[go: up one dir, main page]

WO1996012000A1 - Detergent compositions containing amines and anionic surfactants - Google Patents

Detergent compositions containing amines and anionic surfactants Download PDF

Info

Publication number
WO1996012000A1
WO1996012000A1 PCT/US1994/011779 US9411779W WO9612000A1 WO 1996012000 A1 WO1996012000 A1 WO 1996012000A1 US 9411779 W US9411779 W US 9411779W WO 9612000 A1 WO9612000 A1 WO 9612000A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
detergent composition
amines
liquid detergent
amine
Prior art date
Application number
PCT/US1994/011779
Other languages
French (fr)
Inventor
Joseph Paul Morelli
Dimitris Lappas
Sherri Lynn Randall
Rajan Keshav Panandiker
Jean-Pol Boutique
Chris Efstathios Housmekerides
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU12881/95A priority Critical patent/AU1288195A/en
Priority to PCT/US1994/011779 priority patent/WO1996012000A1/en
Priority to EP95904050A priority patent/EP0785978A1/en
Priority to HU9801065A priority patent/HU215939B/en
Priority to US08/817,152 priority patent/US5981466A/en
Priority to CZ971110A priority patent/CZ111097A3/en
Priority to CA002202506A priority patent/CA2202506C/en
Priority to BR9408622A priority patent/BR9408622A/en
Priority to JP51317696A priority patent/JP4063866B2/en
Priority to PCT/US1995/007824 priority patent/WO1997000929A1/en
Priority to EP95924620A priority patent/EP0833884A1/en
Priority to CN95196637.5A priority patent/CN1168691A/en
Priority to JP8513248A priority patent/JPH10509468A/en
Priority to HU9901140A priority patent/HUT78084A/en
Priority to DE69526360T priority patent/DE69526360T2/en
Priority to AU36869/95A priority patent/AU3686995A/en
Priority to CZ971109A priority patent/CZ110997A3/en
Priority to BR9509349A priority patent/BR9509349A/en
Priority to AT95934562T priority patent/ATE215984T1/en
Priority to PCT/US1995/012469 priority patent/WO1996012004A1/en
Priority to EP95934562A priority patent/EP0785981B1/en
Priority to US08/817,154 priority patent/US5935271A/en
Priority to CA002202505A priority patent/CA2202505C/en
Priority to TR95/01261A priority patent/TR199501261A2/en
Priority to TR95/01262A priority patent/TR199501262A2/en
Publication of WO1996012000A1 publication Critical patent/WO1996012000A1/en
Priority to MXPA/A/1997/002728A priority patent/MXPA97002728A/en

Links

Classifications

    • 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D1/65—Mixtures of anionic with cationic compounds
    • 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
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
    • 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
    • C11D3/0026—Low foaming or foam regulating compositions
    • 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • 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
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/40—Monoamines or polyamines; Salts thereof
    • 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
    • C11D1/42—Amino alcohols or amino ethers
    • 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
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • 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
    • 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
    • C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated
    • 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
    • C11D1/528—Carboxylic amides (R1-CO-NR2R3), where at least one of the chains R1, R2 or R3 is interrupted by a functional group, e.g. a -NH-, -NR-, -CO-, or -CON- group
    • 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

Definitions

  • the present invention relates to detergent compositions containing surfactants selected from amines. More particularly, the invention is directed to detergent compositions containing anionic surfactants selected from the group consisting of alkyl al oxylated sulfates and alkyl sulfates, said composition further containing specific primary and/or tertiary amines.
  • Detergent compositions useful for cleaning purposes, such as laundering of fabrics, have commonly utilized a variety of surfactants.
  • a surfactant system comprising anionic surfactants selected from the group consisting of alkyl alkoxylated sulfates and alkyl sulfates, said surfactant system further comprising a cosurfactant selected from the group of primary or tertiary amines.
  • Liquid detergent compositions formulated with said surfactant system are extremely useful when the liquid detergent compositions are in direct contact with the fabrics such as during pretreatment.
  • EP 160 762, EP 137 615 and EP 137 616 disclose liquid detergents which comprise cyclohexylamine.
  • EP 177 165 discloses detergent compositions which comprise anionics, cellulase and a variety of primary, secondary, tertiary and quaternary amines.
  • EP 11 340 discloses soften through the wash detergent compositions which comprise tertiary amines and clay.
  • DE 32 07 487, GB 2 094 826, GB 2 095 275 and EP 137 397 disclose compositions which comprise anionics and quaternary amines.
  • EP 120 528 discloses compositions comprising anionics, as well as tertiary amines.
  • EP 26 528 and EP 26 529 disclose compositions comprising anionics and quaternary amines.
  • Detergent compositions containing 1) primary or tertiary amines of the type useful herein in combination with 2) oleoyl sarcosinate are disclosed in U.S. Patent Application Serial No. 08/252,127, filed June 1, 1994.
  • Compositions of this invention may or may not contain oleoyl sarcosinate surfactants.
  • the detergent compositions according to the present invention comprise anionic surfactants selected from the group of alkyl alkoxy sulfates and alkyl sulfates, characterized in that said detergent composition further comprises specific primary and/or a tertiary amines.
  • the detergent compositions preferably comprise at least 5%, more preferably from 10% to 65% and most preferably from 15% to 40% by weight of the surfactant system as described hereinabove.
  • the weight ratio of the amine cosurfactant to the alkyl alkoxylated sulfates and alkyl sulfates is from 1:1 to 1:250, more preferably from 1:5 to 1:100 and most preferably from 1:10 to 1:40.
  • the detergent compositions according to the present invention comprise anionic surfactants selected from the group of alkylalkoxy sulfates and alkyl sulfates. Alkyl alkoxylated sulfates and/or alkyl sulfates
  • the alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m S03M wherein R is an unsubstituted CIQ ⁇ C 24 alkyl or hydroxyalkyl group having a c 10" c 24 alkyl component, preferably a 12- 18 alkyl or hydroxyalkyl, more preferably C12-C15 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted- ammonium cation.
  • R is an unsubstituted CIQ ⁇ C 24 alkyl or hydroxyalkyl group having a c 10" c 24 alkyl component, preferably a 12- 18 alky
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include ethanol-, triethanol-, methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and those derived from alkyla ines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are Ci2 ⁇ C15 alkyl polyethoxylate (1.0) sulfate (C12-C15E(1.0)M) , Ci2 _ C 15 alkyl polyethoxylate (2.25) sulfate (C 12 -C!5E(2.25)M) , c 12 _c 15 alkyl polyethoxylate (3.0) sulfate (C12-C15E(3.0)M) , and i2 ⁇ c 15 alkyl polyethoxylate (4.0) sulfate ( ⁇ 2 ⁇ Ci5E(4.0)M), wherein M is conveniently selected from sodium and potassium.
  • the alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C ⁇ Q- C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a c 10" c 18 alkyl component, more preferably a C12-C15 alkyl or hydroxyalkyl, 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.
  • R preferably is a C ⁇ Q- C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a c 10" c 18 alkyl component, more preferably a C12-C15 alkyl or hydroxyalkyl
  • M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substitute
  • methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like) .
  • alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
  • ami-nes refer to primary or tertiary amines which is believed to form a mixed micelle with the anionic surfactant and where the carbon chain length of the alkyl group is equal or greater than Cg.
  • Suitable primary amines for use herein include amines according to the formula R ⁇ R2 R 3 N wherein R ⁇ and R2 are both H, R3 is a C4-C18, preferably Cg-C] ⁇ alkyl chain, R3 alkyl chains may be straight or branched and may be interrupted with up to 12 ethylene oxide moieties, most preferably interrupted with up to 5 ethylene oxide moieties.
  • Preferred amines according to the formula herein above are n-alkyl amines.
  • Suitable amines for use herein may be selected from 1-hexylamine, 1- octylamine, laurylamine, palmitylamine, stearylamine, oleylamine, coconutalkylamine, tallowalkylamine.
  • R1R2R3N amines according to the formula R1R2R3N wherein Ri and R2 are both H ;
  • R3 is R4X(CH 2 )n' x is -0-,-C(0)NH- or -NH- /
  • R4 is a C4-C1.8, preferably Cg-Ci2 alkyl chain and R4 may be branched or straight, n is between 1 to 5.
  • Preferred amines according to the formula herein above 3-isopropoxypropylamine, 3-(2- methoxyethoxy)-propylamine and 2-(2-aminoethoxy)-ethanol, Cg- octyl oxy propylamine, 2-ethylhexyloxypropylamine, lauryl amido propylamine and coco amido propylamine.
  • Suitable tertiary amines for use herein include amines tertiary amines having the formula R1R2R3N wherein neither R ⁇ nor R2 is H, RI and R2 are C ⁇ Cg alkylchains or
  • n is between 2 to 4 and x is between 1 to 6;
  • R3 is either a C4-C ⁇ s, preferably Cg-C] ⁇ alkyl chain, or R3 is
  • R X(CH 2) n' whereby X is -0-, -C(0)NH- or -NH- R 4 is a C4-C 18 , n is between 1 to 5, and R5 is H or C1-C2 alkyl.
  • R3, R4 are preferably Cg-Ci2 alkyl chains and may be straight or branched ; R3 alkyl chains may be interrupted with up to 12 ethylene oxide moieties, most preferably interrupted with up to 5 ethylene oxide moieties.
  • Suitable tertiary amines for use herein include coconutalkyldimethylamine, dimethyloleylamine, hexadecyltris (ethyleneoxy)dimethylamine,tallowalkylbis(2- hydroxyethy1)amine, stearoylbis (2-hydroxyethyl)amine and oleoylbis (2-hydroxyethyl) amine.
  • the preferred materials are the trialkyl amines marketed under the tradename ADOGEN, the long chain alkyldimethyl amines marketed under the tradename ARMEEN and the ethoxylated amines marketed under the tradename ETHOMEEN.
  • the most preferred amines for use in the compositions herein are 1-hexylamine, 1-octylamine, 1- decylamine, 1-dodecylamine.
  • n-dodecyldimethylamine ARMEEN DM12D
  • ETHOMEEN C/12, BEROL 307 bishydroxyethylcoconutalkylamine
  • oleylamine 7 times ethoxylated BEROL 28
  • lauryl amido propylamine and coco amido propylamine.
  • amine cosurfactant and anionic surfactant herein form complexes which enhance packing of the surfactants at the oil/water interface, thereby lowering interfacial tension and improving detergency.
  • the amine surfactants would be at least partially protonated in the product and during the wash thus can form positively charged species capable of complexing with the anionic surfactant.
  • Another aspect of the invention relates to the surprising finding that low amounts of certain primary and/or tertiary amines of the present invention provide suds control to the detergent compositions formulated therewith.
  • the amounts in which the amines are used for controlling the suds are from 0.1 to 10%, preferably from 0.1 to 5%, most preferably from 0.5 to 4% by weight of the detergent composition.
  • Detergent ingredients preferably from 0.1 to 10%, preferably from 0.1 to 5%, most preferably from 0.5 to 4% by weight of the detergent composition.
  • a liquid detergent composition comprising the surfactant system of the present invention mixed with detergent ingredients.
  • a wide range of surfactants can be used in the detergent composition of the present invention.
  • the detergent compositions according to the present invention will preferably comprise a surfactant system which is substantially free of linear alkylbenzene sulfonate surfactant.
  • alkyl ester sulfonate surfactants including linear esters of c 8 ⁇ c 20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329.
  • Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
  • alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula :
  • R 3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof
  • R 4 is a C ⁇ -Cg hydrocarbyl, preferably an alkyl, or combination thereof
  • M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
  • Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine.
  • R 3 is Cio-Cig alkyl
  • R 4 is methyl, ethyl or isopropyl.
  • methyl ester sulfonates wherein R 3 is C ⁇ o -c 16 alkyl.
  • anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, c 8 ⁇ c 22 primary of secondary alkanesulfonates, C ⁇ ⁇ c 24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide) ; alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated Ci2 ⁇ c 18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated Cg-Ci2 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolysaccharides such as the s
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch) . A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference) .
  • the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 5% to about 25% by weight of such anionic surfactants.
  • One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic- lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 14, more preferably from 12 to 14.
  • HLB hydrophilic- lipophilic balance
  • the hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Especially preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C ⁇ .2" C 5 primary alcohols containing 5-8 moles of ethylene oxide per mole of alcohol.
  • Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula
  • Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
  • nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula
  • R 2 - C(O) - NtR 1 ) - Z wherein R 1 is H, or R 1 is C ⁇ _4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R 2 is C5-.31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R 1 is methyl
  • R 2 is a straight C ⁇ _i5 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • compositions of the present invention may comprise amine oxide in accordance with the general formula I:
  • R' is preferably selected from hydrogen, methyl and -CH2OH.
  • R 1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R is a primary alkyl moiety.
  • R is a hydrocarbyl moiety having chainlength of from about 8 to about 18.
  • R may be somewhat longer, having a chainlength in the range c 12 ⁇ c 24-
  • amine oxides are illustrated by C12-14 alkyldimethyl amine oxide,hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates, especially the dihydrates as disclosed in U.S. Patents 5,075,501 and
  • the invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy.
  • amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
  • Highly preferred amine oxides herein are solids at ambient temperature, more preferably they have melting-points in the range 30°C to 90°C.
  • Amine oxides suitable for use herein are - made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
  • Preferred commercially available amine oxides are the solid, dihydrate ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 from Ethyl Corp.
  • Preferred embodiments include hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris(ethyleneoxy)dimethyl-amine oxide, and tetradecyldimethylamine oxide dihydrate.
  • R 1 H
  • R' CH OH
  • hexadecylbis(2- hydroxyethyl)amine oxide tallowbis(2- hydroxyethyl)amine oxide
  • stearylbis(2-hydroxyethyl)amine oxide oleylbis(2- hydroxyethyl)amine oxide.
  • the laundry detergent compositions of the present invention typically comprise nonionic surfactants in the weight ratio of anionic surfactant to nonionic surfactant from 6:1 to 1:3, preferably from 5:1 to 2:1.
  • Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-chain hydrocarbyl group.
  • cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula :
  • R 2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain
  • each R 3 is selected from the group consisting of -CH2CH2-, -CH2CH(CH3>-, -CH2CH(CH2 ⁇ H)-, -CH2CH2CH2-, and mixtures thereof
  • each R 4 is selected from the group consisting of C 1 -C alkyl, C1-C hydroxyalkyl-, benzyl ring structures formed by joining the two R 4 groups, -CH 2 CHOH-CHOHCOR 6 CHOHCH 2 OH wherein R 6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0
  • R 5 is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms of R 2 plus R 5 is not more than about 18
  • each y is from 0 to about 10 and the sum of the
  • Preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula :
  • R ⁇ is Cg-Cig alkyl
  • each of R2, R3 and R4 is independently C1-C alkyl, C1-C hydroxy alkyl, benzyl, and - (C2H4 ⁇ ) x H where x has a value from 1 to 5, and X is an anion.
  • R2, R3 or R4 should be benzyl.
  • the preferred alkyl chain length for R ⁇ is Ci2 ⁇ i5 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis.
  • Preferred groups for R2 R 3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
  • quaternary ammonium compounds of formulae (i) for use herein are : coconut trimethyl ammonium chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide;
  • O-C(O)-C12--14 alkyl and R2R3R4 are methyl).
  • the laundry detergent compositions of the present invention typically comprise from 0.5% to about 5%, preferably from about 1% to about 3% by weight of such cationic surfactants.
  • compositions according to the present invention may further comprise a builder system.
  • a builder system Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
  • phosphate builders can also be used herein.
  • Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R- CH(COOH)CH2 (COOH) wherein R is C10-20 alkyl or alkenyl, preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents.
  • Specific examples include lauryl succinate , myristyl succinate, palmityl succinate 2-dodecenylsuccinate, 2-tetradecenyl succinate.
  • Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
  • polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
  • suitable fatty acid builders for use herein are saturated or unsaturated C10- 18 fatty acids, as well as the corresponding soaps.
  • Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
  • the preferred unsaturated fatty acid is oleic acid.
  • Other preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.
  • Detergency builder salts are normally included in amounts of from 3% to 50% by weight of the composition preferably from 5% to 30% and most usually from 5% to 25% by weight.
  • detergent compositions may be employed, such as enzymes and stabilizers therefore, soil- suspending agents, soil-release polymers, abrasives, bactericides, tarnish inhibitors, coloring agents, foam control agents, corrosion inhibitors and perfumes.
  • enzymes and stabilizers therefore, soil- suspending agents, soil-release polymers, abrasives, bactericides, tarnish inhibitors, coloring agents, foam control agents, corrosion inhibitors and perfumes.
  • the liquid compositions according to the present invention are in "concentrated form"; in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents.
  • the level of water is less than 50%, preferably less than 30%, more preferably less than 20% of water by weight of the detergent compositons.
  • Said concentrated products provide advantages to the consumer, who has a product which can be used in lower amounts and to the producer, who has lower shipping costs.
  • the liquid compositions are especially effective when applied directly to soils and stains in a pretreatment step.
  • the detergent compositions of the present invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.
  • the detergent compositions according to the present invention include compositions which are to be used for cleaning of substrates, such as fabrics,fibers, hard surfaces, skin etc., for example hard surface cleaning compositions(with or without abrasives) , laundry detergent compositions, automatic and non- automatic dishwashing compositions.
  • liquid detergent compositions are made % by weight of the detergent compositions
  • a B C D c 12 ⁇ c 15 Alkyl ethoxylated sulfate 21 11.0 17 16.
  • Octylamine 0.. 1 0. 0.
  • Monoethanolamine 8 8 0.5 9 Sodiumhydroxide 1 1 2.5 1 Propanediol 12.7 14.5 13.1 10.
  • Amylase (300KNU/g) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Lipolase (lOOKNU/g) 0.15 0.15 0.15 0.15 0.15 Protease (34g/l) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Endo-A (5000 CEVU/g) 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05
  • compositions (A-D) are found to be very efficient in the removal of greasy/oily soils under various usage conditions while having a controlled suds profile.
  • octylamine was replaced in Compositions (A-D) by Bis (2-hydroxyethyl) coco amine, Oleyl amine 7EO, lauryl amido propylamine and coco amido propylamine.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

A liquid detergent composition comprising anionic surfactants selected from the group of alkyl alkoxy sulfates and alkyl sulfates, characterized in that said detergent composition further comprises an amine selected from i) primary amines having the formula: R1R2R3N, wherein R1 and R2 are both H; and wherein R3 is C4-C18, or R4X(CH2)n, whereby X is -O-, -C(O)NH- or -NH-, R4 is a C6-C18, n is between 1 to 5; ii) tertiary amines having the formula R1R2R3N, wherein neither R1 nor R2 is H, R?1 and R2¿ are C¿1?-C8 alkylchains or (II), whereby n is between 1 to 5 and x is between 1 to 5, R3 is either C4-C18 or R4X(CH2)n, whereby X is -O-, -C(O)NH- or -NH-, R4 is a C6-C18, n is between 1 to 5 and R5 is H or C1-C2 alkyl; and iii) mixtures of said primary and tertiary amines.

Description

DETERGENT COMPOSITIONS CONTAINING AMINES AND ANIONIC SURFACTANTS
Field of the invention
The present invention relates to detergent compositions containing surfactants selected from amines. More particularly, the invention is directed to detergent compositions containing anionic surfactants selected from the group consisting of alkyl al oxylated sulfates and alkyl sulfates, said composition further containing specific primary and/or tertiary amines.
Background of the invention
Detergent compositions useful for cleaning purposes, such as laundering of fabrics, have commonly utilized a variety of surfactants.
The ability of surfactants to clean a large variety of soils and stains from fabrics present in the typical load of laundry is of high importance in the evaluation of detergent performance. Unfortunately, the relative ability of each surfactant to meet various performance criteria is among others depending on the presence of cosurfactants. The recent trend towards partial or total replacement of Linear alkyl- benzene sulfonate surfactants (LAS) has urged the detergent formulators to rebalance their formulations with different surfactants. For example, quaternary ammonium salts are less efficient in boosting the greasy cleaning performance in Nil-LAS formulations.
There is thus a standing desire for performance and flexibility reasons to make available a surfactant system capable of providing optimum detergency performance which is equivalent to that of LAS-containing detergents.
The above objective has been met by a surfactant system comprising anionic surfactants selected from the group consisting of alkyl alkoxylated sulfates and alkyl sulfates, said surfactant system further comprising a cosurfactant selected from the group of primary or tertiary amines.
It has been surprisingly found that detergent compositions containing said surfactant system exhibit detergency performance equivalent to that of LAS-containing detergents .
In addition, it has been found that a small amount of certain primary and tertiary amines according to the present invention constitutes an efficient and compatible sud suppressing system. This additional benefit allows to use the amines in a dual function, e.g. surfactant and suds suppressor, thereby facilitating the formulation of concentrated liquid detergents.
Liquid detergent compositions formulated with said surfactant system are extremely useful when the liquid detergent compositions are in direct contact with the fabrics such as during pretreatment.
Amines have been described in the art in liquid detergent compositions. EP 160 762, EP 137 615 and EP 137 616 disclose liquid detergents which comprise cyclohexylamine. EP 177 165 discloses detergent compositions which comprise anionics, cellulase and a variety of primary, secondary, tertiary and quaternary amines. EP 11 340 discloses soften through the wash detergent compositions which comprise tertiary amines and clay. DE 32 07 487, GB 2 094 826, GB 2 095 275 and EP 137 397 disclose compositions which comprise anionics and quaternary amines. EP 120 528 discloses compositions comprising anionics, as well as tertiary amines. EP 26 528 and EP 26 529 disclose compositions comprising anionics and quaternary amines. Detergent compositions containing 1) primary or tertiary amines of the type useful herein in combination with 2) oleoyl sarcosinate are disclosed in U.S. Patent Application Serial No. 08/252,127, filed June 1, 1994. Compositions of this invention may or may not contain oleoyl sarcosinate surfactants.
Summary of the invention
The detergent compositions according to the present invention comprise anionic surfactants selected from the group of alkyl alkoxy sulfates and alkyl sulfates, characterized in that said detergent composition further comprises specific primary and/or a tertiary amines.
The detergent compositions preferably comprise at least 5%, more preferably from 10% to 65% and most preferably from 15% to 40% by weight of the surfactant system as described hereinabove.
Preferably, the weight ratio of the amine cosurfactant to the alkyl alkoxylated sulfates and alkyl sulfates is from 1:1 to 1:250, more preferably from 1:5 to 1:100 and most preferably from 1:10 to 1:40.
Detailed description of the Invention
The detergent compositions according to the present invention comprise anionic surfactants selected from the group of alkylalkoxy sulfates and alkyl sulfates. Alkyl alkoxylated sulfates and/or alkyl sulfates
The alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)mS03M wherein R is an unsubstituted CIQ~C24 alkyl or hydroxyalkyl group having a c10"c24 alkyl component, preferably a 12- 18 alkyl or hydroxyalkyl, more preferably C12-C15 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted- ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include ethanol-, triethanol-, methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and those derived from alkyla ines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary surfactants are Ci2~ C15 alkyl polyethoxylate (1.0) sulfate (C12-C15E(1.0)M) , Ci2_ C15 alkyl polyethoxylate (2.25) sulfate (C12-C!5E(2.25)M) , c12_c15 alkyl polyethoxylate (3.0) sulfate (C12-C15E(3.0)M) , and i2~c15 alkyl polyethoxylate (4.0) sulfate ( χ2~ Ci5E(4.0)M), wherein M is conveniently selected from sodium and potassium.
The alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C^Q- C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a c10"c18 alkyl component, more preferably a C12-C15 alkyl or hydroxyalkyl, 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 piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like) . The amine
The ami-nes as used herein refer to primary or tertiary amines which is believed to form a mixed micelle with the anionic surfactant and where the carbon chain length of the alkyl group is equal or greater than Cg.
Suitable primary amines for use herein include amines according to the formula R^R2R3N wherein R^ and R2 are both H, R3 is a C4-C18, preferably Cg-C]^ alkyl chain, R3 alkyl chains may be straight or branched and may be interrupted with up to 12 ethylene oxide moieties, most preferably interrupted with up to 5 ethylene oxide moieties. Preferred amines according to the formula herein above are n-alkyl amines. Suitable amines for use herein may be selected from 1-hexylamine, 1- octylamine, laurylamine, palmitylamine, stearylamine, oleylamine, coconutalkylamine, tallowalkylamine.
Other suitable primary amines include amines according to the formula R1R2R3N wherein Ri and R2 are both H ; R3 is R4X(CH2)n' x is -0-,-C(0)NH- or -NH-/ R4 is a C4-C1.8, preferably Cg-Ci2 alkyl chain and R4 may be branched or straight, n is between 1 to 5. Preferred amines according to the formula herein above 3-isopropoxypropylamine, 3-(2- methoxyethoxy)-propylamine and 2-(2-aminoethoxy)-ethanol, Cg- octyl oxy propylamine, 2-ethylhexyloxypropylamine, lauryl amido propylamine and coco amido propylamine.
Suitable tertiary amines for use herein include amines tertiary amines having the formula R1R2R3N wherein neither R^ nor R2 is H, RI and R2 are Cι~Cg alkylchains or
Figure imgf000007_0001
whereby n is between 2 to 4 and x is between 1 to 6;
R3 is either a C4-Cιs, preferably Cg-C]^ alkyl chain, or R3 is
R X(CH2)n' whereby X is -0-, -C(0)NH- or -NH- R4 is a C4-C18, n is between 1 to 5, and R5 is H or C1-C2 alkyl.
R3, R4 are preferably Cg-Ci2 alkyl chains and may be straight or branched ; R3 alkyl chains may be interrupted with up to 12 ethylene oxide moieties, most preferably interrupted with up to 5 ethylene oxide moieties. Suitable tertiary amines for use herein include coconutalkyldimethylamine, dimethyloleylamine, hexadecyltris (ethyleneoxy)dimethylamine,tallowalkylbis(2- hydroxyethy1)amine, stearoylbis (2-hydroxyethyl)amine and oleoylbis (2-hydroxyethyl) amine.
Of all of the foregoing amines the preferred materials are the trialkyl amines marketed under the tradename ADOGEN, the long chain alkyldimethyl amines marketed under the tradename ARMEEN and the ethoxylated amines marketed under the tradename ETHOMEEN. The most preferred amines for use in the compositions herein are 1-hexylamine, 1-octylamine, 1- decylamine, 1-dodecylamine. Especially desirable for odor characteristics are n-dodecyldimethylamine (ARMEEN DM12D) and bishydroxyethylcoconutalkylamine (ETHOMEEN C/12, BEROL 307)and oleylamine 7 times ethoxylated(BEROL 28), lauryl amido propylamine and coco amido propylamine.
While not intending to be limited by theory, it is believed that the amine cosurfactant and anionic surfactant herein form complexes which enhance packing of the surfactants at the oil/water interface, thereby lowering interfacial tension and improving detergency. The amine surfactants would be at least partially protonated in the product and during the wash thus can form positively charged species capable of complexing with the anionic surfactant.
Another aspect of the invention relates to the surprising finding that low amounts of certain primary and/or tertiary amines of the present invention provide suds control to the detergent compositions formulated therewith.
The amounts in which the amines are used for controlling the suds are from 0.1 to 10%, preferably from 0.1 to 5%, most preferably from 0.5 to 4% by weight of the detergent composition. Detergent ingredients
In another embodiment of the present invention, a liquid detergent composition is provided comprising the surfactant system of the present invention mixed with detergent ingredients. A wide range of surfactants can be used in the detergent composition of the present invention. The detergent compositions according to the present invention will preferably comprise a surfactant system which is substantially free of linear alkylbenzene sulfonate surfactant.
A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in US Patent 3,664,961 issued to Norris on May 23, 1972.
Other suitable anionic surfactants that can be used are alkyl ester sulfonate surfactants including linear esters of c8~c20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula :
R3 - CH(S03M) - C(O) - OR4
wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a Cχ-Cg hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, R3 is Cio-Cig alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is Cιo-c16 alkyl. Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, c8~c22 primary of secondary alkanesulfonates, Cθ~c24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, C8-C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide) ; alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated Ci2~c18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated Cg-Ci2 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below) , and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2θ) jζ-CH2C00- M+ wherein R is a Cg-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch) . A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference) .
When included therein, the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 5% to about 25% by weight of such anionic surfactants. One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic- lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 14, more preferably from 12 to 14. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Especially preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the Cτ.2" C 5 primary alcohols containing 5-8 moles of ethylene oxide per mole of alcohol.
Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula
RO (CnH2n0)tZx
wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
Very suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula
R2 - C(O) - NtR1) - Z, wherein R1 is H, or R1 is Cι_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5-.31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight C ι_i5 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
Highly preferred nonionics are amine oxide surfactants. The compositions of the present invention may comprise amine oxide in accordance with the general formula I:
1 R (EO) (PO) (BO) N(0) (CH R') .qH 0 (I) x y z 2 2 2 In general, it can be seen that the structure (I) provides one long-chain moiety R (EO) (PO) (BO) and two
X V z short chain moieties, CH R' . R' is preferably selected from hydrogen, methyl and -CH2OH. In general R1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R is a primary alkyl moiety. When x+y+z = 0, R is a hydrocarbyl moiety having chainlength of from about 8 to about 18. When x+y+z is different from 0, R may be somewhat longer, having a chainlength in the range c12~c24- The general formula also encompasses amine oxides wherein x+y+z = 0, Ri = Cg-Ciβ, R' = H and q = 0-2, preferably 2. These amine oxides are illustrated by C12-14 alkyldimethyl amine oxide,hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates, especially the dihydrates as disclosed in U.S. Patents 5,075,501 and
5,071,594, incorporated herein by reference.
The invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy. Such amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
Highly preferred amine oxides herein are solids at ambient temperature, more preferably they have melting-points in the range 30°C to 90°C. Amine oxides suitable for use herein are - made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers. Preferred commercially available amine oxides are the solid, dihydrate ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 from Ethyl Corp.
Preferred embodiments include hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris(ethyleneoxy)dimethyl-amine oxide, and tetradecyldimethylamine oxide dihydrate.
Whereas in certain of the preferred embodiments R1 = H, there is some latitude with respect to having R' slightly larger than H. Specifically, the invention further encompasses embodiments wherein R' = CH OH, such as hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2- hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
When included therein, the laundry detergent compositions of the present invention typically comprise nonionic surfactants in the weight ratio of anionic surfactant to nonionic surfactant from 6:1 to 1:3, preferably from 5:1 to 2:1.
Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula :
[R2 (OR3)y] [R (OR3)y]2R5N+X~
wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, -CH2CH(CH3>-, -CH2CH(CH2θH)-, -CH2CH2CH2-, and mixtures thereof; each R4 is selected from the group consisting of C1-C alkyl, C1-C hydroxyalkyl-, benzyl ring structures formed by joining the two R4 groups, -CH2CHOH-CHOHCOR6CHOHCH2OH wherein R6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R5 is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R5 is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.
Preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula :
RlR2R3R4N+x" (i)
wherein R^ is Cg-Cig alkyl, each of R2, R3 and R4 is independently C1-C alkyl, C1-C hydroxy alkyl, benzyl, and - (C2H4θ)xH where x has a value from 1 to 5, and X is an anion. Not more than one of R2, R3 or R4 should be benzyl.
The preferred alkyl chain length for R^ is Ci2~ i5 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis. Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
Examples of suitable quaternary ammonium compounds of formulae (i) for use herein are : coconut trimethyl ammonium chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide;
Ci2-15 dimethyl hydroxyethyl ammonium chloride or bromide; coconut dimethyl hydroxyethyl ammonium chloride or bromide; myristyl trimethyl ammonium methyl sulphate; lauryl dimethyl benzyl ammonium chloride or bromide; lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide; choline esters (compounds of formula (i) wherein Rx is -CH2-
O-C(O)-C12--14 alkyl and R2R3R4 are methyl).
Other cationic surfactants useful herein are also described in U.S. Patent 4,228,044, Cambre, issued October 14, 1980.
When included therein, the laundry detergent compositions of the present invention typically comprise from 0.5% to about 5%, preferably from about 1% to about 3% by weight of such cationic surfactants.
The compositions according to the present invention may further comprise a builder system. Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid. Though less preferred for obvious environmental reasons, phosphate builders can also be used herein.
Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R- CH(COOH)CH2 (COOH) wherein R is C10-20 alkyl or alkenyl, preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents. Specific examples include lauryl succinate , myristyl succinate, palmityl succinate 2-dodecenylsuccinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
Especially for the liquid execution herein, suitable fatty acid builders for use herein are saturated or unsaturated C10- 18 fatty acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid. Other preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.
Detergency builder salts are normally included in amounts of from 3% to 50% by weight of the composition preferably from 5% to 30% and most usually from 5% to 25% by weight.
Other components used in detergent compositions may be employed, such as enzymes and stabilizers therefore, soil- suspending agents, soil-release polymers, abrasives, bactericides, tarnish inhibitors, coloring agents, foam control agents, corrosion inhibitors and perfumes.
Preferably, the liquid compositions according to the present invention are in "concentrated form"; in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents. The level of water is less than 50%, preferably less than 30%, more preferably less than 20% of water by weight of the detergent compositons.
Said concentrated products provide advantages to the consumer, who has a product which can be used in lower amounts and to the producer, who has lower shipping costs.
The liquid compositions are especially effective when applied directly to soils and stains in a pretreatment step. The detergent compositions of the present invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.
The detergent compositions according to the present invention include compositions which are to be used for cleaning of substrates, such as fabrics,fibers, hard surfaces, skin etc., for example hard surface cleaning compositions(with or without abrasives) , laundry detergent compositions, automatic and non- automatic dishwashing compositions.
The following examples are meant to exemplify compositions of the present inventions, but are not necessarily meant to limit the scope of the invention. EXAMPLE I
The following liquid detergent compositions are made % by weight of the detergent compositions
A B C D c12~c15 Alkyl ethoxylated sulfate 21 11.0 17 16. Octylamine 0.. 1 0. 0. c12~c14 alkyldimethyl amine oxide 3 2 12"c15 Alkyl sulfate 5 17.0 10 c12~c14 N-methyl glucamide 5 5.0 4.0 5 c12~c14 fatty alcohol ethoxylate 1 1 1 1 c12~c16 Fatty acid 7 7 4 6 Citric acid anhydrous 4.5 4.5 3 4 Diethylene triamine penta methy¬ lene phosphonic acid 1.0 1.0 2.0 2. Monoethanolamine 8 8 0.5 9 Sodiumhydroxide 1 1 2.5 1 Propanediol 12.7 14.5 13.1 10. Ethanol 1.8 1.8 4.7 5.
Amylase (300KNU/g) 0.1 0.1 0.1 0.1 Lipolase (lOOKNU/g) 0.15 0.15 0.15 0.15 Protease (34g/l) 0.5 0.5 0.5 0.5 Endo-A (5000 CEVU/g) 0.05 0.05 0.05 0.05 Carezyme (5000 CEVU/g) 0.09 0.09 0.09 0.09 Terephthalate-based polymer 0.5 0.5 0.3 Boric acid 2.4 2.4 2 2.8
Sodium xylene sulfonate 3 DC 3225C 03 0.04 0, 03 0.04 2-butyl-octanol 03 0.04 0, 04 0.03 Branched silicone ,3 0.3 0, 3 0.3 Water & Minors -up to 100%-
The above liquid detergent compositions (A-D) are found to be very efficient in the removal of greasy/oily soils under various usage conditions while having a controlled suds profile. The same results were obtained when octylamine was replaced in Compositions (A-D) by Bis (2-hydroxyethyl) coco amine, Oleyl amine 7EO, lauryl amido propylamine and coco amido propylamine.

Claims

What is claimed is:
1. A liquid detergent compositions comprising anionic surfactants selected from the group of alkyl alkoxy sulfates and alkyl sulfates, characterized in that said detergent composition further comprises an amine selected from i) primary amines having the formula R1R2R3N wherein R^ and R2 are both H ; and wherein R3 is C4-C18 or R4X(CH2)n whereby X is -0-, -C(0)NH- or -NH-/ R4 is a C4-C18, n is between 1 to 5; ii) tertiary amines having the formula R1R2R3N wherein neither Rl nor R2 is H, RI and R2 are Ci-Cg alkylchains or
Figure imgf000018_0001
whereby n is between 1 to 5 and x is between 1 to 5, R3 is either C4-C18 °~ 4X(CH2)n whereby X is -0-, -C(0)NH- or -NH-^4 is a C -Cig, n is between 1 to 5, and R5 is H or Cχ-C.2 alkyl; and; iii) mixtures of said primary and tertiary amines.
2. A liquid detergent composition acording to claim 2 wherein said primary amine is selected from n-alkylamines, 8-C14 alkyl amidopropyl amines, χo~c12 alkyl propylene diamines, and C8-C12 alkyl oxypropyl amines..
3. A liquid detergent composition according to claim 2 wherein said n-alkylamine is 1-octylamine.
4. A liquid detergent composition according to claim 1 wherein the amine is selected from the tertiary amine wherein R]_, R2
are both
Figure imgf000018_0002
whereby n is between 1 to 5 and x is between 1 to 5 and wherein R3 is C -C18 alkyl chain and wherein R5 is H or CH3.
5. A liquid detergent composition according to Claim 1 wherein the amine is a tertiary amine selected from C -C12 alkyl dimethyl amines and amines of the formula
Figure imgf000019_0001
wherein R4 is Cg-Cj2 aMcyl and n is 2 or 3.
6. A liquid detergent composition according to claims 1-5 wherein the weight ratio of the primary or/and tertiary amine to the alkyl alkoxylated sulfates and alkyl sulfates is from 1:1 to 1:250, more preferably from 1:5 to 1:100 and most preferably from 1:10 to 1:40.
7. A liquid detergent composition according to Claim 6 wherein the anionic surfactants are selected from the alkyl ethoxylated sulfate and Ci2~ci5 alkyl sulfate.
8. A liquid detergent composition according to Claims 1-7 further comprising a nonionic surfactant selected from the polyhydroxy fatty acid amides and/or amine oxides.
9. A liquid detergent composition according to claim 8 wherein said amine oxide is Ci2~c14 alkyl dimethyl amine oxide.
10. A liquid detergent composition according to Claims 1-9 further comprising other surfactants, builders, enzymes and other conventional detergent ingredients.
11. A liquid detergent composition according to Claims 1-10 which is free of linear alkylbenzene sulfonate surfactant.
12. Use of the primary amines and/or tertiary amines as defined in claims 1-5 in detergent compositions for the controlling of suds
13. Use of a liquid detergent composition according to Claims 1-11 for pretreatment of fabrics.
PCT/US1994/011779 1994-10-13 1994-10-13 Detergent compositions containing amines and anionic surfactants WO1996012000A1 (en)

Priority Applications (26)

Application Number Priority Date Filing Date Title
AU12881/95A AU1288195A (en) 1994-10-13 1994-10-13 Detergent compositions containing amines and anionic surfactants
PCT/US1994/011779 WO1996012000A1 (en) 1994-10-13 1994-10-13 Detergent compositions containing amines and anionic surfactants
EP95904050A EP0785978A1 (en) 1994-10-13 1994-10-13 Detergent compositions containing amines and anionic surfactants
HU9801065A HU215939B (en) 1994-10-13 1994-10-13 Detergent compositions containing amines and anionic surfactants and useing them
US08/817,152 US5981466A (en) 1994-10-13 1994-10-13 Detergent compositions containing amines and anionic surfactants
CZ971110A CZ111097A3 (en) 1994-10-13 1994-10-13 Detergent containing amines and anionic surface-active agents
CA002202506A CA2202506C (en) 1994-10-13 1994-10-13 Detergent compositions containing amines and anionic surfactants
BR9408622A BR9408622A (en) 1994-10-13 1994-10-13 Detergent compositions containing amines and anionic surfactants
JP51317696A JP4063866B2 (en) 1994-10-13 1994-10-13 Detergent composition comprising an amine and an anionic surfactant
PCT/US1995/007824 WO1997000929A1 (en) 1994-10-13 1995-06-20 Detergent compositions containing amines and anionic surfactants
EP95924620A EP0833884A1 (en) 1994-10-13 1995-06-20 Detergent compositions containing amines and anionic surfactants
HU9901140A HUT78084A (en) 1994-10-13 1995-09-29 Laundry detergent compositions containing lipolytic enzyme and amines
AT95934562T ATE215984T1 (en) 1994-10-13 1995-09-29 TEXTILE DETERGENT CONTAINING LIPOLYTIC ENZYME AND AMINE COMPOUNDS
CN95196637.5A CN1168691A (en) 1994-10-13 1995-09-29 Laundry detergent composition containing lipolytic enzyme and amine
DE69526360T DE69526360T2 (en) 1994-10-13 1995-09-29 TEXTILE DETERGENT CONTAINING LIPOLYTIC ENZYME AND AMINE COMPOUNDS
AU36869/95A AU3686995A (en) 1994-10-13 1995-09-29 Laundry detergent compositions containing lipolytic enzyme and amines
CZ971109A CZ110997A3 (en) 1994-10-13 1995-09-29 Detergents containing lipolitic enzyme and amines
BR9509349A BR9509349A (en) 1994-10-13 1995-09-29 Laundry detergent compositions containing lipolytic enzymes to amines
JP8513248A JPH10509468A (en) 1994-10-13 1995-09-29 Laundry detergent composition containing lipolytic enzyme and amine
PCT/US1995/012469 WO1996012004A1 (en) 1994-10-13 1995-09-29 Laundry detergent compositions containing lipolytic enzyme and amines
EP95934562A EP0785981B1 (en) 1994-10-13 1995-09-29 Laundry detergent compositions containing lipolytic enzyme and amines
US08/817,154 US5935271A (en) 1994-10-13 1995-09-29 Laundry detergent compositions containing lipolytic enzyme and amines
CA002202505A CA2202505C (en) 1994-10-13 1995-09-29 Laundry detergent compositions containing lipolytic enzyme and amines
TR95/01261A TR199501261A2 (en) 1994-10-13 1995-10-13 Detergent compositions containing amines and anionic surfactants.
TR95/01262A TR199501262A2 (en) 1994-10-13 1995-10-13 Detergent compositions for laundry containing lipolytic enzymes and amines.
MXPA/A/1997/002728A MXPA97002728A (en) 1994-10-13 1997-04-14 Detergent compositions for laundry quecontain lipolitic enzyme and ami

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1994/011779 WO1996012000A1 (en) 1994-10-13 1994-10-13 Detergent compositions containing amines and anionic surfactants

Publications (1)

Publication Number Publication Date
WO1996012000A1 true WO1996012000A1 (en) 1996-04-25

Family

ID=22243129

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/011779 WO1996012000A1 (en) 1994-10-13 1994-10-13 Detergent compositions containing amines and anionic surfactants

Country Status (9)

Country Link
EP (2) EP0785978A1 (en)
JP (2) JP4063866B2 (en)
AU (2) AU1288195A (en)
BR (2) BR9408622A (en)
CA (2) CA2202506C (en)
CZ (2) CZ111097A3 (en)
HU (1) HUT78084A (en)
TR (2) TR199501262A2 (en)
WO (1) WO1996012000A1 (en)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997012021A1 (en) * 1995-09-29 1997-04-03 The Procter & Gamble Company Detergent compositions containing amines, alkyl sulfates, and other anionic surfactants
EP0833884A1 (en) * 1994-10-13 1998-04-08 The Procter & Gamble Company Detergent compositions containing amines and anionic surfactants
WO1998029527A1 (en) * 1996-12-31 1998-07-09 The Procter & Gamble Company Thickened, highly aqueous liquid detergent compositions
WO1998020964A3 (en) * 1996-11-12 1998-10-29 Clariant Gmbh Novel fatty alcohol sulfates and alkylethersulfates with trialkylammonium counter-ions and well as their production and use
US5916575A (en) * 1997-01-27 1999-06-29 The Procter & Gamble Company Cleaning products
EP0730024B1 (en) * 1995-03-01 1999-10-13 CHEMISCHE FABRIK DR. WEIGERT (GMBH & CO.) Surgical instruments cleaning composition
WO2000046331A1 (en) * 1999-02-08 2000-08-10 The Procter & Gamble Company Diols and polymeric glycols in dishwashing detergent compositions
WO2001019947A1 (en) * 1999-09-16 2001-03-22 The Procter & Gamble Company Dishwashing detergent compositions containing color-stabilizing phosphonates
WO2002022770A1 (en) * 2000-09-13 2002-03-21 Henkel Kommanditgesellschaft Auf Aktien Quick drying washing and cleaning agent, especially washing-up liquid
US6740627B1 (en) 1999-02-08 2004-05-25 The Procter & Gamble Company Diols and polymeric glycols in dishwashing detergent compositions
US7179783B2 (en) 2002-04-17 2007-02-20 Kao Corporation Sulfuric acid amine salt, sulfonic acid amine salt, production thereof and softener composition
WO2010057973A1 (en) * 2008-11-21 2010-05-27 Thermphos Trading Gmbh Solid surface treatment composition containing amine neutralized phosphonate
WO2010057976A1 (en) * 2008-11-21 2010-05-27 Thermphos Trading Gmbh Liquid surface treatment composition with phosphonic acid derivatives neutralized with a binary amine system
KR101859464B1 (en) * 2013-06-28 2018-05-21 라이온 가부시키가이샤 Detergent for dishwasher
US20190185785A1 (en) * 2017-12-20 2019-06-20 Henkel Ag & Co. Kgaa Washing agent containing amine oxide and sugar surfactants
EP3571275A4 (en) * 2017-01-20 2020-11-04 Ecolab USA Inc. CLEANING COMPOSITIONS WITH LONG CHAIN ANIONIC SURFACTANTS
US11306274B2 (en) 2017-06-26 2022-04-19 Kao Corporation Liquid detergent composition for hard surfaces

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5396707B2 (en) * 2007-11-07 2014-01-22 ライオンハイジーン株式会社 Cleaning composition
US7723281B1 (en) * 2009-01-20 2010-05-25 Ecolab Inc. Stable aqueous antimicrobial enzyme compositions comprising a tertiary amine antimicrobial
JP6097639B2 (en) * 2013-06-10 2017-03-15 株式会社Adeka Cleaning composition and method of using the same
JP6118660B2 (en) * 2013-06-28 2017-04-19 ライオン株式会社 Dishwasher cleaner
JP6118664B2 (en) * 2013-06-28 2017-04-19 ライオン株式会社 Liquid detergent for dishwashers
JP6118662B2 (en) * 2013-06-28 2017-04-19 ライオン株式会社 Liquid detergent for dishwashers
JP6118663B2 (en) * 2013-06-28 2017-04-19 ライオン株式会社 Dishwasher cleaner
JP6238451B2 (en) * 2014-04-16 2017-11-29 ライオン株式会社 Liquid detergent for textile products

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1375639A (en) * 1973-07-24 1974-11-27
US3853779A (en) * 1972-06-06 1974-12-10 Colgate Palmolive Co Low foaming detergent compositions
FR2329746A1 (en) * 1975-10-31 1977-05-27 Procter & Gamble Europ Clear liq. cleaning compsn. for glazed surfaces - contg. anionic detergents (quat) amine and gelatin, giving rapid draining
EP0203660A1 (en) * 1985-05-28 1986-12-03 Unilever N.V. Liquid cleaning and softening compositions

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4486195A (en) * 1984-03-05 1984-12-04 Millmaster Onyx Group Inc. Laundering compositions
AU1288195A (en) * 1994-10-13 1996-05-06 Procter & Gamble Company, The Detergent compositions containing amines and anionic surfactants

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3853779A (en) * 1972-06-06 1974-12-10 Colgate Palmolive Co Low foaming detergent compositions
GB1375639A (en) * 1973-07-24 1974-11-27
FR2329746A1 (en) * 1975-10-31 1977-05-27 Procter & Gamble Europ Clear liq. cleaning compsn. for glazed surfaces - contg. anionic detergents (quat) amine and gelatin, giving rapid draining
EP0203660A1 (en) * 1985-05-28 1986-12-03 Unilever N.V. Liquid cleaning and softening compositions

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0833884A1 (en) * 1994-10-13 1998-04-08 The Procter & Gamble Company Detergent compositions containing amines and anionic surfactants
EP0730024B1 (en) * 1995-03-01 1999-10-13 CHEMISCHE FABRIK DR. WEIGERT (GMBH & CO.) Surgical instruments cleaning composition
WO1997012021A1 (en) * 1995-09-29 1997-04-03 The Procter & Gamble Company Detergent compositions containing amines, alkyl sulfates, and other anionic surfactants
US6087321A (en) * 1995-09-29 2000-07-11 The Procter & Gamble Company Detergent compositions containing amines, alkyl sulfates, and other anionic surfactants
WO1998020964A3 (en) * 1996-11-12 1998-10-29 Clariant Gmbh Novel fatty alcohol sulfates and alkylethersulfates with trialkylammonium counter-ions and well as their production and use
US6221825B1 (en) 1996-12-31 2001-04-24 The Procter & Gamble Company Thickened, highly aqueous liquid detergent compositions
WO1998029527A1 (en) * 1996-12-31 1998-07-09 The Procter & Gamble Company Thickened, highly aqueous liquid detergent compositions
US5916575A (en) * 1997-01-27 1999-06-29 The Procter & Gamble Company Cleaning products
WO2000046331A1 (en) * 1999-02-08 2000-08-10 The Procter & Gamble Company Diols and polymeric glycols in dishwashing detergent compositions
US6740627B1 (en) 1999-02-08 2004-05-25 The Procter & Gamble Company Diols and polymeric glycols in dishwashing detergent compositions
WO2001019947A1 (en) * 1999-09-16 2001-03-22 The Procter & Gamble Company Dishwashing detergent compositions containing color-stabilizing phosphonates
US7186675B2 (en) 2000-09-13 2007-03-06 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Quick drying washing and cleaning agent, comprising an anionic/cationic/amphoteric surfactant mixture
WO2002022770A1 (en) * 2000-09-13 2002-03-21 Henkel Kommanditgesellschaft Auf Aktien Quick drying washing and cleaning agent, especially washing-up liquid
US7179783B2 (en) 2002-04-17 2007-02-20 Kao Corporation Sulfuric acid amine salt, sulfonic acid amine salt, production thereof and softener composition
WO2010057973A1 (en) * 2008-11-21 2010-05-27 Thermphos Trading Gmbh Solid surface treatment composition containing amine neutralized phosphonate
WO2010057976A1 (en) * 2008-11-21 2010-05-27 Thermphos Trading Gmbh Liquid surface treatment composition with phosphonic acid derivatives neutralized with a binary amine system
KR101859464B1 (en) * 2013-06-28 2018-05-21 라이온 가부시키가이샤 Detergent for dishwasher
EP3571275A4 (en) * 2017-01-20 2020-11-04 Ecolab USA Inc. CLEANING COMPOSITIONS WITH LONG CHAIN ANIONIC SURFACTANTS
US11591546B2 (en) 2017-01-20 2023-02-28 Ecolab Usa Inc. Cleaning compositions employing extended chain anionic surfactants
US12077726B2 (en) 2017-01-20 2024-09-03 Ecolab Usa Inc. Cleaning compositions employing extended chain anionic surfactants
US11306274B2 (en) 2017-06-26 2022-04-19 Kao Corporation Liquid detergent composition for hard surfaces
US20190185785A1 (en) * 2017-12-20 2019-06-20 Henkel Ag & Co. Kgaa Washing agent containing amine oxide and sugar surfactants
EP3502221A1 (en) * 2017-12-20 2019-06-26 Henkel AG & Co. KGaA Detergent composition containing amine oxide and sugar surfactants
US11136530B2 (en) 2017-12-20 2021-10-05 Henkel Ag & Co. Kgaa Washing agent containing amine oxide and sugar surfactants

Also Published As

Publication number Publication date
JPH10509468A (en) 1998-09-14
CA2202505A1 (en) 1996-04-25
CA2202506A1 (en) 1996-04-25
EP0833884A1 (en) 1998-04-08
JP4063866B2 (en) 2008-03-19
CZ111097A3 (en) 1997-09-17
CA2202505C (en) 2001-02-06
AU3686995A (en) 1996-05-06
TR199501261A2 (en) 1996-06-21
AU1288195A (en) 1996-05-06
EP0785978A1 (en) 1997-07-30
JPH10507469A (en) 1998-07-21
CA2202506C (en) 2001-02-13
CZ110997A3 (en) 1997-09-17
TR199501262A2 (en) 1996-06-21
HUT78084A (en) 1999-08-30
BR9408622A (en) 1997-09-16
BR9509349A (en) 1997-11-25

Similar Documents

Publication Publication Date Title
CA2202506C (en) Detergent compositions containing amines and anionic surfactants
US5916862A (en) Detergent compositions containing amines and anionic surfactants
US5981466A (en) Detergent compositions containing amines and anionic surfactants
US4561998A (en) Near-neutral pH detergents containing anionic surfactant, cosurfactant and fatty acid
EP0551375B1 (en) Polyhydroxy fatty acid amides in zeolite/layered silicate built detergents
EP0095205B1 (en) Fatty acid containing detergent compositions
EP0576778B1 (en) Concentrated aqueous liquid detergent compositions
WO1997000929A1 (en) Detergent compositions containing amines and anionic surfactants
CA2165766C (en) Low sudsing liquid detergent compositions
EP0763091A1 (en) Laundry detergent compositions
CA2602138A1 (en) Laundry detergents containing mid-branched primary alkyl sulfate surfactant
AU682668B2 (en) Detergent composition with suds suppressing system
US6087321A (en) Detergent compositions containing amines, alkyl sulfates, and other anionic surfactants
GB2185991A (en) Liquid laundering composition with detergent softening properties
EP0189225A2 (en) Built liquid detergent containing anionic, ethoxylated nonionic and amide surfactants
WO1997006235A1 (en) Detergent compositions containing amine and specially selected perfumes
CA2233332C (en) Liquid laundry detergents containing selected alkyl amidoalkoyl quaternary ammonium compounds
EP0873387A1 (en) Liquid laundry detergents containing selected quaternary ammonium compounds
MX2014005747A (en) Concentrated alkyl ether sulfate amine salt compositions.
US6017874A (en) Liquid laundry detergents containing selected quaternary ammonium compounds
US5858950A (en) Low sudsing liquid detergent compositions
CA2225458A1 (en) Detergent compositions containing amines and anionic surfactants
US5668095A (en) Detergent composition with suds suppressing system
CA2233451A1 (en) Liquid laundry detergents containing selected quaternary ammonium compounds
HU215939B (en) Detergent compositions containing amines and anionic surfactants and useing them

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 94195207.X

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AM AU BB BG BR BY CA CN CZ EE FI GE HU JP KG KP KR KZ LK LR LT LV MD MG MN NO NZ PL RO RU SI SK TJ TT UA US UZ VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE MW SD SZ AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1995904050

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2202506

Country of ref document: CA

Ref document number: 2202506

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: PV1997-1110

Country of ref document: CZ

WWP Wipo information: published in national office

Ref document number: 1995904050

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 08817152

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: PV1997-1110

Country of ref document: CZ

WWR Wipo information: refused in national office

Ref document number: PV1997-1110

Country of ref document: CZ

WWW Wipo information: withdrawn in national office

Ref document number: 1995904050

Country of ref document: EP