CA2203268A1 - Low sudsing liquid detergent compositions - Google Patents

Abstract

The present invention relates to liquid detergent compositions containing a nonionic surfactant system, said surfactant system comprising one or more surfactants selected from the group of Guerbet nonionic surfactants having formula (I) wherein R1 and R2 are independently C3-C22 alkyl groups, m is 2 to 4, n is greater than 0 and R3 is a hydrogen or a C1-C22 alkyl group.

Description

LOW SUDSING LIQUID
DETERGENT COMPOSITIONS

Field of the invention The present invention relates to detergent compositions having controlled sudsing profile. More particularly, the invention is directed to detergent compositions containing one or more nonionic surfactants selected from the group consisting of Guerbet nonionic surfactants.

~ackground of the invention Detergent compositions useful fcr cleaning purposes, such as laundering of fabrics, have commonly utili2ed a variety of nonionic surfactants. However, said surfactants tend to be high sudsing.

2 PCTrUS95/13576 This problem has been addressed in the prior art by the incorporation of suds suppressing systems in such conventional nonionic detergent mixture compositions. Suds suppresslng systems include for example suds suppressing agents such as silicone. However, suds suppressing systems can be difficult to maintain as a dispersion in liquid compositions and are difficult to process. In addition silicone anti-foam agents are expensive.
Therefore, it is an object of the present invention to provide detergent compositions comprising nonionic surfactants, said composition having a controlled sudsing profile.

It has now been found that this can be achieved by formulating a detergent composition comprising a Guerbet nonionic surfactant.
An advantage of the present invention is that the compositions provide increased hydrophobic greasy stain removal.
Another advantage of the present invention is that the surfactants are easier to formulate due to the increased solubility of the surfactant. Furthermore, said compositions are easier to formulate as so-called 'concentrated' compositions because of the significant reduction of conventional suds suppressing agents. In addition the compositions of the present invention are cheaper to formulate.

Another advantage of the compositions of the present invention is that the liquid detergent compositions are phase stable.
The term "Guerbet" surfactant as used herein refers to branched surfactants derived from 2-alkyl-alkanols.

Guerbet surfactants are known in the art. EP 254 208 discloses a low sudsing surfactant mixture comprising linear W O96/12782 PCTrUS95/13576 and/or branched nonionic surfactants. However, there is no specific mention of Guerbet nonionic surfactants.

DE 40 21 265 discloses the use of Guerbet alcohols as suàs suppressing agents. There is no mention of Guerbet nonionic surfactants.

WO 92/20768 discloses the combination of dialkylethers and Guerbet nonionic surfactants (C16-C20 EO1_s) as a suds suppressing system.

Summary of the invention The present invention relates to detergent compositions containing a nonionic surfactant system, said surfactant system comprising one or more surfactants selected from the group of Guerbet nonionic surfactants having the following formula :
IRl R2-lC-CH20 ~CmH2mO) R3 wherein R1 and R2 are independlently C3-C22 alkyl groups, m is 2 to 4, n is greater than 0 and R3 is a hydrogen or a C1-C22 alkyl group. Preferably, n is between l to 14, more preferably between 1 to 10, most preferably between 3 and 7.

Detailed description of the invention The present invention relates to detergent compositions containing a nonionic surfactant system, said surfactant system comprising one or more surfactants selected from the group of Guerbet nonionic surfactants having the following formula :

R2-C-CH2O (CmH2mO)nR3 H

CA 02203268 l997-04-2l wherein R1 and R2 are independently C3-C22 alkyl groups, m is 2 to 4, n is greater than 0 and R3 is a hydrogen or a Cl-C22 alkyl group. Preferably, n is between l to 14, more preferably between 1 to 10, most preferably between 3 and 7.
All amounts, ratios and percentages are given by weight of the total composition unless otherwise stated.

The detergent compositions preferably comprise at least 1%, more preferably from 1% to 70% and most preferably from 25~ to 40% by weight of the nonionic surfactant system as described herein.
Preferably, the Guerbet nonionic surfactant is present in the nonionic surfactant system in levels from 1%-100%, preferably from 10-90%, more preferably from 30-70~ by weight of the nonionic surfactant system.
Suitable non Guerbet nonionic surfactants for use in the nonionic surfactant system include those produced by condensing ethylene oxide with a hydrocarbon having a reactive hydrogen atom, e.g., a hydroxyl, carboxyl, or amido group, in the presence of an acidic or basic catalyst, and include compounds having the general formula RA(CH2CH2O)nH
wherein R represents the hydrophobic moiety, A represents the group carrying the reactive hydrogen atom and n represents the average number of ethylene oxide moieties. R typically contains from about 8 to 22 carbon atoms. They can also be formed by the condensation of propylene oxide with a lower molecular weight compound. n usually varies from about 2 to about 24.
A preferred class of nonionic ethoxylates is represented by the condensation product of a fatty alcohol having from 12 to 15 carbon atoms and from about 4 to 10 moles of ethylene oxide per mole or fatty alcohol. Suitable species of this class of ethoxylates include: the condensation product of Cl2-C15 oxo-alcohols and 3 to 9 moles of ethylene oxide per mole of alcohol; the condensation product or narrow cut C14-C15 oxo-alcohols and 3 to 9 moles of ethylene oxide per moie W O96/12782 PCTAUS95/1~576 of fatty (oxo) alcohol; the condensation product of a narrow cut C12-C13 fatty~oxo)alcohol and 6,5 moles of ethylene oxide per mole of fatty alcohol; and the condensatlon products of a C10-C14 coconut fatty alcohol with a degree of ethoxylation (moles EO/mole fatty alcohol) in the range from 4 to 8.
Other suitable non Guerbet nonionic surfactants are semi-polar nonionic surfactants including water-soluble amine oxides containing one alkyl or hydroxy alkyl moiety of from about 8 to about 28 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxy alkyl groups, containing from 1 to about 3 carbon atoms which can optionally be joined into ring structures.

Also suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula R2 - C(O) - N(Rl) - Z, wherein R1 is H, or Rl is C1.4 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 C11_1s 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.

The compositions according to the present invention provide improved hydrophobic greasy soil removal on soils such as make-up, spaghetti sauce, shoe polish and other similar stains, while at the same time having a controlled sudsing profile.

WO96/12782 PCT~S95/13576 Detergent Ingredients In another embodiment of the present invention, a detergent composition is provided comprising the surfactant system of the present invention mixed wlth detergent ingredients. A wide range of surfactants can be used in the detergent composition of the present invention.
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.

ANIONIC SURFACTANTS

Suitable anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)mSO3M wherein R is an unsubstituted Clo-C24 alkyl or hydroxyalkyl group having a Clo-C24 alkyl component, preferably a Cl2-C20 alkyl or hydroxyalkyl, more preferably Cl2-Clg 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 propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include 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 Cl2-Clg alkyl polyethoxylate (l.0) sulfate (Cl2-C18E(l 0)M)~ Cl2-Clg alkyl polyethoxylate (2.25) sulfate (Cl2-ClgE(2.25)M), Cl2-Clg alkyl polyethoxylate (3.0) sulfate (Cl2-ClgE(3.0)M), and Cl2-Cl8 alkyl polyethoxylate (4.0) sulfate (Cl2-ClgE(4.0)M), wherein M is conveniently selected from sodium and potassium.

Suitable anionic surfactants to be used are alkyl ester sulfonate surfactants lncluding linear esters of Cg-C20 carboxylic acids (l.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Cil 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(SO3M) - C(O) - oR4 wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a C1-C6 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 C1o-C16 alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is Clo-C16 alkyl.
Other suitable anionic surfactants include the alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C1o-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C1o-C20 alkyl component, more preferably a C12-C1g 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.s. methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). Typically, alkyl chains of C12-C16 are ~ preferred for lower wash temperatures (e.g. below about 50C) WO96/12782 PCT~S95/13576 and Cl6_1g alkyl chains are preferred for hlgher wash temperatures (e.g. above about 50C).

Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the preser.t 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-C20 linear alkylbenzenesulfonates, Cg-C22 prlmary of secondary alkanesulfonates, C8-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 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl 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 C12-C18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C6-Cl2 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2O)k-CH2COO-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 an-:l 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).

CA 02203268 l997-04-2l WO96/12782 PCT~US95/13576 When included thereln, the laundry detergent composi~ions of the present invention typically comprise from about 1~ to about 40~, preferably from about 3~ to about 20~- by weight of such anionic surfactants.

NONIONICS

Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, wlth the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide~ In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 5 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include IgepalTM CO-630, marketed by the GAF Corporation;
and TritonTM X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
The condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant systems of the present invention.
The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Preferred are the condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with from about 2 to about 10 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include TergitolTM 15-S-9 (the WO96/12782 PCT~S95/13576 condensation product of C11-C1s linear alcohol wlth 9 moles ethylene oxide), Te-gitolTM 24-L-6 NMW (the condensatlon product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C14-C1s linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-6.5 (the condensation product of C12-C13 linear alcohol with 6.5 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C14-C1s linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-4 (the condensation product of C14-Cls linear alcohol with 4 moles of ethylene oxide) marketed by Shell Chemical Company, and KyroTM EOB (the condensation product of C13-Cls alcohol with 9 moles ethylene oxide), marketed by The Procter ~ Gamble Company.
Also useful as the nonionic surfactant of the surfactant systems of the present invention are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside). The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-3-, 4-, and/or 6- positions on the preceding saccharide units.
Optionally, and less desirably, there can be a polyalkylene-oxide chain joining the hydrophobic moiety and the polysaccharide moiety. The preferred alkyleneoxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms. Preferably, the alkyl WO96112782 PCT~US95113576 group is a straight chain saturated alkyl group. The alkyl group can contain up to about 3 hydroxy groups and/o_ the polyalkyleneoxlde chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
The preferred alkylpolyglycosides have the formula R20(CnH2nO)t(glYcosyl)x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groùps contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms;
n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position).
The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4-andtor 6-position, preferably predominately the 2-position.
Although not preferred, the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant of the nonionic surfactant systems of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the WO96/12782 PCT~S95/13576 water solubility of the molecule as a whole, and the llquid character of the product is retained up to the point where the polyoxye~hylene content lS about 50~ of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.
Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention, are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80~ by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM
compounds, marketed by BASF.
Preferred for use as the nonionic surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are C8-C14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and Cg-C18 alcohol ethoxylates ~preferably Cln avg.) having from 2 to 10 ethoxy groups, and mixtures thereof.
Highly preferred nonionic surfactants are polyhydoxy fatty acid amide surfactants.
Also suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula R2 - C (O) - N(Rl) - Z, WO96/12782 PCTrUS95/13576 wherein R- l5 :~, or Rl is C1_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl c- a mixture thereof, R2 is Cs-31 hydrocarbyl, and Z is 2 polyhydroxyhydrocarbyl having a llnear hydrocarbyl chain with at least 3 hyàroxyls directly connected to the chain, or an alkoxylated derivative thereof.
Preferably, R1 is methyl, R2 is a straight C~ 5 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.
When included in such laundry detergent compositions, the nonionic surfactant systems of the present invention act to improve the greasy/oily stain removal properties of such laundry detergent compositions across a broad range of laundry conditions.
The laundry detergent compositions of the present invention may also contain ca~ionic, ampholytic, zwitterionic, and semi-polar surfactants, as well as nonionic surfactants other than those already described herein.
Preferred cationic surfactant systems include nonionic and ampholytic surfactants. 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][R4(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(CH2OH)-, -CH2CH2CH2-, and mixtures thereof; each R4 ls selected from the group consisting of Cl-C4 alkyl, C1-Cq hydroxyalkyl, benzyl ring structures formed by joining the two R4 groups, -CH2CHOH-CHOHCOR6CHOHCH20H whereln R6 is any hexose or hexose polymer having a molecular weight less than abou~
1000, and hydrogen when y is not 0; R5 is the same as R4 or is an alkyl chaln wherein the total number of carbon a~oms of R2 WO96/12782 PCT~S95/13576 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 compatlble anion.
Preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula :

RlR2R3R4N+X- ( i ) wherein R1 is C8-C16 alkyl, each of R2, R3 and R4 is independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and ~C2H40)XH where x has a value from 2 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 R1 is C12-C1s 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;
C12_1s 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 R1 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.

CA 02203268 l997-04-2l When included therein, the laundry detergent compositions of the present invention typically comprise from 0~ to about 25~, preferably from about 3~ to about 15~ by weight of such cationic surfactants.
Ampholytic surfactants are also suitable for use in the laundry detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g.
carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35, for examples of ampholytic surfactants.
When included therein, the laundry detergent compositions of the present invention typlcally comprise from 0~ to about 15%, preferably from about 1~ to about 10% by weight of such ampholytic surfactants.
zwitterionic surfactants are also suitable for use in laundry detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 98, for examples of zwitterionic surfactants.
When included therein, the laundry detergent compositions of the present invention typically comprise from 0~ to about 15~, preferably from about 1~ to about 10~ by weight of such zwitterionic surfactants.
Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties se:Lected from the group consisting of alkyl groups and hydroxyaLkyl groups containing from about 1 to about 3 carbon atomsi water-solubie pho5phine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atomsi and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula R3(oR4)XN(o)(R5)2 wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from about 8 to about 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from O to about 3; and each R5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include Clo-Clg alkyl dimethyl amine oxides and Cg-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
When included therein, the laundry detergent compositions of the present invention typically comprise from Q# to about 15~, preferably from about 1~ to about 10# by weight of such semi-polar nonionic surfactants.
The present invention further provides laundry detergent compositions comprising at least 1~ by weight, preferably from about 3~ to about 65~, more preferably from about 10# to about 25~ by weight of total surfactants.

The compositions according to the present invention may further comprise a builder system. Any conventional builder system is suitable fo- use herein including aluminosllicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly J 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 succinate2-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.
The detergent composition according to the present invention may optionally contain bleachlng agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When present, bleaching agents will typically be at levels of from about 1~ to about 30~, more typically from about 5~ to about 20~, of the detergent CA 02203268 l997-04-2l WO96/12782 PCT~S95/13576 composi-lon, especially for fabric laundering. If present, the amount of bleach activators will typically be from about 0.1~ to about 60~, more typically from about 0.5~ to about 40~
of the bleaching composition comprising the bleaching agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning or other cleaning purposes that are now known or become known.
The bleaches suitable for the present invention can be activated or non-activated bleaches.
Bleaches suitable for the present invention include peroxygen bleaches. Examples of suitable water-soluble solid peroxygen bleaches include hydrogen peroxide releasing agents such as hydrogen peroxide, perborates, e.g. perborate monohydrate, perborate tetrahydrate, persulfates, percarbonates, peroxydisulfates, perphosphates and peroxyhydrates. Preferred bleaches are percarbonates and perborates.
The hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process. Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.
Other peroxygen bleaches suitable for the present invention include organic peroxyacids such as percarboxylic acids.
Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,35q, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
A preferred percarbonate bleach comprises dry partlcles havlng an average particle size in the range frcm about 500 micrometers to about 1,000 micrometers, nct more than about 10~ by weight of said particles being smalier than about 200 micrometers and not more than about 10# by weight of said particles being larger than about 1,250 micrometers.
Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
Mixtures of bleaching a~ents can also be used.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator. Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao ~et al, and U.S. Patent 4,41~,934.
The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.
Highly preferred amido derived bleach activators are those of the formulae:

R1N(R5)C(o)R2C(o)L or R1C(o)N(R5)R2C(o)L

wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach actlvator as a consequence of the nucleopAilic attack on the bleach activator by the perhydrolysis anion. A
preferred leaving group is phenyl sulfonate.

WO96/12782 PCT~S9S/13576 Preferred examples of bleach ac~ivators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, ~6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, incorporated hereln by reference.
Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge e~ al in U.S.
Patent 4,966,723, issued October 30, 1990, incorporated herein by reference. A highly preferred activator of the benzoxazin-type is :
o C
~ "C ~

Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:

R6--C--N~ ,C H2 1l wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyi valerolac~am, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl vale-olactam and mixtures thereof. See also U.S. Patent 4,545,784, iss~ed to CA 02203268 l997-04-2l wos6ll2782 PCTAUS95/13576 Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest includes photo activated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25~, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
If deslred, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat.

5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos. 549,271A1, 549,272A1, 544,440A2, and 544,490A1; Preferred examples of these catalysts include MnIV2(u-0)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2tPF6)~, MnIII2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclono-nane)2-(Cl04)2, MnIV4(u-0)6~1,4,7-triazacyclononane) 4 (C104) 4, MnIIIMnIV4(u-O)l(u-OAc)2-(1,4,7-trimethyl-1,4,7-triazacyclononane)2(Cl04)3, MnIV(1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S.
Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455;
5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147;
5,153,161; and 5,227,084.
As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million o the active bleach catalyst species in the aqueous washing l1quor, and will preferably provide from about 0.1 ppm to about 700 r ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.

WO96/12782 PCT~S95/13576 The detergent composition acco-ding to the present invention may comprise amines. Such amines will generally correspond to r the formula :
Rl ~ R3 R~
wherein R1 is C6-C22 alkyl, alkenyl, cycloaliphatic or polycyclic group which may be substituted with up to three hydroxyl or phenyl groups and which may optionally be interrupted with up to 12 ethylene oxide moieties;
wherein R2 and R3 are each H or C1-C1g straight or branched chain alkyl or alkenyl groups which may be substituted with up to 12 ethylene oxide moieties; and wherein R1 and R2 may be taken together to form an imidazoline group of the structure:
N
N

wherein R4 is Cg - C1g alkyl.
Preferably in the above formulas, R1 is C6-C1g alkyl; R2 and R3 are each C1-C4 alkyl, optionally interrupted with 1 or 2 ethylene oxide moieties; and R4 is C1o - C16 alkyl.
Amines of the above formulas, as indicated, are generally known as surfactant amines. Such materials are described in greater detail in Kirk-Othmer; Encyclopedia of Chemical Technology, Fourth Edition, Volume 2, "Fatty Amines," Pages 405-425 (1992). This article is incorporated herein by reference.
Suitable primary amines, i.e., those wherein, in the above formulas, R2 and R3 are both hydrogen, include 1-hexylamine, 1-octylamine, laurylamine, palmitylamine, stearoylamine, oleoylamine, coconutalkylamine, tallowalkylamine, 6-amino-1-hexanol; 3-isopropoxypropylamine, 3-(2-methoxyethoxy)-propylamine, 2-(2-aminoethoxy)-ethanol and cyclohexylamine.
Suitable secondary amines, i.e., those wherein, in the above formulas, only one of R2 and R3 is hydrogen, ir.clude WO96112782 PCTrUS9~/13576 dicoconutalkylamine, di-n-dodecylamine, di-n-hexadecylamine, di-n-octadecylamine, and ditallowalkylamine.
Suitable tertiary amines, i.e., those wherein, in the above formulas, neither R2 nor R3 is hydrogen, include coconutalkyldimethylamine, dimethyloleylamine, di-n-decylmethylamine, dicoconutalkylmethylamine, tri-n-octylamine, tri-n-dodecylamine, hexadecyltris(ethyleneoxy)dimethylamine, tallowalkylbis~2-hydroxyethy])amine, stearoylbis(2-hydroxyethyl)amine, and oleoylbis(2-hydroxyethyl)amine.
Suitable imidazolines useful herein are those of the formula:

R~ I

C2H~OH

wherein R4 is Cg - Cl3 alkyl. Such materials are commercially marketed under the trade name VARINE.
Suitable polycyclic amines include those based on rosin acids. Examples of such amines are those of the formula:

Me`~ N~O~(EO~

wherein x and y range from l to 3. Amines of this type are marketed under the trade name POLYRAD.
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 l-hexylamine, l-octylamine, n-dodecyldimethylamine ~ARMEEN DMl2D) and bis-hydroxyethylcoconutalkylamine (ETHOMEEN C/12).

WO96/12782 PCTrUS95/13576 Without being bound by theory, it is believed that amines of the foregoing type are protonated under the pH conditions of use for the detergent compositlons herein. The resulting cationic protonated amine species then interacts with the oleoyl sarcosinate, and perhaps other anionic surfactants, to form a lipophilic surfactant pair. This in turn leads to greater surface absorptivity and superior detergency for greasy/oily soils. The alkylamines useful herein, which generally have pKa's 9-11, can also provide buffering capacity for the detergent compositions in which they are used.

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.

The detergent compositions according to the invention can be in liquid, paste, gels, bars or granular forms. Granular compositions according to the present invention can also be in "compact form", i.e. they may have a relatively higher density than conventional granular detergents, i.e. greater than about 600 g/l; in such case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate "compact" detergents typically comprice not more than 10 filler salt.

Preferably, the liquid compositions according to the present invention are in "concentrated form"; in such case, the liquid detergent compositions according to the present 1nvention 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.

WO96/12782 PCTrUS95/13576 Said concentrated products provlde advantages to the consumer, who has a product which can be used in lower amounts r and to the producer, who has lower shipping costs.

J The liquid compositions are expecially 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 addltive 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, skin etc., for example laundry detergent compositions and 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.

W O96/12782 2~ PCT~US95/13576 .~
~ o ~ ~ o ~ ".~ o _, r '., a r~ ~ r~ I I I I , h I I l-- ~ ", ,~, O ,_, o ~ o ~ ~ o "~ O ,,, .,-r. ~
~
C" r ~ O ,,, D.
~ aC
.c aS a ,.-. In , , , o ,, . ~
o a u u~
~ O

o ~
r J' m rrl I , ~
r O
. ~
V ~ , ~, o ~ O _, ,~ a ~a R h a o ~n a) ~ o c -1 a) a~ I r~
s~ r,- >1 I
a) _ ~ Y v ~ ~ `' a) o ro o ~ ~a ra ro ~ u ro ~D r, r) .C
o I O --I ~
-~ C' r,o I I Z r,~l Z ~ I ~ ~ V ~
:~ ~ ~ rv r.~ ~r.~ ~ ~ r.~ V _1 ~ - r_) V _I V _I r ) _ V ~ r,r~ r~
-1 rOr_)r3r_) rv rv r~ r~ C ) a~ ~; ~ r~
v _ _ v V V r v -- r,~ r cl~ r ~ ~ r~
n xr~ xr~ r- .r ~ ~ _I
2 G ~ O r Or ~ . , r ~ I I h ~ `` ~ ~ C ) -- ~--r.~lr~ V
rv V-- V--J rv _ rv I_ D~ r~ r" - ~n ~ rn r.~
~CC V

W 096/12782 27 PCT~l'S95/13576 r ~ f~r--f O f. ~ O rD _ Lf~
o O O
f-~f" O r ~r) ,o~ f~ ~r f~
, ,~ o O O _! o o r,r~ f.~ O f- f~ fD r f'~
_ --~ O O --~ o o f~ rr~ O 1~ r~ -f ~ r f, r, o O ~ o O ~
,_ ~.

L f7 ~ f' ~ --~ o o ~ o o --' O ~ ~ ~ L"
O o O O

L~ f." O ~-- ~ o fD ,, ~f, _I o ' ~ O O

f'') r~-~ O r-- ~ _1 fD r r O O O ~ o o f~f~ '. ~ O X) _I ,"
O O f~ ~I O O

V
~l C
- u ~ 5 0 ~, - fl ~ ~ C5~ f '- ~ r~ 3 ,_ _f. f f Z f, f 3 L
O
0 '-I fV O ~ ~
~l 'C J-~ O O ~ O n ~ f'J~f "~ , r~-, O f_ O r~` I
.. f~~" ~ f qr f !
--I fV V ~ _I f~ f~ -- ,_ ~ ~ r~S I ~ rl) fll G_ fv ~ ~ ~- ~. f~ . ~ -.
:~ _I f-' >- 0 0 ~ ~ O
.C '. ~ X ,C ~I ~v -- ~ ~ f~
V _ ~ o ~ ~`V V O o 'V o .¢ O f.~l f 5~ C fV ~ O _ ~ V ~n 0 ~ fl.C 0 .'1'- C, 0 ~
a, ~: z ,~ ~ 3 --W O96/12782 PCTrUS95/13576 Q, ~, o U~ ~ ~ o o ~ U~ o ~
._ a C
,S, ~ ~ o V ~ ~
., I

U ~ ~ ~ ~ O
c C
a o s~
v a m o V
U V

C s ~ ~ ~ O
O V O
V ~
._ O
t,. V
C .,, V
o ' ~ 3 C U~ X o a~ o s -~
a~ E
~ O o ~
V U ~ ~ C
a~ ~. o C o ~ V~
U ~ V
~ 3 ~ c , O ~ u~ a _I o c ~ ~ u~ a~
~ ~ t-- o ~ ~ V
o o ~ ~ o u ~c o o S
a~ v v ~ ~ a) _I ~ o O ~ 1 V
~ ~ o ~ . ~ - ~ o o o Q
c ~ ~ ~ ~ ~ ~ - m o ~
z s

Claims (8)

1. A detergent composition comprising a nonionic surfactant system, said nonionic surfactant system comprising one or more of a surfactant selected from the group of Guerbet nonionic surfactants having the following formula :

wherein R1 and R2 are independently C3-C22 alkyl groups, m is 2 to 4, n is greater than 0 and R3 is a hydrogen or a C1-C22 alkyl group.

2. A detergent composition according to Claim 1 wherein n is between 1 to 14, more preferably between 1 to 10, most preferably between 3 and 7.

3. A detergent composition according to Claims 1-2 wherein the Guerbet nonionic surfactant is present in the nonionic surfactant system in levels from 1-100%, preferably from 10-90%, more preferably from 30-70% by weight from the nonionic surfactant system.

4. A detergent composition according to Claims 1-3 further comprising a nonionic surfactant selected from the polyhydroxy fatty acid amides.

5. A detergent composition according to Claims 1-4 wherein the nonionic surfactant is C12-C14 N-methyl glucamide.

6. A detergent composition according to Claims 1-5 wherein the anionic surfactant is selected from an alkyl ethoxylated sulfate and/or alkyl sulfate.

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

8. Use of a detergent composition according to Claims 1-7 for pretreatment of fabrics.