CA1299962C - Liquid detergent composition - Google Patents

Abstract

LIQUID DETERGENT COMPOSITION

Abstract of the Disclosure High sudsing liquid detergent composition containing anionic surfactant and symmetrical polymeric nonionic surfactant at ratios of anionic:nonionic from 500:1 to 1:2. Such low levels of polymeric nonionic surfactant relative to the level of anionic surfactants provide a means whereby the polymeric nonionic surfactant prevents grease from coalescing in suspension or redepositing at the grease surface on dishware without interfering with the effectiveness of the anionic surfactant in cutting grease away from the surface of dishware. The anionic surfactant forms stable complexes with the polymeric surfactant for improved grease handling. The symmetrical block structure of the polymeric nonionic surfactant provides liquid detergent compositions with superior grease cutting and grease capacity.

Description

LIQUID DETERGENT COMPOSITION
Eugene J. Pancheri Young S. Oh and Rodney M. Wise Technical Field and Background Art The invention relates to aqueous high sudsing liquid deter-gent compositions containing specified amounts and types of surfactants especially useful in the washing of tableware, kitchenware and other hard surfaces.
~he compositions of this invention have superior ability to handle grease.
The performance of a deterger~t con position for cleaning tableware and kitchen utensils is evaluated by its ability to handle grease. The detergent solution shou~d readily remove grease and minimize its redeposition.
There is continuing need for impro~lred compositions and - - methods wmch can be emplayed during, dlshwashing operations to ~
- ~ - improve the appearance o~ kitchen-utensifs and articles. Such compositions and methods should provide improved removal of grease in conventional dishwashing soil removal operations while maintaining the sudsing attributes of an acceptable dishwashing detergent composition.
Summary of the Invention The present invention comprises a high sudsing liquid deter-gent composition containing by weight:
(a) from about 5% to about 50% anionic surfactant;
(b) from about 0.19~ to about 12% of polymeric surfactant having the formula sel,ected from,the group consisting -- of AnBAm, BnP~Bm, BA, B and mixtures- thereof - 30 wherein each B Is a hydrophobic group, each A is a - ~ hydrophi!ic group; each n and m are either 0 or an integer from one to about 50; the sum of n + m is from one to about 50; the molecule contains from about 5 to about 1,000 ether linkages; when the formula is BA, B
contains from about 5 to about 500 ether linkages; when the formula is B, the ratio of -CH2- groups to ether ., linkages is at least about 2.1:1 and less than about 3:1; the molecular weight is from about 400 to about 60 000; and the percentage of tC2H4O~ groups in the molecule is less than about 90%;
s (c) from 0% to about 10~ of a suds stabllizlng nonionic surfactant selected from the group consistlng of fatty acid amides trialkyl amine oxides and mixtures thereof;
(d ~ from 0% to about 10% of a detergency builder selected from inorganic phosphates inorganic polyphosphates inorganic silicates and inorganic carbonates organic carboxylates organic phosphonates and mixtures thereof;
le) from 096 to about 15% alkanol containing from one to about six carbon atoms; and (f) from about 20~ to about 90% water said composition containing sufficient magnesium ions to neutralize at least.
- ~ about 10% of said anionic-surfactant when less than-about ~0%
of the anionic surfactant is an~ alkylpolyethoxylate sulfate surfactant containing from about ~ to about ten ethoxy groups per molecule on the average (or there is no betaine surfactant present); said composition having a pH of greater than about six when the composition contains said alkylpolyethoxylate sulfate surfactant; said composition having a viscosity of greater than about 100 cps or being substantially free of alkylpolyethoxylate detergent surfactants when the amount of anionic surfactant is less than about 20% (and there is no betaine surfactant present).
Dishware glassware and ~ther tableware and icitchenware are . washed in water- soluttons of the detergent composition -- 30 generally at a weight concentration of from~aboutØ05% to.about 0.4% of tfie composition in water at-a temperaturq of from about 60F to about 120F.
Detailed Descri tion of the Invention P
The liquid detergent compositions of the present invention contain two essential components:

(a) anionic surfactant which when there is no betaine surfactant present is either a magnesium salt andl or an alkylpolyethoxylate sulfate containing an average of from about ~ to about ten ethoxy groups per molecule, said average being computed herein by treating any alkyl sulfate surfactant as an alkylpolyethoxylate sulfate containing 0 ethoxy groups, as described hereinbefore, to provide good sudsing, and preferably a low interfacial tension; and (b~ the polymeric surfactant, which improves grease handling .
Optional ingredients can be added to provide various perfor-mance and aesthetic characteristics.
Anionic Surfactant The compositions of this invention contain from about 5% to about 50% by weight of an anionic surfactant or mixtures thereof - - ~ preferably~con,srising at least ~about-5%,-more preferably- at~least about 8%, and most preferably more than about 1096 of an alkyl polyethoxylate (polyethylene oxide) sulfate having from about 10 to about 20, preferably from about 10 to about 16 carbon atoms in the alkyl group and containing from about ~ to about t0, preferably from about 1 to about 8, most preferably from about 1 to about 6 ethoxy groups on the average. Preferred compositions contain from about 20% to about 40% of anionic surfactant by weight.
Most anionic detergents can be broadly described as the water-soluble salts, particularly the alkali metal, alkaline earth - metal, ammonium or amine ~ salts, of organic sulfuric reaction products having In their molecular structure an~ alkyl radical ~ 30 containing from about 8 to about 22 carbon atoms and a radical - selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. Included in the term alkyl is the alkyl portlon of acyl radicals. Examples of the anionic synthetic deter-gents which can form the surfactant component of the composi-tions of the present invention are the salts of compatible cations, i299962 e.g. sodium, ammonium, monoethanolammon3um, diethanolammonium, triethanolammonium, potassium and/or, especially, magnesium cations with: alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms), 5 alkyl benzene, or alkyl toluene, sulfonates, in which the alkyl group contains from about 9 to about ~ 5 carbon atoms, the ali~yl radical being either a straight or branched aliphatic chain;
paraffin sulfonates or olefin sulfonates in which the alkyl or alkenyl group contains from about 10 to about 20 carbon atoms;
10 sodium C10 20 alkyl glyceryl ether sulfonates, especially those ethers of alcohols derived from tallow and coconut oil; coconut oil fatty acid monoglyceride sulfates and sulfonates;
alkylphenolpolyethylene oxide ether sulfates with from about 1 to about 10 units of ethylene oxide per molecule on the average in 15 which the alkyl radicals contain from 8 to about 12 carbon atoms;
- the reaction prpducts of fatty acids esterified with is~th\onic acid --- ~ where-, for=example, the fatty acids are deri~ed from coconut oil, fatty acid amides of~a methyl tauride in which the fatty acids, for example, are derived from coconut oil; and beta-acetoxy- or 20 beta-acetarrido-alkanesulfonates where the alkane has from 8 to 22 carbon atoms.
Specific examples of alkyl sulfate salts which can be em-ployed in the instant detergent compositions include sodium, potassiùm, ammonium, monoethanolammonium, diethanolammonium, 25 triethanolammonium, and magnesium: lauryl sulfates, stearyl sulfates, palmityl sulfates, decyl sulfates, myristyl sulfates, tallow alkyl sulfates, coconut alkyl sulfates, C12 15 alkyl sulfates - and mixtures of these surfactants. Preferred alkyl sulfates - Include the C12_15 alkyl sulfates.
- 30 Suitable alkylbenzene, or alkyltoluene, sulfonates include the-alkall metàl (llthiun~, sodium, andlor potassium), alkaline earth (preferably magnesium), ammonium and/or alkanolàmmonium salts of straight, or branched-chain, alkylbenzene, or alkyltoluene, sulfonic acids. Alkylbenzene sulfonic acids useful as precursors 35 for these surfactants include decyl benzene sulfonic acid, undecyl 129~962 benzene sulfonic acld, dodecyl benzene sulfonlc acld, tridecyl benzene sulfonic acid, tetrapropylene benzene sulfonic acid and mixtures thereof. Preferred sulfonic acids as precursors of the alkyl-benzene sulfonates useful for compositions herein are those s in which the alkyl chain is linear and averages about 11 to 13 carbon atoms in length. Examples of commercially avallable alkyl benzene sulfonic acids useful in the present invention include "Conoco"SA 515 and SA 597 marketed by the Continental Oil Com-pany and "Calsoft LAS 99" marketed by the Pilot Chemical Compa-10 ny.
The preferred anionic surfactants herein, which are essentialif there are no, e.g., magnesium ions or betaine surfactant present, are alkylpolyethoxylate sulfates having the formula RO(C2H4O)xSO3M wherein R is alkyl, or alkenyl, of from about 15 10 to about 20 carbon atoms, x is rom about ~ to about ten on - the average, treating alkyl suifates as if they had 0 ethoxy - - groups, pre~erabiy fronr about ~ to about eight-, most preferabiyfr~m about one to about six, and M is a water-soluble compatible cation such as those disclosed hereinbefore. The 20 alkylpolyethoxylate sulfates useful in the present invention are sulfates of condensation products of ethylene oxide and mono-hydric alcohols having from about 10 to about 20 carbon atoms.
Preferably, R has 10 to 16 carbon atoms. The alcohols can be derived from natural fats, e.g., coconut oil or tallow, or can be 25 synthetic. Such alcohols can be reacted with from about ~ to about 20, especially from about one to about 14, and more especially from about one to about eight, molar proportions of ethylene oxide and the resulting n~ixture of molecular species is - sulfated and neutralized. - -There should be more than about 10%, preferably more than about 15% of such molecules~ containing one to lO ethoxilate groups calculated as a percehtage of the total anionic surfactant in the composition. When these molecules are mixed with alkyl sulfates which are treated as containing 0 ethoxylate groups, the 35 computed average degree of ethoxylation should be more than A * Trademark ** Trademark ~;~99962 about 0. 5, preferably more than about 0. 6 . One can use a similar approach in computing the minimum desired amount of the alkyl polyethoxylate sulfate which should be present when ad-mixed with any anionic surfactant. E.g. the other anionic sur-5 factant can be treated as if it were an alkyl sulfate to computethe average degree of ethoxylation.
Specific examples of alkylpolyethoxylate sulfates of the present invention are sodium coconut alkylpolyethoxylate (3) ether sulfate, magnesium C12 15 alkylpolyethoxylate (3) ether sulfate, 10 and sodium tallow alkylpolyethoxylate (6) ether sulfate. A
particularly preferred example is a water soluble, e.g.
magnesium~ C12_13 alkylpolethoxylate (1) ether sutfate.
Preferred alkyl polyethoxylate sulfates are those comprising a mixture of individual compounds, said mixture having an average 15 alkyl chain length of from about 10 to 16 carbon atoms and an - - average deg-ree. of ethoxylation of from about 1 to about 8 -moles - -of ethylene oxide. : - ~ ~ ~ ~ -For use in completely soft water, the compositions should contain magnesium ions, and/or at least about 10~, preferably at 20 least about 1596 by weight of the anionic surfactant, of the preferred alkyl polyethoxylate sulfates described hereinbefore. It is preferred that the compositions of this invention, including those that contain the preferred alkylpolyethoxylate sulfates, also contain magnesium and/or calcium ions, most preferably magnesium 25 ions, to act as cations for a portion of the anionic surfactant. If the composition is to be used primarily in water containin~3 more than about 2 grains/gal, of hardness, added magnesium may not be essential. In use, from about- 10% to about 100~, preferably - ~- from about 20~ to~about 90%, of the anionic surfactant ~hould-be 30 the magnesium salt.
The formulation of anionic surfactant systems that will re-duce the interfacial tension is well within the skill of the typical detergent formulator. For the purposes of this invention, the surfactant system minus the polymeric surfactant should pre-35 ferably reduce the interfacial tension to below about 2~ dynelcm, -~ 1299962 , preferably below about 2 dyneslcm, agalnst triolein at a concen-tration of o. 2% and a temperature of 115F (46C) in a spinning drop Tensiometer. Interfacial tension is lowered by any deter-gent surfactant, but the efflciency can be improved by selection 5 of surfactants which have longer alkyl chain lengths, use of cations such as magnesium which mlnimize charge effects when anionic surfactants are used, and use of anionic surfactants combined with cosurfactants like trialkylamine oxides which form cornplexes with the anionic surfactant. A more complete 10 discussion of such effects can be found in Milton J. Rosen, Surfactants and Interfacial Phenomena, 149-17~ (1978) The Polymeric Surfactant Preferably, the compositions of the present invention contain 15 from about 0.1% to about 10%, more preferably frorn about ~% to - about 4~, and most preferably from abPut 1/2%to about 2~ of the polymeric surfactant descri~ed generically: hereinbefore and discussed in detail hereinafter.
In the generic formula for the polymeric surfactant set forth 20 hereinbefore, B is preferably a polypropylene oxide group, containing more than about 5 propylene oxide groups, which can contain some ethylene oxide groups, n and m are preferably from about 1 to about 2 and the sum of n+m is from about 2 to about 4, the molecule contains from about 20 to about 500 ether 25 linkages, and the molecular weight is from about 1000 to about 40, 000.
The polymeric surfactant is preferably represented by the ' - ' formula~
I R1 ~R2Otn ~R3O~mly[ R~] ~
30 wherein each R is selected from t~e group conslsting of hydrogen, alkyl groups containing from one to about' 18 carbon atoms, acyl groups containing from two to about 18 carbon atoms, -SO"M, -SO3M, -COOM, -N(RS)2 -- O, -N(R5)3~1, amide groups, pyrrolidone groups, saccharide groups, and hydroxy groups in 35 which each M is a compatible cation and each R5 is either an alkyl A

or hydroxy alkyl group containing from one to about four carbon atoms; wherein each R2 or R3 is an alkylene group containing from two to about six carbon atoms with no more than about 9o~
of said molecule comprising R2 and R3 groups containing two carbon atoms; wherein R4 is selected from the group consisting of alkylene groups containing from one to about 18 carbon atoms and having from two to about six valences, polyhydroxyalkylene oxide groups wherein each alkylene group has from one to about six hydroxy groups and contains from three to about eight carbon atoms and there are from two to about 50 hydroxyalkylene oxide groups and ~rom two to about 50 hydroxy groups, (=NR2N=), hydrogen, =NtR2NH~X, polyester groups containing from one to about 20 ester linkages and each ester group containing from about 4 to about 18 carbon atoms; wherein n is from o to about 500, m is from 0 to about 500, n + m is from about 5 to about 1000, x is from a~out 2 to-about 50, and y is-from one to about - ~ 50 and equal to the valences of ~ R~: wherein the molecular v~eight .
is from about 400 to about 60,000; and wherein the tR2O~ and the ~R30t groups are interchangeable;
While not wishing to be bound by theory, it is believed that the polymeric surfactant functions by forming complexes with the hydrophilic portions of the anionic surfactants, thereby minimizing the ability of the anionic surfactants to leave a micelle or other interfacial region once formed. Therefore, long terminal hydrocarbon groups are not preferred, and are not acceptable when the formula is of the BA type. Long terminal hydrocarbons pu!l the polymer into any oil phase, thereby minimizing the number of anionic surfactant molecules that~ arc stabJlized.
~ Simibrly, if the hydrophillc portion of the molecule is too hydr-30 ophilic, the molecu~e is pulled into the aqueous phase too far.
The molecu1e should be balanced between hydrophobicity and hydrophilicity and have enough ether and/or amine linkages ~299962 g spread throughout the structure to complex the anlonic surfactant. The anionic surfactant also must be one that wlll form the complex. Magnesium cations, ether linkages, and amine or ammonium groups form stable complexes with the polymerlc 5 surfactants.
Preferably the surfactant contains a hydrophillc group comprising polyethylene oxide andlor ethylenelmlne groups containing from about 1 to about 500 ethylene oxlde and/or ethyleneimine derived moieties. Sulfonate or sulfate groups, can 10 also be present. The polymeric surfactant also contains at least one hydrophobic group, preferably comprising polyalkylene oxide groups wherein the alkylene contains from three to about six, most preferably three, carbon atoms and the molecular weight is from about 400 to about 60,000. The alkylene groups containing fronm about 7 to about 18, preferably fro~. about 10 to about 18, - carbon atoms can also be used,- b~t preferably only short chain - relatively nonoieophilic~alkyl or ~cyl groups containing iess tt~n about ten carbon atoms are pendant on the polymeric surfactant.
Preferred surfactants are block copolymers comprising one or 20 more groups that are hydrophilic and which contain n-ostly ethylene oxide groups and one or more hydrophobic groups which contain mostly propylene oxide groups attached to the residue of a compound that contained one or more hydroxy or amine groups onto which the respective alkylene oxides were polymerized, said 25 polymers having molecular weights of from about 400 to about 60,000, an ethylene oxide content of from about 10% to about 90%
by weight and a propylene oxide content of from about 10% to ~ :about iO~ by weight. ~
- Preferred surfactants are those in which propylene oxlde is-30 condensed with an amine, especlally ethylenediamlne,to provide a ~ hydrophobic base having a molecular welght of from about 350 to-about 55,000, preferably from about 500 to about 40,000. This hydrophobic base is then condensed wlth ethylene oxide to pro-vide from about 10% to about 90%, preferably from about 20% to 35 about 80% ethylene oxide. Reverse structures in which the A

~29996Z
- lo -ethylene oxide Is condensed first are also deslrable. These structures are especially easy to formulate Into desirable single phase liquid compositions.
Similar structures in which the ethylenediamine is replaced 5 by a polyol, especially propylene glycol, or glycerine, or condensation products of glycerine, are also deslrablq.
In similar compositions, the polypropylene glycol portion can be replaced by an alkyl, or alkylene group containing from about S to about 18, preferably from about 8 to about 16 carbon atoms lo and the polyethylene oxide groups can be replaced either totally, or, preferably in part, by other water solubilizing groups, especially sulfate and sulfonate groups.
Specific examples of such compounds include:
A. R tOCH2CH~ R2 tOCH2CH2t~0Rl 15 where: - R is H, or CH3, or CH3(CH2)n, or unsaturated - analogues ~
- - where - n=i-17 ~~ ~~
- x ,y=2-500 - R2=nothing or O(CH2)z or unsaturated analogues of these where z=1-18 B. CH
R3R4toCH2CHtAR4R3 where: - R is sulfate or sulfonate - R4 is nothing; ~OCH2CH2tB; or other groups capable of bonding to propylene oxide, including sulfate or sulfonate groups.
- A is 5-500 - B ~ A12 - Specific preferred examples of such compounds include:
2CH23~0(CH2~tOCH2CH2~H
3~CH2~(OCH2CH21x+y O(CH2) CH3 C. C~H3 NaO3S~OCH2CHtA OS03NacH
NaO3S~OCH2CH2tB (OCH2CH~A (CH2cH2~53Na where: - x, y, z, n, A, B are as previously defined.

A

Suds Stabilizing Nonionic Surfactant The compositions of this invention contain from 09~ to about 1096, preferably from about 1% to about 8%, of suds stabilizing nonionic surfactant or mixtures thereof.
Suds stabilizing nonionic surfactants operable in the instant compositions are of two basic types: fatty acid amides and the trialkyl amine oxide semi-polar nonionics.
The amide type of nonionic surface active agent includes the ammonia, monoethanol and diethanol amides of fatty acids having an acyl moiety of from about 8 to about 18 carbon atoms and represented by the general formula:
Rl-CO-N(H)m(R OH)2_m wherein R1 iS a saturated or unsaturated, aliphatic hydrocarbon radical having from 7 to 21, preferably from 11 to 17 carbon ator.~s; R2 represents a methylene or ethylene group; and m is 1 or 2. SQecific examples of said amides are co~onut fatty acid -- - - monoethanol am,de and dodecyl fatty acid diet~anol amide. T~ese acyl moieties may be derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum, or hydrogenation of carbon monoxide by the Fischer-Tropsch process . The monoethanol amides and diethanolamides of C1 2 14 fatty acids are preferred.
Amine oxide semi-polar nonionic surface active agents com-prise compounds and mixtures of compounds having the formula:
R

Rl (C2H40)nN ~0 - - whereirl Rl is an alkyl, i-hydroxyalkyl, 3-hydroxyalkyl, - or 3Q 3-alkoxy-2-hydroxypropyl radical in whiclr the alkyi and alkoxy, respectively, contain from about 8 to about 18 carbon atoms, R2 and R3 are each a methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl radical and n is from 0 to about lO. Particularly preferred are amine oxides of the formula:

-~ 1299962 R1 _ N ~0 wherein R1 ;5 a C10 14 alkyl and R2 and R3 are methyl or ethyl.
The preferred sudsing characteristics of the compositions of the invention are those which will provide the user of the product with an indication of cleaning potential in a dishwashing solution.
Soils encountered in dishwashing act as suds depressants and the presence or absence of suds from the surface of a dishwashing solution is a convenient guide to product usage. ~ixtures of anionic surfactants and suds stabilizing nonionic surfactants are utilized in the compositions of the invention because of their high sudsing characteristics, their suds stability in the presence of food soils and their ability to indicate accurately an adequate level of product usage in the presence of soil.
- - In preferred embodiments of the invention, the ratio of anionic surfactants to suds stabilizing nonionic surfactants in the composition will be in a molar ratio of fro~ about 11-:1 to about 1:1, and more preferably from about 8:1 to about 3:1.
Other Optional Surfactants The compositions of the invention can desirably contain optional surfactants, especially ampholytic andlor zwitterionic surfactants. However, when the level of anionic surfactant is less than about 20%, the composition should not contain any substantial an~unt of conventional nonionic surfactant, e.g., an alkylpolyethoxylate, in addition to the polymeric surfactant.
Large amounts of conventional nonionic surfactants, e.g., more than about three or four percent, tend to harm the slldsing ability of the composition. ~ ~ - - ~
When larger amounts ( ~ 20%) of anionic swfactan~s are present it is sometimes deslrable to have a low level, up to about 5%, of conventional nonionic surfactants "conventional nonionic surfactants- are, e.g., C8_18 alkyl polyethoxylates (4-15) or C8_15 alkyl phenol polyethoxylates (4-15).

i299962 An;pholytic surfactants can be broadly described as deriva-tives of aliphatic amines which contain a long chain of about 8 to 18 carbon atoms and an anionic water-solubilizing group, e.g.
carboxylate, sulfonate or sulfate. Examples of compounds falling within this definition are sodlum-3-dodecylamino propane sulfonate, and dodecyl dimethylammonium hexanoate.
Zwitterionic surface active agents operable in the Instant compositlon are broadly described as internally-neutralized deriva-tives of aliphatic quaternary amnlonium and phosphoniun;. and tertiary sulfonium compounds in which the aliphatic radical can be - straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon aton s and one contains an anionic water solubilizing group, e . g ., carboxy, sulfo, sulfato, phosphato, or pnosphono.
Highly preferred are betaine detergent surfactants which - - - synerqistically interact -with the polyrr,eric surfactant to_ provide- -in-.proved~grease handling. ~ ~ ~-The Betaine Detergent Surfactant The betaine detergent surfactant has the general formula:
(+) (~) R-N(R6)2R7Coo wherein R is a hydrophobic group selected from the group con-sisting of alkyl groups containing from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms, 25 alkyl aryl and aryl alkyl groups containing a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon atoms, and simtlar structures interrupted by amido or ether llnkages: each R6-is an-alkyl~group contiining from one :
to about 3 carbon atoms; and R -Is an-alkylene group containing 30 -from one to about 6 carbon atoms.
Examples of preferred betaines are dodecylamidopropyl dimethylbetaine; dodecyldimethylbetaine; tetradecyldin~ethyl-betaine; cetyldimethylbetaine; cetylamidopropyldimethylbetaine, tetradecyldimethylbetaine, tetradecylamidopropyldimethylb~etaine, 3s and docosyldimethylammonium hexanoate and mixtures thereo~.

8etaine surfactants are unique ingredlents that provide exceptional benefits. When betaine surfactant and polymeric surfactant are combined with any anionic surfactant with, or without magnesium ions being present, superior grease holding 5 benefits are provided.
Betaines containing a C1 2 14 alkyl provide a much bigger benefit when combined with polymeric surfactant than when used by themselves.
The betaine is preferably present at a level of from about ~%
10 to about 15% by weight of the formula, preferably from about 1~
to about 10%, most preferably from about 196 to about 8~. The ratio of anionic detergent surfactants to the betaine is from about 1 to about 80, preferably from about 1 to about 40, more preferably from about 2 to about 40.
When betaines are present, the composition should preferably have a ratio ~f betaine to polymeric surfactant of more than about -- 7:1,~preferably more than~abo~t 9:1. ~ ~ ~ ~ --Solvents Alcohols, such as ethyl alcohol, and hydrotropes, such as 20 sodium and potassium toluene sulfonate, sodium and potassium xylene sulfonate, trisodium sulfosuccinate and related compounds (as disclosed in U.S. Patent 3,915,903) and urea, can be utilized in the interests of achieving a desired product phase stability and viscosity. Alicanols 25 containing from one to about six carbon atorr.s, especially two, and especially ethyl alcohol can be present. Ethyl alcohol at a level of fronm 0% to about 15%, preferably from about 1% to about 1- 6%, and potasslum andlor sodlum toluene! xylene, andlor cumene sulfonates at- a level of from about 1% to-abo~t ~6% can be-used In - 30 the colr.positions of the~ invention. The viscosity should be greater than about 100 centipolse; more preferably more than 150 centipoise, most preferably more than about 200 centipoise for consumer acceptance.
However the polymeric surfactant can be used to reduce the 35 viscosity and provide phase stability, e.g., when either the A
. .

preferred alkyl polyethoxylate sulfate or magnesium ions are present in the composition. For viscosity reduction, the percentage of ethylene oxide in the polymer should be less than about 70~, preferably less than about 50~. Preferred 5 compositlons contain less than about 2g~ alcohol and less than about 3% hydrotrope and preferably essentlally none while maintaining a viscosity of from about 150 to about 500 centipoise, preferably from about 200 to about 400 centipoise. If viscosity reduction is not desired the percentage of ethylene oxide in the 10 polymer should be more than about 5096, preferably more than - about 70%. The polymeric surfactant reduces viscosity ~or all water soluble anionic surfactants.
The compositions of this invention contain from about 20% to about 90~, preferably from about 30~ to about 80%, water.
15Additional Optional Ingredients - The compositions of this invention ca~ contain up to about ~ t0%, by weight~ of-deterge'ncy~builders e;ther of the organic or lnorganic type. Examples of water-soluble inorganic builders which can be used, alone or in admixture with themselves and 20 organic alkaline sequestrant builder salts, are alkali metal carbonates, phosphates, polyphosphates, and silicates. Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, potassium carbonate, sodium pyrophosphate, potassium pyrophosphate, and potassium tripolyphosphate. Examples of 25 organic builder salts which can be used alone, or in admixture with each other or with the preceding inorganic alkaline builder salts, are alkali metal polycarboxylates, e.g., water-soluble citrates,'tartrates, etc. s'uch as sodiu~i~ and:potassium citrate and - - - -sodium and potasslum tartrate. ln general, l~owever, detergency 30 bullders have lin~ited value In dishwashing detergent compositlons and use at levels above about 10% can restrict formulation flexibil-ity in liquid compositions because'of solubliity and phase stability' considerations. It is preferred that any builder used be relatively specific to control of calcium as opposed to magnesium.
35 Citrates, tartrates, malates, maleates, succinates and malonates are especially preferred.
I

The detergent compositions of thls Invention can contaln, If desired, any of the usual adjuvants, dlluents and addltlves, for example, perfu~,es, electrolytes, enzymes, dyes, antltarnishlng agents, antimicrobial agents, and the like, wlthout detracting 5from the advantageous properties of the compositions. Alkallnlty sources and pH buffering agents such as monoethanolamlne, triethanolan;ine and alkali metal hydroxides can also be utlllzed.
When the anionic surfactant is a sulfate surfactant or alkylpolyethoxylate sulfate surfactant, the pH should be above 1 0about 6, preferably above about 7 to avold hydrolysis of the ester linl<age. Also, it is desirable that the composition be substantially free of antibacterial agents such as N-trichloromethyl-thio-4-cyclohexene-1,2,dicarboximide for safety.
Eow levels of antibacterial agents that will prevent growth of 15aacteria, molds, etc. in the product, but which have essentially - no effect in use can be desirable, especially when Jow levels of ~ ~ alcohoi are~present. ~ ~ - ~- -All percentages and ratios herein are by weight unless otherwise indicated.
20The following examples are given to illustrate the composi-tions of the invention.
In the following examples, the compounds have the following definitions. E stands for an ethoxylate group and P stands for a propoxylate group.
25Name Formula MW HLB
Pluronic 1~38 E45,5 P17 E45.5 5000 30.5 "Pluronic"41~ E1 .5 P22 E1 .5 1~00 4 -"Pluronic"42 E3 5 P22 E3.5- 163P- 8 ~ "Pluronic"45~ E13 5 P22 E13.5 2400 18-- 30"Pluronic'47~ E36 5 P22 E36.5 4600 26 "Pluroriic"68 E76 P29 E76 8350 29 Pluronic 81 E3 P41.5 3 2750 2 ~PIuronic~l82~ E7,5 P41.5 7.5 3200 6 "Pluronic"85 E26 P41.5 E26 4600 16 35"Pluronic"87 E61 P41.5 E61 7700 24 i ~A
I

i299962 " Pluronlc" 88 E98 P41 S E9B 10800 28 "Pluronic"108 127 5 48 E127.5 14000 27 " Pluronic" 121 E5 P;0 E5 4400 ~5 "Pluronic"122* E11 P70 E11 5 500a 4 "Pluronic"125* E51 5 P70 Es1 5 9100 15 " Pluronic" 127 Eg9 5 P70 E99 5 12500 22 "Pluronic" 17R4 P14 E24 5 P14 2700 16 "Tetronic' 504 ~E8P8 5j4(=NCH2CH2 ) 15.5 Tetronic' 702 (E4 5j14)4(=NCH2CH2 Tetronic 704 (E12.5P14)4(=NCH2CH2N=) 5500 15 Tetronic 707 ( 47,5P14)4(=NCH2CH2N=) 12000 27 Tetronic~'902* (E6P17)4(=NCH2CH2N=) 5300 6.5 Tetronic"904* (E17P17)4(=NcH2cH2N=1 7500 14.5 " Tetronic"907* (E55P17)4(=NCH2cH2N ) 13900 26 lS " Tetronic"908 (E91P17)4(=NCH2cH2N ) 20000 30.5 " Tetronic"1307 (Et4P~4)4~=~C~2C~H2N ) 18600 ~ 23.5 Tetronic 1502 (EloP31)4( NCH2CH2N-)9000 ~--'rTetronic"1504 (E28 5P31)4(=NCH2CH2N=) 12500 13 " Tetronic' 70R4 (P~E12J5).~(=NCH2CH2N=) 5500 20 * Prepared by ~lendlng other commercially available materials.
Name Definition Compound A Polyethyleneimine (MW=600) condensed with 42 mols of polypropylene oxide followed by 42 mols of polyethylene oxide Compound B Polyethyleneimine (MW=600) condensed with 14 mols of polypropylene oxide Corr.pound C Po!yethyleneimine tMW=600) condensed with 42 - : mols of polypropylene oxide Compound D - Polyethyleneimlne (MW=600) condensed with - 98 mols of polypropylene oxide 'hurocol" WS100 " Random" copolymer of ethylene oxide (50%) and propylene oxide (50~) (MW=4600] lBASF) Compound E Pluronic 81 di-sulfated and NH~4OH neutralized Con~pound F HOtC2H4Otlg(CH2tl2O~C2HqOtl8H
PPG 4000 Polypropylene glycol MW=4000 "Pluronic" and Tetronic" are trademarks * Trademark -~299962 PEG 6000 Polyethylene glycol MW=6000 Compound G Polyethyleneimine (MW=189) acylated wlth 2 mols of coconut fatty acid and condensed with 80 mols of ethylene oxide Compound H Polyethyleneimine (MW=189) condensed with 105 mols of ethylene oxide Compound I Methyl capped hexamethylenediamine condensed with 60 mols of ethylene oxlde Compound J Triethanol amine condensed with 15 mols of ethylene oxide Compound K Triethanol amine condensed with 33 mols of ethylene oxide .. "*
Compound L Dobanol 91-10 CH3tCH2~8_1 o-tCH2CH2)10 ~H _ Corr,pour~d M C13H27CH CH2-CH - _ ~ C~ /CH2CH2OH 11 . 8 ~CH2CH2OH
Compound N CH31CH2)11_12 O-CH C~H2 OH OH
,CH3 Compound O CH3-otcH2cH2otii~tcH2cHo~H
25 HA-q30** Polyethylene glycol/polypropylene glycol heteric block copolymer (BASF) The base product contains about 5% magnesium C12 13 alkyl - sulfate, about- 23% miXed magnesium and ammonium C12 13 alkyl polyethoxylate (1) sulfate, about 2.7% C1-2_13 alkyl dimethyl amine 30 oxides about 5% ethyl alcohol, about 3% sodium toluene sulfonate, about 60% water, and the~balance ~eing- inorganic salts, minor ingredients, etc.
In the following examples, "grease cutting" is determined by the following test. A preweighed 250 cc. polypropylene cup has 35 3 cc. of a melted beef grease applied to its inner bottom surface.

*Trademark ~ A* * Trademark ~299962 After the grease has solldlfied, the cup Is rewelghed. Then a .4~ aqueous solutlon of the composltion to be tested is added to the cup to completely fill it. The aqueous solutlon has a temperature of 46C . After 15 minutes, the cup is emptied and 5 rinsed with distilled water. The eup is dried and then weighed to determine the amount of grease removal. The amount removed by the base product is indexed at 100.
In the following examples, "grease capacity" is determlned by modifying the above grease cutting test by using 10 ml of an 10 easier to remove fat which is an 80/ 20 mixture of a solid vegetable shortening and a liquid vegetable shortening, lowering the detergent concentration to about 0.2%, and soaking for 30 minutes to allow equilibrium to occur.
In the Examples "~" indicates a significant difference and the 15 figures in parentheses under the headings "Grease Capacity" and "Grease Cutting" are the number- o~ repl~cates run and averaged to give the-indicate~ test scores. ~ -~ ~ ~
In all of the Examples, the viscosity of the composition is greater than about 150 centipoise and less than about 500 20 centipoise.
EXAMPLE I
This test shows the improvement in grease capacity and grease cutting obtainable with various Pluronics.
IA
Grease Grease Capacity Cutting Total 14) (5) Base Product 1~0 ~ 100 200 ~
" + 1.3% P!uronic-127 - - - 125*- 116* 24~*
~ " +~1.3% PJuronic q7 129* - 119~ 248*
" + 1.3% Pluronic 87 ~ 123* 111* 234*
" + 1.396 Pluronic 122 124* 108* 232*
" ~ 1.39~ Pluronic q2 128* 124* 252*
" ~ 1.34 Pluronic 82 124* 120* 244*
" + 1.3~ Pluronic 125 130* 112* 242*

+Trademark + 1,3% Pluronic 45 134* 119* 253*
" + 1,3~ Pluronic 85 129* 120* 249 IB
S Grease Grease Capacity Cutting Total 13) (3) 13aseProduct 100 100 200 "+ 1.3~ Pluronic 121 113* 104 217*
10 " + 1.3% Pluronic 81112* 106 218*
" + 1.3~ Pluronic41 109 113* 222*
" + 1.396 Pluronic 85 116* 110 226*
LSDlo 10 11 15 Grease Grease - ~ - . Capacity ~tt7ng ~ Total - -: - - (3} ~2) Base Product 100 100 200 " + 1.3~ Pluronic 38 113* 102 215*
" + 1.3~ Pluronic 68 118* 101 219*
" + 1.3~ Pluronic 88 116* 93 209 " + 1.3% Pluronic 108 125* 93 218*
LSDlo 10 13 15 EXAMPLE l l This test shows the improvement obtained with various - "retronics"+
~ -Grease Grease Capacity Cutting Total (6) (5) Base Product 100 100 200 n + 1.3% Tetronic 504 108* lt6* 224*
I~ + 1.3% Tetronic 702113* 113* 226*
ll + 1.3% Tetronic 707108* 111* 219*

Trademark " ~ 1.3% Tetronic 902 120~ 104 224*
" + 1.3% Tetronic 904 108~ 99 207 " + 1.3% Tetronic 907 113* 108~ 221 " + 1.3~ Tetronic 1502 111* 108* 219 " + 1.3~ Tetronic 1504 106* lll* 217 " + 1.3% Tetronic 1307 108* 97 205 LSDl o 6 8 10 IIB
Grease Grease Capacity Cutting Totai Reps (3) (2).
Base Product 100 100 200 " + 1.3% Tetronic 908121* 87 208 EXAMPLE l l l - - This example demonstrates that reversing the order of - -additlon - of the ethylene- oxi~e and propylene oxide to create a hydrophilic center and hydrophobic ~ends provides compounds which are equally as effective as the Pluronics or Tetronics.
Grease Grease Capacity Cutting Total (4) (4) Base Product 100 100 200 " + 1.3% Pluronic 85 121* 98 219*
" + 1.3% Pluronic 17R4 125* 94 219*
" + 1.3% Tetronic 704 131~ 99 230*
" + 1.3% Tetronic 70R4 129* 96 225*
- - LSD10 - - - . 8 9 12- -- . - - - EXAMPLE IV - - - -- This example demonstrates.tha~ a polymeric surfactant with a - somewhat hydrophilic center, two . or -more intermediate hydrophobic moieties and terminal hydrophilic moieties provides almost the same benefits as the Pluronics or Tetronics.

G rease G rease Capacity Cutting Total (9) (5) Base Product 100 100 200 s " + 1.396 Pluronic 85 108* 105 213*
" + 1.3% Tetronic 704 111* 98 210*
" + 1.3~ Compound A 116* 100 216*
LSDlo 6 9 10 EXAMPLE V
This example demonstrates that a compound with a hydrophilic chain with grafted polypropylene oxide hydrophobic chains can provide grease capacity and grease cutting benefits about the same as Pluronics.
Grease Grease Capacity Cutting Total (5) (1~) -~ ~ - - . Base Product ~ - - 100- ~ - 100. 200 - ~-" + 1.3% Pluronic 85 112* 1~2 214*
" + 1.3~ Compound B111 * 92 203 " + 1.3~ Compound C109* 92 201 " + 1.3% Compound D116* 107 223*
LSDlo 7 10 12 EXAMPLE Vl This example shows that random structures of ethylene oxide 25 and propylene oxide are as effective as their analog block structures .
Grease Grease . . .Capacity C~tting Total - (4) (4) - 30 Base Product - 100 . 100 200 - " + 1.3% Pluronic 85 115* 111* 226*
" + 1.3~ Plurocol W5100 114* 106 220*
LSDlo 8 10 13 EXAMPLE Vll 35This example shows that similar structures in which anionic moieties substitute, at least in part, for polyethoxylate moieties or alkylene chains are substituted, at least in part, for polypropoxylate moieties provide benefits similar to the Pluronics.
Grease Grease Capacity Cutting Total (7) (5) Base Product 100 100 200 " + 1.3% Pluronic 65 107* 103 210 " + 1 . 3~ Compound E 114* 97 211*
" + 1 . 396 Compound F 110* 98 209 EXAMPLE Vl l l This example demonstrates that mixtures of polypropylene glycol and polyethylene glycol, and the individual materials do not provide the benefits.
Grease Grease Capacity Cutting Total (2) (2) Base Product 100 100 200- - -" + 0.65% PPG 4000(A) 102 106 208 " + 0.65% PEG 6000(B) 91 101 192 " ~ 0.65~ A + 0.65% B 99 101 200 " + 1 . 3% A 95 104 199 " + 1 . 3% B 89 98 187 LSDlo 12 13 18 EXAMPLE IX
This example demonstrates that excessively water-soluble compounds and compounds which are more like conventional - - surfactants and contaln termi~nal oleophilic hydrophobic groups do~ ~
' not provide the beneflts. ' ~ -Grease G,rease ' ' Capacity Cunlng Total ~ ~
. (6) `(4) Base Product 100 100 200 ; " + 1.3% Compound G102 98 200 ~ 35 " + 1.3% Compound H102 93 195 ~ 24 -n ~ 1.3% Compound 1 98 97 195 " + 1.3~ Compound J 99 96 195 + 1.3~ Compound K 94 93 187 I~ + 1.3% Compound L 93 95 1a8 LSDlo 7 9 11 EXAMPLE X
This example is a continuation of Example IX.
Grease Grease Capaclty Cuttlng Total (3) (3) Base Product, " 1 100 100 200 " + 1,3% Methocel A15LV 103 103 206 + 1.3% NHq C12_13E12 4 96 98 194 ~ + 1.3% NH4C12_13SO4 102 99 201 ~ + 1.3~ Cl2-l3N(cH3)2 101 106 207 " +-1.3% Gelatin (Type A) 106 96- 202 - ~ LSDlo - - ~O 11 ~ ~5' EXAMPLE Xl This example also demonstrates that other conventional 20 surfactants do not provide the benefits.
Grease Grease Capacity Cutting Total (5) (3) Base Product 100 100 200 " + 1.3% C12_13 Glucoside ~2) 102 100 202 " + 1.3% Cn monoethanol amide 104 101 205 " + 1.3~ Compound M 101 100 201 " + 1.3~"Lexaine LM ,,,2100 100 ~-200 u ~ 1.3% Compound N - 99 - 10~ -199 EX~MPLE, X l l : ' -This example shows ' that' some low molecular weight polypropylene oxldes provide the beneflt, although they do adversely affect sudsing.
~' 35 ., Trademark for methylcellulose ~rademark Grease Grease Capacity Cutting T
(9) (5) Base Product 100 100 200 " + 1.3% Pluronic 85 108* 105 213 " + 1.3% PEG 6000 105 98 203 " + 1.396 PPG 4000110* 115~ 225 LSD1o 6 9 10 EXAMPLE X l l l This example demonstrates yet another polymeric surfactant structure that is operable.
Grease G rease Capacity Cutting Total (5) (4) Base Product 100 100 200 - - '' + 1.3% Pluronic 85 112* --102 . 214*
+-1.39~ Compound O 114* ~ -- 106 220* ~ -~ LSD ~ ~ ~ ~ ~- 7 10 12 EXAMPLE X IV
This example demonstrates that increasing the amount of the polymeric surfactant, a heteric block copolymer of ethyiene oxide and propylene oxide on a glycerol base, improves Grease Capacity, but, eventually, lowers the Grease Cutting unacceptably. High levels above about 4%, and especially above about 9%, lose good grease cutting when the basic formula is optimlzed for grease cutting.
Grease Grease Capacity Cuttina Total --(3) (3) ¦- 30~ Base Product 100 i00 ~ 200 , " + 1.3% HA 430 115* 113* 228*
i " I 16% HA 430 195* 29* 225*
LSDlo 10 11 15 EXAMPLE XV
This example, like Example XIV, shows the effect of increased (Tetronic) surfactant. Again, above about 4%, there is .

" ~Z9996Z

a loss which becomes substantial before a level of about 9% is reached.
Grease Grease CapacityCutting Total (3) (3) Base Product 100 100 200 " + 0.25~ Tetronic 704112* 121~ 233 " I 0.50% Tetronic 704118~ 119* 237 " + 1.0% Tetronic 704119* 120* 239*
" + 4.09~ Tetronic 704136* 96 232*
" +-8.0~ Tetronic 704 168* 74* 242*
" I 16.0% Tetronic 704221* 47* 268*
LSD1o 10 11 15 COMPARAT IVE EXAMPLE XVI
15This example shows the effect of using twice the amount of a -- - commercial detçrgent. The Grease Capacity and Grease Cutting - ~ - - are increased, but at~ a ~much greater cost than ~s~ociated~ with the invention. - -~
GreaseGrease CapacityCutting Total Reps (4) (4) Base Product 100 100 200 Base Product (Double Usage) 140* 130* 270*
LSD1o 8 10 13 EXAMPLE XVI I
A high sudsing, light duty liquid detergent composition is as follows:
. % : -Sodium C11- 8 alkylbenzene sulfonate - - : 14.8 ~-30 Sodium C12_13 alkylioolyethoxylate (0.8) sulfate 17.3 ~12 l4 alkyldimethylbetaine- - 1.5 Pluronic 64 (as hereinafter defined) 0.175 C10 alkYIpOIyethoxylate (8-10) 4.7 Coconut fatty acid monoethanol amide 3.8 Urea 5.0 I

-`` 1299962 Ethanol 6.0 Water and minors Balance In a similar con~position the urea is replaced by 4% sodium xylene sulfonate and the ethanol Is reduced to 3.5~.
In a similar composition the Pluronic 64 is replaced by Pluronic 85.
EXAMPLE XVI I I
GreaseGrease CapacityCutting Total (2) (2) - Base Product 100 100 200 " + 4~ Lexaine LM 134* 134* 268*
~% Pluronic 85 " + 4-3/4% Lexaine LM 98 138* 236*
~ Pluronic 85 LSD10 - ~ - - 22 10 24 - ' -'rhis ~ example - demanst~rates the excellent performance of mixtures of betaine surfactants and the~ polymeric surfactants. At ratios up to about 20:1 grease cutting is improved, but the 20 optimum ratio is lower, e.g. about 9:1 or less where both grease cutting and grease capacity are improved.
EX AMPLE X I X
Viscosity Reduction Viscosity % Reducition Ethoxylate (CPS) ~ ~ Base Pr'oduct (Visco'sity = 270 centieoise) Base - - -' - " +t% Pluronic 121 - io -62 . . 30 - " +t% Pluronic 123 . 30 -40 ' " +t% Pluronic 127 70 -30 " +t% Pluronic 72 20 -55 " +t% Pluronic 75 50 -41 +t% Pluronic 77 70 -31 " +t% Pluronic 61 10 -70 +t% Pluronic 63 30 59 " +~% Pluronic 64 40 -59 " +t% Pluronic 68 80 -20 " +~% Tetronic 1302 20 -42 " +~% ~etronic 1304 40 -32 " +~ Tetronic 1307 70 -15 This example demonstrates the large reductions in viscosity obtained by adding the polymeric surfactant. The viscosity can be adjusted back up by reducing alcohol andlor hydrotrope 10 levels. As can be seen, the higher the level of ethoxylate moieties in the polymers, the less the reduction in viscosity.
Additional Materials Description The additional polymeric surfactants not defined hereinbefore are as follows:
Name Formula MW H LB
Pluronic 123- E4s,s P70 E45.5 ~ 8 - Pluronic 72 - E6 5 P36 E6 5 - 2750 ~ 6.5 ~-Pluronic 75 F23.5 P36 E23.5 4150 --16.5 Pluronic 77 E52,5 P36 52.5 6600 24.5 Pluronic 61 E2,5 P29 E2,5 2000 3 Pluronic 63 Eg P29 Eg 2650 11 Pluronic 64 E13 P29 E13 2900 15 Tetronic 1302 (Eg P24)4 (=NCH2CH2N=) 7800 5.5 TetroniC 1304 (E24 P24)4 [=NCH2C 2 ) 13.5 EXAMPLE XX
Polymer compounds are added at 0.5~, 1%, and 5% to the National Brand composition previously described, replacing water in'~the 100-part formula. Clear solutions result.
- Viscosities are measured on these compositions at 70F with a -~ 30 Brookfleld LyF viscometer, spindle No. 2, at 60 rpm.
' ' Results are snown for the three additives and are compared against equal' parts of added ethanol also'replacing water in the formula. Ethanol ts typically used to trim vtscostty and is already present tn the formula at about 4.5 parts/100 prlor to the added parts.
:1 .

Surprisingly, the addition of the polymers all drop the viscoslty further than does the added ethanol The Pluronic 61 Is even more effective at 1% than is ethanol at 5~.
Viscosity of National Brand with Added Polymers CPS Vlscosity Addit~ve Level: 0~ 0.5~ 1 ~ 5 Additive Type Compound H 370 250 220 NA
Pluronic 35 370 ~A 195 113 10 Pluronic 61 370 NA 163 83 Ethanol 370 275 240 190 In a similar manner, the national brand formula is composited with a 0.25~ level of several Pluronic polymers. Viscosities are again read as above.
15 Additive Viscosity in Centipoise at 70F
-- - None - 320 -~- Pluronic 6~ ~ 265- ~ ~ -- - ~ ~ -Pluronic 92 247 Pluronic 42 237 20 Pluronic 31 242 Note that the additive compounds provide different levels of viscosity reduction. The Compound H in the first experiment is one of the poorer (more hydrophilic) performers of Example IX
and, though effective on viscosity reduction, did not show as 25 great a benefit, The Pluronic compounds of lower HLB (lower second digit) and moderate molecular weight (first digit) are more effective. If the purpose for adding ti e polymer is to lower viscosity, lower levels provide the biggest benefit per part of ~ polymer added. - - - - - - -~ - EXAMPLE XXI
- This test was conducted in water with no hardness.
l - -Grease Grease ; CapacityCutting Total t2) l4) 35 A. Sodium coconut alkyl sulfate 100 100 200 ,j B. A + 4.5~ Lexaine IM +
0~5% Pluronic 85 215~ 1'06~ 321 C. B + MgCI2 to replace the sodium 325~ 110* 435 D. 1:1 mixture of sodium coconut s alkyl sulfate and sodium coconut alkyl polyethoxylate(1) sulfate 96 98 194 E, D + 4.5% Lexaine LM I 0.5%
Pluronic 85 300~ 90~ 390*
F, E + MgCI2 to replace the sodium 266~ 114 380 This example clearly shows that when a mixture of polymeric surfactant and betaine is used, it is not necessary to have either an alkyl polyethoxylate sulfate surfactant or magnesium ions present.
EXANIPLE XXII
- . _ Grease Grease ~~~ ~-- ~ ' - - . Capacity Cutting Total - (4) (2) National Brand 100 100 200 20 " " +1.3~ MAPEGl 6000DS 112* 99 211 +1.39v MAPEG1400 DS 107 99 206 ~1,3% MAPEG1400 DL 112~ 101 213 " " +1.3~ MAPEG1400 DO 116~ 100 216*
LSD1o 8 13 15 Definition of Polymeric Surfactants MAPEG 6000DS ldialkyl polyethoxylate) C18 E136 C18 9 %
MAPEG 400DS (dialkyl polyethoxylate) C18 Eg C18 44% E
- MAPEG 400DL (dialk'yl polyetho~ylate) C12 Eg C12 54% E
-- MAPEG 400 DO ldialkylene polyethoxyl?te) C18 Eg C~8 45% E
3~ Thls example clearly shows that alkyt groups can be used as termirial hydrophobic groups, but do not provlde the best results, especially when the h'ydrophilic portion of the molecule represents less than about 45~ of the molecular welght in compounds with saturated groups each of which Is longer than 35 about 16 carbon atoms.

A~
1 MAPEG is a Trademark . .
. . : .
.

EX~IUPLE XXIII
In this example, a differcnt type of test ~vas used to demonstrate another aspect of grease control by the detergent composltlons. ~n most cases, ~his test S~ives a ranklng betwoen formulations similar to that of the total Index value of the preceeding examples.
This test de~ermines ~he off~ctiveness ~r str~ngth of the grease emuisir~cation by ~he detergent by measuring the level of g~ease deposltion on a hydrophobic surface a~ter Its exposure ~o 10 a detergent solution to which a grease has been added. ~his test models the actual sltuation of redepositlon of greases onto later washed Items, especially plastics.
For this experiment, 2 gallons of median hardness ~vater (6 gta;nslciallon) . ~ere held a~ . loS~F, a common end-of-wash lS tempcrature for dishwater! A 0,1~ solution of the detergent product ~as made and mlld a3itation was begun. Liquid ~e~etable oil was added In 6cc ir~rrements. At totals of 18cc, 36ct, and 54cc, plastic items (3 for each grease level, 9 total) are dipped in succession into the water. After drying, the mean weight gain 20 per plastic ISem unit area is calculated ~nd indexed to a reference product.
The reference product used here is the base product. The polymeric s~rfactant is added at ~he 1~ le~el to the base, A "*" ihd;ca~es a statis~ically slgniflcant (L~Do5) reduction 25 In grease redep~sition compared to the Base Product.
The con~pounds tested hereln that were not previously defined are as follows:
Formula for P-T:
O O
., ~1 CH3(ocH2c:H2)xoc~cH2)yco(a~2c~2 )X 3 P X-8, Y-4 Q X=8,Y-14 R X-43, Y-4 5 X=43, Y=14 T X-17, Y~10 ' ~299962 FOrmUIa fOr ~ nd V:
O C~t C~3 (OCH~C~ XO(C (~)~COC~I2~;~20)Y(CH2CH20)X 3 jJ )~-16, Y=2.75 V X=7,5, Y~2.~S
DePO5;t;0n IndeX
BaSe PrOdUCt 1 00 I~ M~PEG 1540 DS ~
n n ~IAPEG 600 MO 76*
" " ~1~ MAPEC 600 I~O 75~ .
~1~ PIUrOn;C 85 . 84 Il n ~l9o Te~rOn;C ~04 107 ~1~ MethOCe1 A15LV 8B
IS " " ~1~ CDmP~Ut d E . 84 U ~ ~1% PPG 4000 64 " " ~19~ Compound F 89 ~1~ Compound i? 84 ~1~ Compound C~ 80~
" " ~1~ Compound R ~07 " 1' ~1~ Comp~und S 117 Compound T 85 Compound U 71 n n ~19o Compound V 53~
Note frO~n the above that Tetronic 704 and Compound ~ did not exc-l In ~his test, but dld PerfOrrn well in the previous exan~ples. Again, the Nletho~el polymer does n~t provide s-lfrlcient benefiS.
~lso, cer~a;n very hl9h n~Olecular weight compounds (R and S) of the ABA type do not show any adv~ntage.
OtherW;Se, all are exemplary of the in~ention.

Claims (11)

1. A high sudsing liquid dishwashing detergent composition containing, by weight:
(a) from about 5% to about 50% anionic surfactant;
(b) from about 0.1% to about 10% of polymeric surfactant selected from the group consisting essentially of:

[1] [R1(R2O)n (R3O)m]y[R4]
wherein each R1 is hydrogen, wherein each R2 or R3 is an alkylene group containing from two to about six carbon atoms with no more than about 90% of said molecule comprising R2 or R3 groups containing two carbon atoms; wherein R4 is selected from the group consisting of alkylene groups containing from one to about 18 carbon atoms and having from two to about six valences, (-NR2N=), and -N(R2NH)x, wherein n is from 0 to about 500, m is from 0 to about 500, n + m is from about 5 to about 1000, x is from about

2 to about 50, and y is from two to about 50 and equal to the valences of R4, and z is from 1 to about 6, and the product of z and x is from 2 to about 50;

[2] R1(OCH2CH2)x R2 (OCH2CH2)y OR1 where: - R1 is H, or CH3, or CH3(CH2)n, or unsaturated analogues where: - n=1-17 - each of x and y = 2-500 - R2=O(CH2)z or unsaturated analogue of these where z=1-18;

[3] where: - R3 is sulfate or sulfonate - R4 is nothing or (OCH2CH2)B
- A is 5-500 - B < A/2;

[4]
CH3(OCH2CH2)XO?(CH2)Y?O(CH2CH2O)XCH3 wherein X is from 8-17, and Y is from 4-14; and

[5] wherein X is from 7.5-16,and Y is about 2.75;
(c) from 0% to about 10% of a suds stabilizing nonionic surfactant selected from the group consisting of fatty acid amides, trialkyl amine oxides, and mixtures thereof;
(d) from 0% to about 10% of a detergency builder selected from inorganic phosphates, inorganic silicates, and inorganic carbonates, organic carboxylates, organic phosphonates, and mixtures thereof;
(e) from 0% to about 15% alkanol containing from one to about six carbon atoms; and (f) from about 20% to about 90% water, said composition containing sufficient magnesium ions to neutralize at least about 10% of said anionic surfactant when there is less than about 10% alkylpolyethoxylate sulfate surfactant containing from about 1/4 to about ten ethoxy groups per molecule in the composition on the average; said composition having a pH
of greater than about six when the composition contains said alkylpolyethoxylate sulfate surfactant; and said composition having a viscosity of greater than about 100 cps or being substantially free of alkylpolyethoxylate detergent surfactants when the amount of anionic surfactant is less than about 20%.

2. The composition of Claim 1 wherein there is from about 0.1% to about 7%
polymeric surfactant.

3. The composition of Claim 2 wherein there is from about 1/2% to about 4%
polymeric surfactant and where the anionic detergent is selected from the group consisting of sodium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, potassium and magnesium salts of alkyl sulfates containing 8-18 carbon atoms, alkyl benzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, and alkyl polyethoxylate sulfates in which the alkyl group contains from about 10 to about 20 carbon atoms and there are from about 1 to about 10 ethoxylate groups on the average, and mixtures thereof.

4. The composition of Claim 3 wherein there is less than about 2% polymeric surfactant and in which from about 10% to about 100% of the anionic surfactant is in the form of magnesium salt.

5. The composition of Claim 2 wherein there is at least about 8% of an alkylpolyethoxylate sulfate containing from about 10 to about 16 carbon atoms in the alkyl group and from about 1/2 to about 8 ethoxylates on the average; wherein there is from about 20% to about 90% of the anionic surfactant is the magnesium salt; and wherein there is from about 1/2% to about 4% of the polymeric surfactant.

6. The composition of Claim 5 containing from about 2% to about 8% of suds stabilizing nonionic surfactant.

7. The composition of Claim 2 wherein there is from about 1/2% to about 4%
polymeric surfactant and wherein the anionic surfactant comprises at least about 10% alkylpolyethoxylate sulfate in which the alkyl group contains from about 10 to about 20 carbon atoms and containing from about 1 to about 6 ethoxylates on the average, alkyl sulfates containing from about 8 to about 18 carbon atoms on the average, and mixtures thereof and wherein the suds stabilizing nonionic surfactant is an amine oxide semipolar nonionic surface active agent comprising compounds having the formula:

wherein R1 is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy groups, respectively contain from about 8 to about 18 carbon atoms, R2 and R3 are each a methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl radical and n is from 0 to about 10.

8. The composition of Claim 2 wherein there is from about 1/2% to about 4%
polymeric surfactant and wherein the anionic surfactant is selected from the group consisting of alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, alkylpolyethoxylate sulfates in which the alkyl group contains from about 10 to about 16 carbon atoms and there are from about 1 to about 6 ethoxylates on the average, and mixtures thereof.

9. The composition of Claim 8 wherein there is less than about 2% polymeric surfactant and in which the suds stabilizing nonionic surfactant is a fatty acid amide represented by the general formula:

R1-CO-N(H)m(R2OH)2-m wherein R1 is a saturated or unsaturated, aliphatic hydrocarbon radical having from 7 to 21, R2 represents a methylene or ethylene group; and m is 1 or 2 and there is from about 2% to about 8% of said fatty acid amide.

10. The composition of Claim 2 wherein there is from about 1/2% to about 4%
polymeric surfactant and containing less than about 2% alcohol and less than about 3% hydrotrope and having a viscosity of from about 150 to about 500 centipoise.

11. The composition of Claim 10 wherein there is less than about 2% polymeric surfactant and wherein the viscosity is from about 200 to about 400 centipoise.