CA2202506C

CA2202506C - Detergent compositions containing amines and anionic surfactants

Info

Publication number: CA2202506C
Application number: CA002202506A
Authority: CA
Inventors: Joseph Paul Morelli; Dimitris Lappas; Sherri Lynn Randall; Rajan Keshav Panandiker; Jean-Pol Boutique; Chris Efstathios Housmekerides
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1994-10-13
Filing date: 1994-10-13
Publication date: 2001-02-13
Anticipated expiration: 2014-10-13
Also published as: AU3686995A; AU1288195A; WO1996012000A1; CA2202505C; HUT78084A; JPH10509468A; CZ111097A3; TR199501262A2; EP0833884A1; EP0785978A1; TR199501261A2; CA2202505A1; JP4063866B2; BR9509349A; JPH10507469A; CZ110997A3; BR9408622A; CA2202506A1

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 C6C18, n is between 1 to 5; ii) tertiary amines having the formula R1R2R3N, wherein neither R1 nor R2 is H, R1 and R2 are C1-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 alkoxylated 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 inthe 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.

W O 96112000 PCTlUS941I1779 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 aad EP 137 616 disclose liquid- detergents- which comprise cyclohexylamine.
EP 177 165 discloses detergent compositions which comprise ' avionics, cellulose and a variety of primary, secondary, tertiary and quaternary amines. EP il X40 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 anionic:s 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 sarcosinat:e are disclosed in WO 95/33035, published December 7, 1995. 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 tertiary amines.
The detergent compositions preferably comprise at least 5%, more preferably from loo to 65% and most preferably from 15% to 40o 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 px°eferably from 1:5 to 1:100 and most preferably from 1.:10 to 1:40.
In one particularly preferred embodiment there is provided a liquid detergent composition comprising: (a) from about 5% to about 25%, by weight, of an anionic surfactant 3a selected from the' group consisting of alkyl alkoxy sulfates, alkyl sulfates and mixtures thereof; (b) from 0.5% to 4%, by weight, of an amine :elected from the group consisting of ( I } primary amines having the formula RlRzR3N wherein R1 and Rz are both H, R3 is a C4-Cle alkyl or R4X(CHZ)n, X is -O-, -C (O) NH-, or -NH-, R4 is a C4-C1g alkyl, and n is between 1 to 5; (ii) tertiary amines having the formula RlRzR3N wherein Rl and R2 are each independently a Cl-Cg alkyl or Rs I
-y CH2-CH-O~H
wherein x is from 1 to 5, R3 is a C4-Cle alkyl or R4X (CH2) n, X
is -O-, -C (O) NH-, or -NH-, R4 is a C6-Cle alkyl, n is between 1 to 5, and RS is H or Cl-CZ alkyl; and (iii) mixtures thereof; and (c) a nonionic surfactant selected from the group consistincl of polyhydroxy fatty acid amides, amine oxides and mixtures thereof; and (d} an aminopolyphosphonate selected from the group consisting of ethylenediamine tetramethylene phosphonic acid, diethylene triamine pentamethylenephosphonic acid and mixtures thereof; wherein the weight ratio of component (b) to the anionic surfactant selected from the group consisting of alkyl alkoxy sulfates, alkyl sulfates and mixtures thereof is from 1:10 to 1:40 and the weight ratio of anionic surfactant to nonionic surfactant is from 5:1 to 2:1.
In another preferred embodiment there is provided a liquid detergent composition comprising: (a) from 10% to 65a, by weight, of an anionic surfactant selected from the group consisting of alkyl alkoxy sulfates, alkyl sulfates and mixtures thereof; from 0.5o to 4%, by weight, an amine selected from the group consisting of (i) primary amines having the formula R1R2R3N wherein R1 and RZ are both H, and 3b wherein R3 is a C4-C18 alkyl or R4X (CH2) n, X is -O-, -C (O) NH-, or -NH-, R4 is a C4-Cl8 alkyl, and n is between 1 to 5; (ii) tertiary amines having the formula R1R2R3N wherein R1 and RZ
are each independently a C1-Ce alkyl or Rs i -C CH2-CH-O~H
wherein x is from 1 to 5, R3 is a C4-C18 alkyl or R4X (CH2) ", X is -O-, -C' (O) NH-, or -NH-, R4 is a C6-Cla alkyl, and n is between 1 to 5, and RS is H or Cl-C2 alkyl; and (iii) mixtures thereof; (c) water in an amount of less than 30% by weight of the composition; (d) nonionic surfactant; and (e) an enzyme selected from the group consisting of annylases, lipolases, proteases and mixtures thereof; wherein the weight ratio of anionic surfactant to nonionic surfactant is from 5:1 to 2:1.
The invention is further directed to a method of pretreating fabrics with the detergent composition described herein.
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 Clp-C2q alkyl or hydroxyalkyl group having a C10-C2q alkyl: component, preferably a C12-Clg alkyl or- , hydroxyalkyl, more preferably C12-C15 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 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 propoxylatedsulfates 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 C12-C15 alkyl polyethoxylate (1.0) sulfate (C12-C15E(1.0)M), C12-C15 alkyl polyethoxylate (2.25) sulfate (C12-C15E(2.25)M), C12-C15 alkyl polyethoxylate (3.0) sulfate --(C12-C15E(3.0)M), and C12-C15 alkyl polyethoxylate (4.0) sulfate (C12-C15E(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 C10-C2q hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-Clg alkyl component,.more preferably a C12-C15 alkyl or hydroxyalkyl, and M is H or a canon, 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 amines - as - used herein refer to primary= -or tertiary amines which is believed to form a mixed micelle with the c anionic surfactant and where the carbon chain length of the alkyl group is equal or greater than C6.
Suitable primary amines for use herein include amines according to the formula RlR2RgN wherein.Rl and R2 are-both H, R3 is a Cq--Clg~ preferably-C6-C12 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 S 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 .forntula RlR2RgN wherein Rl and R2 are both H t Rg is RqX(CH2)n, X is -O-,-C(O)NH- or -NH-~ Rq is a Cq-Clg preferably C6-C12 alkyl chain and Rq may be branched or straight, n is between 1 to S-. Preferred amines according to the formula- herein above 3-isopropoxypropylamine, 3-(2-methoxyethoxy)-propylamine and 2-(2-aminoethoxy)-ethanol, Cg-Cip 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 RlR2RgN wherein neither R1 nor R2 is H, R1 and --R2 are C1-Cg alkylchains or Rs -C CH2-CH-p~H
whereby n is between 2 to 4 and x is between 1 to 6;
Rg is either a Cq-Clg~ preferably Cg-C12 alkyl chain, or R3 is RqX(CHZ)n, whereby X is -O-, =C(O)NH- or -=NH- Rq is a Cq-Clg~
n is between 1 to 5, and R5 is H or C1-C2-alkyl.
' Rg, Rq are preferably Cg-C12 alkyl chains and may be straight or branched ; Rg 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-hydroxyethyl)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 trademark ADOGEN, the long chain alkyldimethyl amines marketed under the trademark ARMEEN and the ethoxylated amines marketed under the trademark 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 t=imes ethoxylated($EROL 28), lauryl amido propylamine and coco amido propylamine.
While not intending to be limited by theory, it is believed that tlae amine cosurfactant and anionic surfactant herein form complexes which enhance packing of the surfactants at the oil/water interface, thereby lowering interfacial tension and improving detergency. The amine surfactants would be at least partially protonated in the product and during the wash thus can form positively charged species capable of complexing with the anionic surfactant.
Another aspect of the invention relates to the surprising finding that low amounts of certain primary and/or tertiary amines of the present invention provide suds control to the detergent compositions formulated therewith.
The amounts in which the amines are used for controlling the suds are from 0.1 to 10$, preferably from 0.1 to 5~, most preferably from 0.5 to 4$ by weight of the detergent composition.

Detergent-ingredi-ents 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--caw 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.-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 Cg-C2p hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a C1-C6 hydrocarbyl, preferably an alkyl, or-combination thereof, and-M is a 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 Clp-C16 -alkyl, and R4 -is methyl, ethyl or -isopropyl. Especially preferred are the methyl ester sulfonates wherein R3-is Clp-C16 alkyl.

Othez anionic s~srfactants useful for detersive purposes car.
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-C2q olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of th.e pyralyzed product of alkaline earth metal citrates, e.g., a.s described in British patent specification No. 1,082,179, Cg-C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide): alkyl glycerol sulfonates, fatty acyl gly~~erol sulfonates, fatty oleoyl glycerol sulfates, alkyl p',henol 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 C12-Clg monoesters) and diesters of sulfosuccinates (:especially saturated and unsaturated C6-C12 diesters), sulfates of alkylpolysaccharides such as the sulfates of al~:ylpolyglucoside (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 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.
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 td 14, more preferably from 12 to 14. The hydrophobic Ilipophilic) moiety may be aliphatic oraromatic 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 pref-erred nonionic surfactants of this type are the Cg-C15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C12-C15 primary alcohols containing 5-8 moles ofethylene oxide per mole of alcohol.
Another class of nonionic surfactants comprises alkyl polyglucoside compounds 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 508 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 - CIO) - N(Rl) - Z, wherein R1 is H, or R1 is C1_q hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture -thereof, R2 is Cg-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 redur_ing 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) (PO) (BO) N(0) (CH R' ) .qH 0 (I) x y z 2 2 2 In general, it can be seen lthat the structure (I) provides one long-chain moiety R (EO) (PO) (BO) and two x y z short chain moieties, CH2R'. R' is preferabry selected from hydrogen, methyl and -CH20H. In general R1 is a primary or branched hydrocarbyl moiity which can be saturated or unsaturated, preferably, R is a primary alkyl moiety. When x+y+z = 0, RI is a hydrocarbyl moiety having chainlength of from about 8 to about 1B. 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, R1 - Cg-Clg, 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.
The invention also encompasses amine oxides wherein x+y+z is differen i 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: E0 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 ADMOXM16 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 R' - H, there is some :Latitude with respect to having R' slightly larger than H. Specifically, the invention further encompasses embodiments wherein R' ~, = CH20H, such as hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)ami.ne 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 o:ne long-chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alk;yldimethylammonium halogenides, and those surfactants having the fonaula [R2 (OR3) yl [RQ (OR3) yJ 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 t:he group consisting of -CH2CH2-. -CH2CH(CH3)-, -CH2CH(CH20H)-, -CH2CH2CH2-, and mixtures thereof; each R4 is selected f=om the group consisting of-C1-Cq alkyl, C1-Cq hydroxyalkyl-, benzyl ring structures formed by joining the two Rq groups, -CH2CHOH-CHOHCOR6CHOHCH20H wherein R6=is any hexose or hexose polymer having a molecular weight--lessthan about s 1000, and hydrogen when y is not 0; RS is the same as Rq or is an alkyl chain wherein the total number of carbon atoms of R2 plus RS is-not more than about 18; each y is from 0 to--about 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 RlR2RgR4N+X- (i) wherein R1 is Cg-C16 alkyl, each of R2, R3 end Rq is independently Cl-Cq alkyl, C1-Cq hydroxy alkyl, benzyl, and -(C2Hq0)xH where x has a value from 1 to 5, and X is an anion.-Not more than one of R2, Rg or Rq should be benzyl.
The preferred -alkyl chain length for R1 is C12-C15 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 R2Rg and Rq 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;
C12-15-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)q ammonium chloride or bromide R'O 96112000 PC1'IUS94J11779 choline esters (compounds of formula (i) wherein R1 is -CH2-O-C(O)-C12:14 alkyl and R2R3R4 are methyl).-Other cationic shrfactants usefuh herein are also described in U.S. Patent 4,228,044, Cambre, issued October 14, 1980.
a When included therein, the laundry detergent compositions of the present invention typically comprise from 0.5$- to about ' S$, preferably from about 18 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 far liquid compositions is based on dodecenyl succinic acid and citric acid.
Detergency builder salts are normally included in amounts of from 38 to 508 by weight-of the composition preferably from 58 to 308 and most usually from 58 to 258 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 508, preferably less than 308, more -preferably less than 208 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 ons e .
compositi ar made % by w~aight of the detergent compositions A H C D

C12-C15 Alkyl eth.oxylated sulfate21 11.0 1~
16.0 Octylamine 0.5 1 0.5 0.5 C12-C14 alkyldimethyl amine oxide3 - 2 2 C12-C15 Alkyl sulfate 5 17.0 -C12-C14 N-methyl glucamide 5 5.0 4.0 5 C12-C14 fatty alcohol ethoxylate 1 1 1 1 C12-C16 Fatty aced 7 7 4 6 Citric acid anhydrous 4.5 4.5 3 4 Diethylene triam:ine penta methy-lene phosphoric acid 1.0 1.0 2.0 2.0 Monoethanolamine 8 8 0.5 9 Sodiumhydroxide 1 ~, 1 2.5 1 Propanediol 12.7 14.5 13.1 10.0 Ethanol 1.8 1.8 4.7 5.4 Amylase (300FQ~tU/g) 0.1 0.1 0.1 0.1 Lipolase (100I4~1tJ/gl 0.15 0.15 0.15 0.15 Protease (34g/1) 0.5 0.5 0.5 0.5 Endo-A (5000 CEVU/g) 0.05 0.05 0.05 0.05 CarezymeM(5000 CEW/g) 0.09 0.09 0.09 0.09 Terephthalate-based polymer 0.5 0.5 - 0.3 Boric acid 2.4 2.9 2.8 2.8 Sodium xylene sulfonate - - 3 -DC 3225C 0.03 0.04 0.03 0.04 2-butyl-octanol 0.03 0.04 0.04 0.03 Branched silicone 0.3 0.3 0.3 0.3 Water b Minors ----- -up 100$------to 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 His(2-hydroxyethyl)coco amine, Oleyl amine 7E0, lauryl amido propylamine and coco amido propylamine.

Claims

What is claimed is:

1. A liquid detergent composition comprising:
(a) from about 5% to about 25%, by weight, of an anionic surfactant selected from the group consisting of alkyl alkoxy sulfates, alkyl sulfates and mixtures thereof;
(b) from 0.5% to 4%, by weight, of an amine selected from the group consisting of (i) primary amines having the formula R1R2R3N wherein R1 and R2 are both H, R3 is a C4-C18 alkyl or R4X(CH2)n, X is -O-, -C(O) NH-, or -NH-, R4 is a C4-C18 alkyl, and n is between 1 to 5;
(ii) tertiary amines having the formula R1R2R3N wherein R1 and R2 are each independently a C1-C8 alkyl or wherein x is from 1 to 5, R3 is a C4-C18 alkyl or R4X (CH2)n, X
is -O-, -C(O)NH-, or -NH-, R9 is a C6-C18 alkyl, n is between 1 to 5, and R5 is H or C1-C2 alkyl; and (iii) mixtures thereof; and (c) a nonionic surfactant selected from the group consisting of polyhydroxy fatty acid amides, amine oxides and mixtures thereof; and (d) an aminopolyphosphonate selected from the group consisting of ethylenediamine tetramethylene phosphonic acid, diethylene triamine pentamethylenephosphonic acid and mixtures thereof;
wherein the weight ratio of component (b) to the anionic surfactant selected from the group consisting of alkyl alkoxy sulfates, alkyl sulfates and mixtures thereof is from 1:10 to 1:40 and the weight ratio of anionic surfactant to nonionic surfactant is from 5:1 to 2:1.

2. A liquid detergent composition according to claim 1, wherein said primary amine is selected from n-alkylamines, C8-C14 alkyl amidopropyl amines, C10-C12 alkyl propylene diamines, 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 group consisting of tertiary amines wherein R1 and R2 are both wherein x is between 1 to 5, R3 is a C4-C18 alkyl chain and R5 is H or CH3.

5. A liquid detergent composition according to claim 1, wherein the amine is a tertiary amine selected from C4-C12 alkyl dimethyl amines and amines of the formula wherein R4 is C8-12 alkyl and n is 2 or 3.

6. A liquid detergent composition according to claim 1, wherein the anionic surfactants are selected from the alkyl ethoxylated sulfate and C12-C15 alkyl sulfate.

7. A liquid detergent composition according to claim 1, wherein the nonionic surfactant is C12-C14 alkyl dimethyl amine oxide.

8. A liquid detergent composition according to claim 1, further comprising an ingredient selected from the group consisting of other surfactants, builders, enzymes and mixtures thereof.

9. A liquid detergent composition according to claim 1, which is free of linear alkylbenzene sulfonate surfactant.

10. A liquid detergent. composition comprising:
(a) from 10% to 65%, by weight, of an anionic surfactant selected from the group consisting of alkyl alkoxy sulfates, alkyl sulfates and mixtures thereof;
(b) from 0.5% to 4%, by weight, an amine selected from the group consisting of (i) primary amines having the formula R1R2R3N wherein R1 and R2 are both H, and wherein R3 is a C4-C18 alkyl or R4X (CH2)n, X is -O-, -C: (O)NH-, or -NH-, R4 is a C4-C18 alkyl, and n is between 1 to 5;
(ii) tertiary amines having the formula R1R2R3N wherein R1 and R2 are each independently a C1-C8 alkyl or wherein x is from 1 to 5, R3 is a C4-C18 alkyl or R4X (CH2)n, X is -O-, -C (O) NH-, or -NH-, R4 is a C6-C18 alkyl, and n is between 1 to 5, and R5 is H or C1-C2 alkyl; and (iii) mixtures thereof;
(c) water in an amount of less than 30% by weight of the composition;
(d) nonionic surfactant; and (e) an enzyme selected from the group consisting of amylases, lipolases, proteases and mixtures thereof;
wherein the weight ratio of anionic surfactant to nonionic surfactant is from 5:1. to 2:1.

11. A liquid detergent composition according to claim 10, wherein the nonionic surfactant is selected from the group consisting of polyhydroxy fatty acid amides, amine oxides and mixtures thereof.

12. A liquid detergent composition according to claim 10, wherein the nonionic surfactant comprises an amine oxide having a melting point in the range of from 30°C to 90°C.

13. A method of pretreatment of fabrics comprising contacting the fabric with a liquid detergent composition according to claim 10.

14. A method of controlling suds in liquid detergent compositions comprising less than 30%, by weight, water; an amine oxide having a melting point in the range of from 30°C
to 90°C; and an anionic surfactant selected from the group consisting of alkyl alkoxy sulfates, alkyl sulfates and mixtures thereof, comprising the step of adding to the detergent compositions from 0.1% to 10%, by weight, of an amine selected from the group consisting of:
(i) primary amines having the formula R1R2R3N wherein R1 and R2 are both H, R3 is a C4-C18 alkyl or R4X (CH2)n, X is -O-, -C (O)NH-, or -NH-, R4 is a C4-C18 alkyl, and n is between 1 to 5;
(ii) tertiary amines having the formula R1R2R3N wherein R1 and R2 are each independently a C1-C8 alkyl or wherein x is from 1 to 5, R3 is a C4-C18 alkyl or R4X (CH2) n, X
is -O-, -C (O) NH-, or -NH-, R4 is a C6-C18 alkyl, n is between 1 to 5, and R5 is H or C1-C2 alkyl, and (iii) mixtures thereof, wherein the weight ratio of the amine to the anionic surfactant selected from the group consisting of alkyl alkoxy sulfites, alkyl sulfates and mixtures thereof is from 1:5 to 1:100.

15. A method according to claim 14, wherein the detergent composition further comprises a nonionic surfactant selected from the group consisting of polyhydroxy fatty acid amides.

16. A liquid detergent composition according to claim 1, further comprising from about 1% to about 3%, by weight, cationic surfactant.

17. A liquid detergent composition according to claim 10, further comprising an aminopolyphosphonate selected from the group consisting of ethylenediamine tetramethylene phosphonic acid, diethylene triamine pentamethylenephosphonic acid and mixtures thereof.

18. A liquid detergent composition according to claim 10, further comprising from about 1% to about 30, by weight, cationic surfactant.