 CH(CH 2 OH)-, -CH 2 CH 2 CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of C ⁇ -C 4 alkyl, Cj-C 4 hydroxyalkyl, benzyl,
  • cationic surfactants useful herein are also described in U.S. 4,228,044, Cambre, issued October 14, 1980, Mono-alkoxylated and di-alkoxylated ammonium salts may also be used herein, and are commonly available from suppliers such as Clariant Corporation, Charlotte North Carolina, USA and Akzo Nobel nv, Arnhem, the Netherlands.
  • Zwitterionic surfactants may also be useful herein and can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S.
  • Zwitterionic surfactants particularly useful herein include commonly- available betaine surfactants, particularly lauryl amido propyl betaine, C ⁇ 2 -C ⁇ 6 cocoamido propyl betaine, and a mixture thereof.
  • Nonionic surfactants useful herein are generally disclosed in U.S. Patent 3,929,678 to Laughlin, et al., issued December 30, 1975, at column 13, line 14 through column 16, line 6.
  • Other nonionic surfactants useful herein include the 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 about 10 to about 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 18 moles of ethylene oxide per mole of alcohol.
  • Examples of commercially available nonionic surfactants of this type include TERGITOL® 15-S-9 (the condensation product of C1 1-C15 linear secondary alcohol with 9 moles ethylene oxide), TERGITOL® 24-L-6 NMW (the condensation product of C 12 -C ⁇ 4 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation;
  • NEODOL® 45-9 (the condensation product of C 14 -C ⁇ 5 linear alcohol with 9 moles of ethylene oxide), NEODOL® 23-6.5 (the condensation product of Cj 2 -C ⁇ 3 linear alcohol with 6.5 moles of ethylene oxide), marketed by Shell Chemical Company, and KYRO® EOB (the condensation product of C 13 - 5 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company, Cincinnati, Ohio, U.S.A.
  • Other commercially available nonionic surfactants include DOBANOL 91-8® marketed by
  • nonionic surfactant selected from the group consisting of an alkyl polyglycoside surfactant, a fatty acid amide surfactant, a C ⁇ 0 -C 20 ammonia amide, a monoethanolamide, a diethanolamide, an isopropanolamide, and a mixture thereof.
  • nonionic surfactants are known in the art, and are commercially-available.
  • a particularly preferred nonionic surfactant useful herein is a C 1 0-C1 2 alkyl polyglycoside from Cognis Corp.
  • alkylpolyglycosides have the formula: R 2 O(C n H 2n O) t (glycosyl) x , wherein R 2 is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7.
  • the glycosyl is preferably derived from glucose.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position).
  • the additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2- position.
  • Fatty acid amide surfactants include those having the formula: O fi l l 7 R 6 CN(R 7 ) 2 wherein R 6 is an alkyl group containing from about 10 to about 21 (preferably from about 10 to about 17) carbon atoms and each R 7 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C ⁇ -C hydroxyalkyl, and -(C 2 H 4 O) x H where x varies from about 1 to about 3.
  • Preferred amides are C 1 o-C 20 ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.
  • composition herein may comprise up to about 20%, preferably from about 2% to about 10%, of a polyhydroxy fatty acid amide surfactant.
  • the polyhydroxy fatty acid amide surfactant component is typically of the formula: O R 2 CNZ A' wherein R 1 is H, C ⁇ -C 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C 1 -C 4 alkyl, more preferably Cj or C 2 alkyl, even more preferably Cj alkyl (i.e., methyl); and R 2 is a C 5 -C 3 ⁇ hydrocarbyl, preferably straight chain C 7 -Cj 9 alkyl or alkenyl, more preferably straight chain C -C ⁇ alkyl or alkenyl, even more preferably straight chain Cn-C 15 alkyl or alkenyl, or a mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl
  • R 2 -C(O)-N ⁇ is preferably selected from cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, and a mixture thereof.
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z will be a glycityl.
  • Suitable 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.
  • Z preferably will be selected from the group consisting of -CH 2 -(CHOH) n -CH 2 OH, -CH(CH 2 OH)-(CHOH) ⁇ .,-CH 2 OH, -CH 2 - (CHOH) 2 (CHOR ' )(CHOH)-CH 2 OH, and alkoxylated derivatives thereof, where n is an integer from 3 to 5, inclusive, and R is H or a cyclic or aliphatic monosaccharide. Even more preferred are glycityls wherein n is 4, particularly -CH 2 -(CHOH) 4 -CH 2 OH.
  • the solvent useful herein is typically selected from the group consisting of water, an alcohol, a glycol, an ether, an ether alcohol, a carbitol, and a mixture thereof, more preferably the group consisting of water, a C1. 20 glycol, ethanol, a glycol ether including aryl, alkyl, branched, non-branched variants thereof and a mixture thereof, even more preferably the group consisting of propylene carbonate, propylene glycol, tripropyleneglycol n-propyl ether, diethylene glycol n-butyl ether, water, and a mixture thereof. To maintain an appropriate flash point in the final composition, higher flash point solvents are preferred, either alone or in combination with other solvents herein.
  • the solvent herein preferably has a solubility in water of at least about 12%, more preferably of at least about 50%, by weight of the solution.
  • the solvent is typically present at a level of from about 10% to about 70%, preferably from about 15% to about 60%, and more preferably from about 18% to about 55% by weight of the composition.
  • the balance of the composition contains adjunct detergent ingredients, such as, for example, a low water-soluble oil, a viscosity modifier, a thickener, an enzyme, an antioxidant, a free radical inhibitor, an alkalinity source, a perfume, a dye, a reducing or oxidizing bleach, an odor-control agent such as cyclodextrin, and a mixture thereof, preferably a low water-soluble oil, a thickener, an enzyme, an antioxidant, a free radical inhibitor, and a mixture thereof.
  • adjunct detergent ingredients such as, for example, a low water-soluble oil, a viscosity modifier, a thickener, an enzyme, an antioxidant, a free radical inhibitor, an alkalinity source, a perfume, a dye, a reducing or oxidizing bleach, an odor-control agent such as cyclodextrin, and a mixture thereof.
  • a low water-soluble oil such as, for example, a low water-soluble oil, a viscosity modifier,
  • a low water-soluble oil is typically present at a level of from about 0.25% to about 50%, preferably from about 0.3% to about 45%, and more preferably from about 0.5% to about 35%, by weight of the composition.
  • the low water-soluble oil useful herein has a solubility in water of less than about 5,000 ppm, preferably from about 0 part per million (ppm) to about 1,500 ppm, by weight of the solution, and more preferably from about 1 part per trillion to about 100 ppm.
  • Preferred low water-soluble oils useful herein include terpenes, isoparaffins, other oils having the above solubility, and a mixture thereof.
  • Highly preferred low water-soluble oils useful herein include limonene (CAS # 138-86-3; 13.8 ppm [Massaldi, H. A.; King, C. J.; Simple Technique to Determine Solubilities of Sparingly Soluble Organics- Solubility and Activity Coefficients of D- Limonene, n-Butyl benzene and n-Hexyl Acetate in Water and Sucrose Solutions.; J. Chem. Eng Data; 18(4): 393-397; 1973]), methyl oleate (CAS # 112-62-9; 0.00184 ppm (Krop, H.
  • Limonene (aka, dipentene; p-mentha-1,8 diene) is especially preferred for use herein, and may be purchased from a variety of chemical suppliers, for example, Sigma- Aldrich Corp., St. Louis, Missouri, USA. Without intending to be limited by theory, it is believed that a composition containing d-limonene provides significantly faster speed of oil absorption as well as a significantly higher overall capacity for oil absorption, as compared to isoparaffins and other low-water-soluble oils. In addition, the d-limonene form is easily biodegradable and therefore is highly desirable from an environmental and regulatory standpoint.
  • Terpineol (aka, l-Methyl-4-isopropyl-l-cyclohexen-8-ol) is also especially preferred for use herein, and may be purchased from a variety of chemical suppliers, for example, Sigma-Aldrich Corp., St. Louis, Missouri, USA. Without intending to be limited by theory, it is believed that a composition containing terpineol also provides significantly faster speed of oil absorption as well as a significantly higher overall capacity for oil absorption, as compared to isoparaffins and other low- water-soluble oils.
  • the composition herein contains the combination of a glycol ether and a low water-soluble oil, wherein the weight ratio of glycol ether to low water-soluble oil is from about 20:1 to about 1:20, preferably from about 15:1 to about 1:15, and more preferably from about 10:1 to about 1:10.
  • the glycol ether is selected from the group consisting of C 2 . 6 alkyl glycol ether, aryl C 2 - 6 alkyl glycol ether, and a mixture thereof, more preferably phenyl ethylene glycol ether, phenyl propylene glycol ether, and a mixture thereof.
  • the composition contains from about 1% to about 20%, preferably from about 2% to about 16% of a viscosity modifier.
  • the viscosity modifier useful herein is selected from the group consisting of a hydrotrope, naphthalene, and a mixture thereof.
  • Hydrotrope generally means a compound with the ability to increase the solubilities, preferably aqueous solubilities, of certain slightly soluble organic compounds.
  • the hydrotrope herein has a carbon chain length of less than 10 carbon atoms in the longest alkyl chain and/or alkaryl group.
  • hydrotrope has such a short alkyl/alkaryl chain length, it is typically considered separate from the class of surfactants, as such a short alkyl/alkaryl chain does not provide sufficient hydrophobicity to sufficiently draw hydrophobic soils into solution.
  • a short chain length is appropriate to provide hydrotrophic effects which may significantly reduce viscosity. It is believed that surfactant aggregates in the surfactant phase are what result in the high viscosity of compositions having high surfactant levels. Thus, for mixed surfactant systems, it is extremely difficult to predict the complex surfactant interactions of a surfactant system when multiple surfactants are employed therein.
  • viscosity modifiers achieve a viscosity reduction by inserting themselves into the surfactant phase and solubilizing the surfactant aggregates into the solvent. While it is known to reduce viscosity via adding ethanol, the present invention has recognized that such an approach in and of itself is insufficient and less preferred than adding a viscosity modifier, as shown by the correspondingly reduced flash point when ethanol alone is added.
  • Preferred hydrotropes herein include the alkyl aryl sulphonates or alkyl aryl sulfonic acids.
  • Preferred alkyl aryl sulphonates include: sodium, potassium, calcium and ammonium xylene sulphonates; sodium, potassium, calcium and ammonium toluene sulphonates; sodium, potassium, calcium and ammonium cumene sulphonates; sodium, potassium, calcium and ammonium substituted or unsubstituted naphthalene sulphonates; and mixtures thereof.
  • Preferred alkyl aryl sulfonic acids include xylene sulfonic acid, toluene sulfonic acid, cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid and mixtures thereof.
  • a thickener known in the art is also present, preferably selected from a xanthan gum, laponite, a fumed silica, a polyvinyl alcohol, a polyacrylic acid, a polyvinyl pyrrolidone, a cellulose, a modified cellulose, a guar gum, a gum arabic and a mixture thereof, preferably a xanthan gum with a molecular weight of approximately 10 6 .
  • Derivatives of xanthan gum can be used provided they retain the anionic side chains and, preferably, hydroxyl groups.
  • a thickener is typically present at from about 0.1% to about 5%, by weight to adjust the composition to the desired viscosity.
  • Thickeners useful herein are found in, for example, US Patent No. 4,648,987 to Smith and Munk, issued on March 10, 1987; and US Patent No. 5,106,609 to Bolich, et al., issued on May 12, 1992.
  • Other thickeners useful herein include those described as "water-soluble thickening polymers" in U.S. Patent Application Serial No. 10/705567, filed on Nov. 10, 2003, to Castro, et al. (P&G Ref. No CM2691M).
  • an enzyme is also present.
  • the enzyme useful herein includes a cellulase, a hemicellulase, a peroxidase, a protease, a gluco-amylase, an amylase, a lipase, a cutinase, a pectinase, a xylanase, a reductase, an oxidase, a phenoloxidase, a lipoxygenase, a ligninase, a pullulanase, a tannase, a pentosanase, a malanase, a ⁇ -glucanase, an arabinosidase and a mixture thereof.
  • a preferred combination is a detergent composition having a cocktail of conventional applicable enzymes such as protease, amylase, lipase, cutinase and/or cellulase.
  • An enzyme is typically present at from about 0.0001% to about 5% of active enzyme, by weight.
  • Preferred proteolytic enzymes are selected from the group consisting of ALCALASE ® (Novo Industri A/S), BPN', Protease A and Protease B (Genencor), and mixtures thereof.
  • Protease B is more preferred.
  • Preferred amylase enzymes include TERMAMYL®>
  • antioxidants and free radical inhibitors such as BHT (2,6-Di-t-butyl-4-methylphenol), and others known in the art, are included to limit oxidation of active ingredients.
  • BHT 2,6-Di-t-butyl-4-methylphenol
  • compositions herein may be formed by methods known in the art, such as simple stirring and mixing in a standard tank or mixer. Alternatively, premelting and emulsification techniques known in the art may also be employed for specific formulations, as desired. Method of Use
  • the composition herein is particularly suited for use as a cleaning composition, more preferably as a dishwashing composition, and even more preferably as a hand dishwashing composition with a foam-generating dispenser.
  • the composition may be used at a wide range of temperatures, for example, from 5 °C or lower in the winter, to even above 40 °C in the summer, depending upon the ambient temperature during use.
  • the invention herein is especially useful in the direct-application context where the composition is applied via a foam-generating dispenser to a substrate such as a sponge, a wiping substrate, a scrubbing substrate, a nonwovern material, etc.
  • a substrate such as a sponge, a wiping substrate, a scrubbing substrate, a nonwovern material, etc.
  • Water is usually then added to the substrate to dilute the composition, preferably in or on the substrate itself.
  • the ME is then applied directly or indirectly to a surface to be cleaned, such as a dish, a glass, flatware, etc., and preferably soaked for from about 2 seconds to about 1 hour.
  • the composition may be applied from the dispenser directly onto an item to be cleaned, such as a pan or other hard surface.
  • the surface is then usually rinsed to remove the dirt, soil, and composition and then preferably, dried.
  • Such a method effectively cleans not only dishes, glasses, and flatware, but may also clean kitchen countertops, tile, bathrooms, hardwood floors, and other hard surfaces.
  • other methods of use are also useful, such as forming a wash bath by diluting the composition in, for example, a sink or wash basin, contacting the surface to be cleaned with the wash bath, preferably soaked for from about 2 seconds to about 1 hour, and then rinsed to remove the dirt, soil, and composition.
  • Foam-generating dispensing containers are known in the art, and will typically comprise a hand-held bottle having an aesthetically desirable and/or ergonomic shape, and a dispensing spout, or nozzle through which the composition is passed, emerging as a foam.
  • Preferred foam-generating dispensers useful herein include: T8900, OpAd FO, 8203, and 7512 series foamers from Afa-Polytek, Helmond, The Netherlands; Tl, F2, and WR-F3 series foamers from Airspray International, Inc., Alkmaar, The Netherlands or North Pompano Beach, Florida, U.S.A.; TS-800 and Mixor series foamers from Saint- Gobain Calmar, Inc., City of Industry, California, U.S.A.; pump foamers and squeeze foamers from Daiwa Can Company, Tokyo, Japan; TS1 and TS2 series foamers from Guala Dispensing USA, Inc., Hillsborough, New Jersey, U.S.A.; and YT-87L-FP, YT- 87L-FX, and YT-97 series foamers from Yoshino Kogyosho Co., Ltd., Tokyo, Japan.
  • foam-generating dispensers discussed in the Japanese-language publications Food & Package, (2001) vol. 42, no. 10, pp 609-13; Food & Package. (2001) vol. 42, no. 11, pp 676-79; and Food & Package. (2001) vol. 42, no. 12, pp 732-35.
  • Variations and modifications of existing foam-generating dispensers are especially useful herein, especially by modifying air pisto product piston volume ratio, mesh/net sizes, impinging angle, etc., as well as optimization of the sizes and dimensions of the cylinder, rod, dip tube, nozzle, etc.
  • Test Methods The viscosity herein is measured on a Brookfield viscometer model # LVDNII+ at 5 °C and at 20 °C.
  • a temperature-controlled water jacket is employed around the test sample to maintain a constant temperature during the viscosity measurements.
  • the spindle used for these measurements is a S31 spindle with the appropriate speed to measure products of different viscosities; e.g., 12 rpm to measure products of viscosity greater than 1 Pa*s; 30 rpm to measure products with viscosities between 0.5 Pa*s - 1 Pa*s; 60 rpm to measure products with viscosities less than 0.5 Pa*s.
  • the viscosity of the sample is measured three times and the viscosity for the given temperature is calculated as the average of these three measurements.
  • the invention herein typically has an viscosity at 5 °C of less than about 0.15 Pa*s, preferably from about 0.15 Pa*s to about 0.0001 Pa*s, more preferably at least about 0.001 Pa*s to about 0.1 Pa*s, even more preferably from about 0.005 Pa*s to about 0.08 Pa*s, and still even more preferably from about 0.01 Pa*s to about 0.06 Pa*s.
  • the viscosity is then plotted vs.
  • viscosity-temperature slope (5 °C viscosity - 20 °C viscosity)/(5 °C - 20 °C).
  • the viscosity-temperature slope for the compositions herein is more than about -0.008 Pa*s/°C, preferably form about -0.008 Pa*s/°C to about 0 Pa*s/°C, more preferably from about -0.006 Pa*s/°C to about 0 Pa*s/°C, and even more preferably from about -0.004 Pa*s/°C to about 0 Pa*s/°C.
  • the liquid composition herein may have a Newtonian or non-Newtonian behavior. However, as long as the viscosity and temperature profiles are as described herein, even non-Newtonian liquids fall within the invention herein.
  • the flash point of the test sample is defined as the lowest temperature at which a liquid gives off vapor within a test vessel in sufficient concentration to form an ignitable mixture with air near the surface of the liquid.
  • the lower the flash point the easier it is to ignite the material, while the higher the flash point, the more difficult it is to ignite the material.
  • the flash point is measured using the ASTM D93-02a Pensky-Martens Closed Tester (closed cup) flashpoint method. While the D93-02a method is only specifically intended for 40-360 °C, the methodology is also used to measure lower temperature flash points. However, no noticeable datapoint deviations have been observed at temperatures below 40 °C, and reproducibility is comparable to that of temperatures above 40 °C.
  • the flash point for the compositions herein is at least about 40 °C, more preferably at least about 43 °C, and has no upper limit, as anything above these ranges is considered very safe. However, it is recognized that for practical purposes, the flash point will typically be less than about 500 °C, and preferably less than about 350 °C. Without intending to be limited by theory, it is believed that the use of a balance of a solvent and low-water soluble oil is especially useful in order to provide the desired balance between viscosity-temperature slope and the flash point.
  • Composition D prior to the dilution with 4% ethanol, contained approximately 15% sodium C 12 _ ⁇ 3 alkyl ethoxy 2 .o sulfate, 4.6% amine oxide, 12.4% C ⁇ 0 . ⁇ 2 alkyl polyglycoside, 1.6% sodium toluene sulfonate, 6.3% ethanol, 0.3% phosphoric acid, 0.3% limonene, 0.1% citric acid, and the balance water and minor ingredients.
  • the Composition A representing the invention possesses both an acceptable viscosity- temperature slope and an acceptable flash point, whereas the currently marketed commercial products (Compositions C and D) do not.
  • compositions C and D had to be diluted in order to reach a desired viscosity of less than 0.1 Pa*s. Furthermore, even when diluted, the viscosity-temperature slope of Composition C was unacceptable, whereas the flash point of Composition D was unacceptable.
  • EXAMPLE 2 A liquid detergent composition similar to composition A in Example 1 was prepared, except that it contained 7% terpineol and 3% propyleneglycol phenyl ether. The viscosity was about 0.045 Pa*s at 20 °C and about 0.11 Pa*s at 5 °C, providing an acceptable viscosity-temperature slope of about -.0043 Pa*s/°C. The flash point was about 48 °C.

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FR2867196A1 (fr) 2005-09-09
WO2005078063A3 (en) 2008-01-17
AR047608A1 (es) 2006-01-25
EP1761625A2 (en) 2007-03-14
JP2006521417A (ja) 2006-09-21
US20050192196A1 (en) 2005-09-01

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