CA2233332C - Liquid laundry detergents containing selected alkyl amidoalkoyl quaternary ammonium compounds - Google Patents

Abstract

This invention relates to a liquid laundry detergent composition comprising a Nil-LAS surfactant system said surfactant system comprising: i) anionic surfactants selected from the group of alkyl alkoxy sulfates and alkyl sulfates, and ii) a quaternary ammonium surfactant having formula (I), where by R1 is a C6-C18 alkyl; y is from 1 to 6; R2, R3 and R4 are either the same or different and can be H, a C1-C8 alkyl, C1-C8 alkoxy, aryl, alkaryl or alkoxyaryl; X is a counterion.

Description

LIQUID LAUNDRY DETERGENTS CONTAINING SELECTED
ALKYL AMIDOALKOYL QUATERNARY AMMONIUM COMPOUNDS
Field of the Invention The present invention relates to detergent compositions containing surfactants selected from quaternary ammonium surfactants. More particularly, the invention is directed to detergent compositions containing a nil-LAS
surfactant system comprising anionic surfactants selected from the group consisting of alkyl alkoxylated sulfates and alkyl sulfates, said composition further containing specific quaternary ammonium surfactants.
Background of the Invention The present invention relates to liquid detergents containing a surfactant ~ 5 system which is free of linear alkyl benzene sulfonate surfactants (LAS), said liquid detergent having optimum greasy stain removal performance.
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.
2o 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 25 sulfates, said surfactant system fiurther comprising a cosurfactant selected from the group of quaternary ammonium surfactants which are stable in the detergent product.
It has been surprisingly found that detergent compositions containing said surfactant system exhibit detergency performance equivalent to that of LAS
containing detergents.
30 In addition, it was found that the liquid detergent compositions containing the selected quaternary ammonium surfactants of the present invention, provide excellent greasy stain removal performance without detriment to the suds ' characteristics of the compositions. This finding allows the formulator to reduce the level of suds suppressing agents, thereby facilitating the formulation of concentrated 35 liquid detergents.
Quaternary ammonium surfactants are described in the art. The properties of these surfactants are very strongly influenced by the type of substituent.
Chain length, degree of saturation, branching or the presence and number of hydroxylic or ethoxy groups mainly determine the properties of the surfactant. Whereas typical textile-conditioning actions are performed by cationic surfactants with two long alkyl chains. cationic surfactants with only one long alkyl chain have been reported to improve the detergency performance in laundry detergents. EP-A-224 describes liquid built laundry detergent compositions comprising a general class of quaternary ammonium surfactants. Decyltrimethyl ammonium chloride is described. EP 8142 describes a liquid builder-free heavy duty detergent comprising a quaternary ammonium compound of a general formula. Octyldihydroxyethylmethyl ammonium 1 O halides are described.
For optimum grease detergency performance, however, these compositions of the prior art require high level of cationic surfactant. These high levels of cationic surfactants in turn, generate excessive foaming, thereby raising problems of automatic washing machine compatibility. If, on the other hand, the cationic surfactant is reduced at a level at which foam regulation is no longer a problem, the beneficial grease detergency characteristics of quaternary compounds are diminished.
In contrast, the surfactant system of the present invention provides optimum grease and oil removal performance, thereby not adversely affecting the suds characteristic of the detergent compositions formulated therewith.
In addition, it has been found that 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.
Summary of the Invention The present invention relates to liquid detergent compositions comprising a nil-LAS surfactant system (less than 5%, preferably substantially free of LAS, e.g., less than 0.1 % by weight of detergent composition). Said surfactant system comprising anionic surfactants selected from the group of alkyl alkoxy sulfates and alkyl sulfates and selected quaternary ammonium surfactants. The detergent compositions comprise at least 5%, more preferably from about 10% to about 65%, even more preferably from about 15% to about 40%, by weight, of the anionic surfactant as described herein. The quaternary ammonium surfactant is present in an amount ranging from about 0.5% to about 10%, preferably from about 1% to about ' 4%, by weight, of the total detergent composition.
Detailed description of the Invention The surfactant system of 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 C l0-C24 alkyl or hydroxyalkyl group having a C l 0-C24 alkyl component, preferably a C 12-C
1 g alkyl or hydroxyalkyl, more preferably C 12-C 15 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably 1 O 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 alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.

Exemplary surfactants are C 12-C 15 alkyl polyethoxylate ( 1.0) sulfate (C 12-C 15E( 1.0)M), C 12-C 15 alkyl polyethoxylate (2.25) sulfate (C 12-C 15E(2-25)M), 2o C 1 ~-C 1 ~ alkyl polyethoxylate (3.0) sulfate (C 12-C
1 SE(3.0)M), and C 1 ~-C 1 ~ alkyl polyethoxylate (4.0) sulfate (C 12-C 15E(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 ROS03M wherein R preferably is a Cl0-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C l 0-C 1 g alkyl component, more preferably a C 12-C 15 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 quaternary ammonium compound - The quaternary ammonium surfactant according to the present invention has the formula:

R i-CI -NH-(CH~y-N ~ R3 X-whereby R 1 is a C6-C 1 g alkyl, preferably a C 12-14 alkyl; y is from about 1 to about 6, preferably from about 1 to about 3, more preferably 3; R2, R3 and R4 are either the same or different and can be H, a Cl-Cg alkyl, preferably a Cl-C3 alkyl, Cl-Cg alkoxy, aryl, alkaryl or alkoxyaryl; X- is a counterion, preferably a halide, e.g., chloride, acetate, sulfate, OH-, or methylsulfate.
Preferred quaternary ammonium surfactants are those whereby Rl is C12-C 14, R2, R3, and R4 are CH3.
1 O Preferred quaternary ammonium surfactants have the above formula, and are present in the detergent compositions herein in an amount ranging from about 0.5%
to about 10%, by weight, of the total 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 secondary surfactants can be used in the detergent composition of the present invention.
The detergent compositions according to the present invention 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.
When included therein, the laundry detergent compositions of the present invention typically comprise from about 1% to about 35%, preferably from about 5%
to about 20%, by weight of secondary surfactants.
Other suitable anionic surfactants that can be used are alkyl ester sulfonate surfactants including linear esters of Cg-C2p carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous S03 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.
3o The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprise alkyl ester sulfonate surfactants of th;e structural formula R3 - CH(S03M) - C(O) - OR4 wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, o:r combination thereof, R4 is a C1-C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a i. 5 canon which forms a water soluble salt with the alkyl ester sulfonate.
Suitable salt-forming canons include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium canons, such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, R3 is Cl0-CI6 alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is C 1 p-C I 6 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, Cg-C22 primary of secondary alkanesulfonates, Cg-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, Cg-C24 alkylpolyglycolethersulfates (containing up to IO moles of ethylene oxide);
~ 5 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 C 1 ~-C 1 g monoesters) and diesters of sulfosuccinates (especially saturated and 20 unsaturated C6-C12 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(CH2CH20)k-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 25 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 Coltunn 23, line 58 through Column 30 29, line 23.
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 35 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 I4. 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 Cg-C 15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C 12-C 15 primary alcohols containing 5-8 moles of ethylene oxide per mole of alcohol.
Another class of nonionic surfactants comprises alkyl polyglucoside compounds 1 o of general formula RO (CnH2nO)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, 0 075 995 and 0 094 118.
Very suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula R2 - C(O) - N(R1) - Z, wherein R1 is H, or R1 is C1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is CS_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 C11-15 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:
R1(EO)x(PO)y(BO)zN(O)(CH2R)2.qH2O (I).
In general, it can be seen that the structure (I) provides one long-chain moiety R1(EO)x(PO)y(BO)z and two short chain moieties, CH2R'. R' is preferably selected from hydrogen, methyl and -CH20H. In general R1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R1 is a primary alkyl moiety. When x+y+z = 0, R1 is a hydrocarbyl moiety having chainlength of from about 8 to about 18. When x+y+z is different from 0, Rl may be somewhat longer, having a chainlength in the ranee C l 2-C~.1. The general formula also encompasses amine oxides wherein x+y+z = 0, R 1 = C g-C l g, R' =
H
and q = 0-2, preferably 2. These amine oxides are illustrated by C 1 ~_ 14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide. octadecylamine oxide and their hydrates, especially the dihydrates as disclosed in U.S. Patents 5,07,501 and 5,071,594.
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, Rl is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon t o 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 ~ 5 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 2o 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, dodecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, 25 hexadecyltris (ethyleneoxy)dimethyl-amine oxide, and tetradecyldimethyl-amine oxide dehydrate.
Whereas in certain of the preferred embodiments R' is H, there is some latitude with respect to having R' slightly larger than H. Specifically, the invention further encompasses embodiments wherein R' is CH20H, such as hexadecylbis(2-30 hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)arnine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2-hydroxyethyl)amine oxide, dodecyldimethylamine oxide dehydrate.
The compositions according to the present invention may further comprise a builder system. Any conventional builder system is suitable for use herein including 35 aluminosilicate materials,, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetra-acetate, metal ion sequestrants such as aminopoly-phosphonates, particularly ethylenediamine tetramethylene phosphoric acid and diethylene triamine pentamethylene phosphonic 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 C 10-20 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 C 10-18 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 builders are normally included in amo~.mts of from 3% to 50% by weight of the composition preferably from 5% to 30% and most usually from 5%
to 25% by weight.
Optional detergent ingredients - Preferred detergent compositions of the present invention may further comprise one or more enzymes which provide cleaning performance and/or fabric care benefits. Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, J3-glucanases, arabinosidases or mixtures thereof.
A preferred combination is a detergent composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with the lipolytic enzyme variant D96L at a level of from SO
LU to 8500 LU per liter wash solution.
The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5.
Suitable ' cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also ' disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.

Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM
1800.
Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about SOKDa, an isoelectric point of 5.5 and containing 415 amino acids. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in United States patent No. 5,520,838 issued May 26, 1996 (Novo).
Peroxidase enzymes are used in combination with oxygen sources, e.g.
1 o percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
Peroxidase-containing detergent compositions are disclosed, for example, in published PCT International Application WO 89/099813 and in Canadian Patent application No. 2,122,987, filed on October 28, 1992.
Said cellulases and/or peroxidases are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of active enzyme by weight of the 2 o detergent composition.
Preferred commercially available protease enzymes include those sold under the trademarks Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Nordisk A/S (Denmark), those sold under the trademarks Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold 2 5 under the trademarks Opticlean and Optimase by Solvay Enzymes. Also proteases described in our co-pending application CA 2,173,105 can be included in the detergent composition of the invention. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001%
to 2%
active enzyme by weight of the composition.
3 o A preferred protease herein referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for the amino acid residue at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue 35 positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to ., the numbering of Bacillus amyloliquefaciens subtilisin, as described in the patent of A. Baeck et al. entitled "Protease-Containing Cleaning Compositions" U.S.
Patent No. 5,679,630 issued October 21, 1997.
Highly preferred enzymes that can be included in the detergent compositions 5 of the present invention include lipases. It has been found that the cleaning performance on greasy soils is synergistically improved by using lipases.
Suitable lipase enzymes include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases include those which show a positive immunological 1 o cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade mark Lipase P "Amano,"
hereinafter referred to as "Amano-P". Further suitable lipases are lipases such as M 1 Lipase~ and Lipomax~ (Gist-Brocades). Highly preferred lipases are the D96L
lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa as described in US Patent No. 5,837,010. Preferably the Humicola lanuginosa strain DSM 4106 is used. This enzyme is incorporated into the composition in accordance with the invention at a level of from 50 LU to 8500 LU per liter wash solution.
Preferably the variant D96L is present at a level of from 100 LU to 7500 LU
per liter 2 0 of wash solution. More preferably at a level of from 150 LU to 5000 LU per liter of wash solution.
By D96L lipolytic enzyme variant is meant the lipase variant as described in patent application WO 92/05249 viz. wherein the native lipase ex Humicola lanuginosa aspartic acid (D) residue at position 96 is changed to Leucine (L).
2 5 According to this nomenclature said substitution of aspartic acid to Leucine in position 96 is shown as : D96L.
Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation.
Addition of cutinases to detergent compositions have been described in e.g. WO-A-3 0 (Genencor).
The lipases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of active enzyme by weight of the detergent composition.
Amylases (& and/or (3) can be included for removal of carbohydrate-based 3 5 stains. Suitable amylases are TermamylR (Novo Nordisk), FungamylR and BANK
(Novo Nordisk).

'' 11 The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial. fungal and yeast origin.
Said enzymes are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in European Patent application 553607 published August 4, 1993. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
Other components used in detergent compositions may be employed, such as 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 ~ 5 present invention will contain a lower amount of water, compared to conventional liquid detergents. The level of water is Iess than ~0%, preferably less than 30% 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 20 shipping costs.
The liquid compositions are especially effective when applied directly to soils and stains in a pretreatment step before washing the fabrics.
' The detergent compositions of the present invention can also be used as detergent additive products. Such additive products are intended to supplement or 25 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 30 dishwashing compositions.
The following examples are meant to exemplify compositions of the present inventions, but are not necessarily meant to i~mn the scope of the invention.

O
R'~OH O CH3C1 O
~N~NH~ toluene - I + ~
I (p~ ~N~N R CH3CN ~N~N~R
R=Ctt/~s 0 ~ H a ~ H
-Hz0 1 2 (Cocoylamidopropyl)dimethylamine (1}. Coconut fatty acid (150.00 g, 0.749 mol), N,N dimethyl-1,3-propanediamine (86.00 g, 0.933 mol), and p-toluenesulfonic acid (7.12 g, 0.037 mol) are combined with toluene (300 mL) in a I
L flask fitted with a Dean-Stark trap, condenser, and argon inlet. The mixture is heated to reflux for 18 h at which time the theoretical amount of water is collected.
The mixture is concentrated by rotary evaporation, taken-up in 1500 mL of dichloromethane and washed twice with 200 mL of 50°ro K2C03 solution.
The organic layer is dried over MgS04, filtered, and concentrated by rotary evaporation to give 196.38 g (92.2%) of 1 as an off white solid. The structure is confirmed by 1 H and 13 C NMR.
(Cocoylamidopropyl)trimethylammonium chloride (2).
GCocoamidopropyl)di-methylamine (100.00 g, 0.343 mol) and acetonitrile (100 mL) are combined in a glass autoclave liner. The liner is placed in an autoclave and its contents are treated with methyl chloride gas (65 psig, 6~-85 °C) for 18 h. The cooled mixture is removed with the addition of dichloromethane (500 mL). The mixture is concentrated by rotary evaporation to give 109.63 g (93.5%) of 2 as an off white solid. The structure is confirmed by 1H and 13C NMR.
Example II

R'~OH O (CH30)zsOz O
~ i ~NHZ tol~ ~N~N~R CH3CN ~N~N~R
(pTSA) I H ~~ I H
R~~ ~ O (CH3S04) (Lauroylamidopropyl)dimethylamine (3}. Lauric acid ( 140.28 g, 0.711 mol), N,N dimethyl-1,3-propanediamine (72.65 g, 0.711 mol), and p-toluenesulfonic acid (3.47 g, 0.018 mol) are combined with toluene (250 mL) in a 1 L flask fitted with a Dean-Stark trap, condenser, and argon inlet. The mixture is heated to reflux for 18 h at which time the theoretical amount of water is collected. The mixture is -washed twice with 200 mL of 50% K2C03 solution. The organic layer is dried over MgS04, filtered, and concentrated by rotary evaporation to give 184.80 g (92.4%) of 3 as a white solid. The structure is confirmed by 1H and 13C NMR.
(Lauroylamidopropyl)trimethylammonium methylsulfate (4).
(Lauroylamido-propyl)dimethylamine (184.00 g, 0.654 mol) and acetonitrile (500 mL) are combined in a round bottomed flask fitted with a condenser and argon inlet.
The mixture is magnetically stirred until it is homogeneous. At this point, dimethylsulfate (82.46 g, 0.654 mol) is added to the reaction mixture. The mixture is heated to reflux for 2 h. The cooled mixture is concentrated by rotary evaporation to give 259.39 g (97.3%) of 4 as a white solid. The structure is confirmed by 1 H and 13 C NMR.

EXAMPLE III
Liquid detergent compositions are made according to the following.
by weight Of the detergent cnmnncitinr,~
B C D

C 1 ~-C 1 ~ alkyl ethoxylated sulfate2 8 11 5 Quaternary Surfactant* 2 2 2 1 C 1 ~-C 14 alkyIdimethyl amine oxide- _ C 1 ~-C 15 alkyl sulfate 17 12 7 8 C I 2-C 14 N-methyl glucamide 5 4 4 3 C I ~-C I 4 fatty alcohol ethoxylate6 1 1 I

C12-Clg fatty acid I 1 4 4 3 Citric acid anhydrous l 3 3 2 Diethylenetriamine pentamethylene 1 1 1 0.5 phosphoric acid Monoethanolamine g -Sodium hydroxide 1 2.5 1 1.5 Propanediol 14.~ 13.1 10.0 8 Ethanol 1.8 4.7 s.-1 1 I

Amylase (300KNU/g) 0.1 0.1 0.1 O.I

Lipase D96/L ( 100KNU/g) 0.1 0.15 0.1 0.15 S ~

Protease (35g/1) 0.5 0.5 0.5 0.5) Endo-A (5000 CEVLJ/g) 0.05 0.05 0.05 0.5 Carezyme~ (5000 CEW/g) 0.09 0.09 0.09 0.9 Terephthalate-based polymer 0.5 - 0.3 0.3 Boric acid ?:4- 2.8 2.8 2.4 Sodium xylene sulfonate - 3 - _ DC 3225C 0.04 0.04 0.03 0.03 2-butyl-octanol I 1 1 1 Branched silicone 0.3 0.3 0.3 0.3 , ~

Water & minors ~ Up to 100%

The quaternary surfactant are chosen from those of E.rample I or II.
The above liquid detergent compositions i A-Dl are found to be very efficient in the removal of greasy/oily soils under various usage conditions while having a controlled suds profile.

Claims (5)

What is claimed is:

1. A liquid laundry detergent composition comprising a nil-LAS surfactant system said surfactant system comprising i) from about 10% to about 65%, by weight of total composition, of anionic surfactants selected from the group of alkyl alkoxy sulfates and alkyl sulfates;
and ii) from about 0.5% to about 10%, by weight of the total detergent composition, of a quaternary ammonium surfactant having the formula whereby R1 is a C6-C18 alkyl; y is from about 1 to about 6; R2, R3 and R4, are either the same or different and can be H, a C1-C8 alkyl, C1-C8 alkoxy, aryl, alkaryl or alkoxyaryl; X- is a counterion.

2. A liquid detergent composition according to Claim 1 wherein R1 is C12-14;
R2, R3, and R4, are CH3, and y is 3.

3. A liquid detergent composition according to Claim 2 wherein the anionic surfactants are selected from the alkyl ethoxylated sulfate and C12-C15 alkyl sulfate.

4. A liquid detergent composition according to Claim 1 further comprising other secondary surfactants, builders, enzymes, and other conventional detergent ingredients.

5. Use of a liquid detergent composition according to Claim 1 for pretreatment of fabrics.