CA1059867A - Detergent composition having enhanced particulate soil removal performance - Google Patents

Abstract

DETERGENT COMPOSITION HAVING ENHANCED
PARTICULATE SOIL REMOVAL PERFORMANCE
Robert G. Laughlin and Vincent P. Heuring ABSTRACT OF THE DISCLOSURE

Detergent compositions are disclosed incorporating combinations of specified alkoxylated zwitterionic compounds with other types of surfactants and with detergent builders to give enhanced particulate soil removal.

Description

BACKGROUND OF I'HE: INVENTION
This invention relates to detergent compositions having improved particulate soil removal capability.
More particularly, this invention relates to detergent compositions incorporating certain alkoxylated compounds which provide unexpectedly good clay soil removal.
Zwitterionic surfactants, i.e., those surface active compounds that contain both positive and negative charge centers in the same molecule while being electrically neutral, are known. Furthermore, zwitterionic surfactants in which the charge centers are separated by oxygen-containing groups are also disclosed in for example, U.S. Patent Nos. 3,668,240; 3,764,568; 3,332,875;
3,452,066; 2,781,390; 3,769,311 and 3,684,427. The latter two patents disclose zwitterionic compounds having ethylene oxide groups between the charge centers but both fail .. . .
to recognize the effect of the various structural parameters on the performance of the molecule :in removing soil, especially particulate soil.
In contrast, the present invention concerns detergent compositions incorporating into certain z~itterionic surfactants a polyalkenoxy group of a size that permits not only adsorption of the rnolecule from an aqueous system onto particulate and other soils, and the subsequent removal -of the soil by emulsification or dispersion but also the continued maintenance of the rernoved soil in suspension in the aqueous solution.
^ The applicants have found that certain alkoxylated zwitterionic surfactants in cor~ination with certain other surfactant and detergent builder materials can provide ..

unexpectedly good particulate soil removal and also good . ., ' .

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oily soil removal from hard surfaces and textile materials.
The alkoxylated, and particularly the ethoxylated zwitter-ionic compounds useful in the present invention, possess an ability to remove particulate soil that is independent of water hardness over a very wide range of Ca and Mg levels. Furthermore, this performance is relatively ; insensitive to temperature changes in the range of 70F~
140F the normal range for domestic cleaning functions.
The importance of such a development is readily apparent as it permits a high level of soil removal performance to be obtained with a range of detergent formulations. Furthermore, the nature and ievel of other components of the formulation can be controlled by the selection of an alkoxylated zwitterionic material having the appropriate level of performance.
Accordingly, it is an object of the present invention to provide detergent compositions incorporating alkoxylated zwitterionic compoun~s that have good particulate and oily soil removal performance.
Another ob~ect of the present invention is the provision of detergent compositions having improved particu-late and oily soil removal performance in both liquid and granular forms.

: .
SUMMARY OF THE VENTION
- In its broadest aspect the present invention embraces a detergent composition comprising:
A) 1% to 99% by weight of the composition of a compound having a formula selected from the group consisting of :,,, ~ 2-10 59 ~f ~?7 l2 ~;
(1) 1 1 (c2~l4o)y[c2El3(c~l3)o] R4X-: R3 wherein R] and R2 are independently selected from the group consisting of straight and branched chain Cl-C30 alkyl and alkenyl moieties, alkaryl moieties in which the alkyl -group has 1-24 carbon atoms and C4-C6 heteror-` ing entities in which two R moieties are joined . 10 with Y, R3 is selected from the group conslstlng of straight and branched chain Cl-C21 alkyl :~
-. and alkenyl moieties, alkaryl moieties in which the alkyl group has 1-16 carbon atoms, C4-C6 heteroring entities in which two R moieties ;~
are joined with Y and -(C2H4O)XH wherein x :
~. has a value of 3 20; R4 is selected from the -~
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group conslsting of Cl-C~ alkylene, C3-C~ alkenylene,

2-hydroxy propylene, 2- and 3-hydroxy butylene moieties and Cl-C4 alkarylene moieties provided that where R3 is - ~C2H40) xH then R4 is -CH2-C~2~;
Y is nitrogen or phosphorus ,o X~ is an anion ~elected from the group consisting of sulate, sulfonate and carboxylate radicals; and y and z independently have a valu~ in the xange of 0-20 10 provided that y ~ z is-an integer from 2-20 and proYided that where R3 is -~C2H4O)X~ then z = 0 and x + y > 10;
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. .` (C2H40) X--l-C~2CH2 . . ~ .
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~ . , ' : wherein Rl is selected from the group consisting : .
of linear and branched C~-C30 alkyl and al~enyl :

., radicals; R~ is selected from the group consisting ::

` of linear and branched C8-C30 alkyl. and alkenyl ~` radicals and Cl~C4 alkyl and hydroxyalkyl radicals;

2 ~ x is selected from the group consisting of sulfate and sulfonate; y and x have values in the range of .
~ 100 provided that y + x ~ 12; :.

`: M is a cation selected from the group consisting ~! of alkali metal, ammonium and alkanolammonium '. ions; and `. B) 99~ to 1~ by weight of the composition of an organic detergent.
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In the contex-t of the present invention, alkoxylated zwitterionic compounds having hydroxy substituents on the carbon atoms immediately adjacent the positive charge center and/or ~ moiety are not preferred as they are unstable in water, especially at pH's other than neutrality, and are extremely diff.icult to prepare compared to other hydroxy substituted compounds.
Preferably, the al~oxylated zwitterionic compound is one of either:
~-(N-C16 18 alkyl, N-Cl 3 alkyl, N-polyethenoxy ammonio)-; 2-polyethenoxyethane-1-sulfonate wherein the total number ` of ethylene oxide groups lies in the range 15-20 or ~-; (N-C12 18 al]cyl,N,N-di-Cl-C3 alkylammonio)-2-polyethenoxy ethane-l-sulfonate wherein the number of ethylene oxide ` groups in the polyethenoxy chain is in the range 6-12.
Descri~tion of the Drawing The Figure illustrates the sudsing characteristics ; of a series of blends of an ethoxylated zwitterionic compound (C16EZ) and an anionic cosurfactant (Cll 8LAS).
The Figure constitutes a plot of the suds height (in cms.) -- developed by the Recirculating Suds Generator (R.S.G.) as a function of time (in minutes) for C16 EZ alone, for blends of C16EZ:C11 8 LAS of 19:1, 7:1, 3:1 and 1:1 by weight and for Cll 8 LAS alone--Performance Testing In this specification the assessment of particulate - and oily soil removal performance both of detergent formulations of the invention and of comparative formulations -~ is carried out using the following procedures.
` 30 (a) Particulate soil removal testing This is carried out in a washing machine simulator - and involves a 12-minute wash cycle at 105F in ~5~

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5 . 5 or 7 grains per U. S . gallon hard water (~alculated as CaCO3) using a 3:1 or 2:1 ratio of Ca:Mg salts. The fabrics are washed, rinsed ' and tumble-dried prior to being graded on a Gardner whiteness meter. The fabric-load for particulate soil removal testing comprises a, mix~ure of white cotton, polycotton (65% DACRON /
35% cotton~, and polyester (KODEL~ swat~hes which are stained with a standardized illite 0 ~lay soil.
- The results (expressed as relative'clay removal index) for each formulation represents a percentage of the whiteness value achieved by a co~mercial synthetic detergent , standard tested at the same time under identical conditions.
This standard formulation hereinaftex designated as "A" has the following composition by weight: ~' :~
'' .Sodium C12 alkylbenzene sulphonate 7.55 '~
Sodium Tallow alkyl sulphate 9.25 ~ . .
,~ Coconut alcohol + 6 mole EO 0.60 2 0Diethanolamide 1.60 " Sodium Tripolyphosphate 50.00 Sodium Silicate solids 5,90 Sodium sulphate 14.20 Moisture 10.00 Miscell~neous 0.30 100 . 00 '' .~ .

, 8~7 (b) Grease and oil removal testinq Identical equipment and washing conditions are used to evaluate grease and oil removal performance. The fabric load comprises a mixture of ~reen polycotton ~65% DAC~O~ /35% cotton) and poly ester (KODEL ) swatches. Two triglyceride stains, namely bacon grease and vegetable oil, and two h~drocarbon-based stains, namely dirty motor oil and simulated lipid soil are employed.
Following washing and drying, the swatches are graded visually on a six-point scale and the results ., ~`~ are expressed as a percentage of the soil removal :- ' '~ achieved by the standard A uncler the same conditions.

(c) Sudsing Evaluation The evaluation of the suclsing characteristics ~: .
,, of detergent compositions is carried out using a ~ ' :!
, Recirculating Suds Generator. This apparatus basically consists of a graduated cylinder which holds the bulk of the test solution and a circulating pump ~hich is .. . , :
` 2~ connected to the base of the cylinder and which discharges to an exit ~et located in the c~linder above the level ..
.; .
of the test solution. In operation, the test solution is placed in the cylinder and continuously circulated : - .

`~ at a selected temperature~ The force of the downward`

~ directed solution from the exit jet onto the bulk of ., ~ the test solution in the graduated cylinder generates a ,; le~el os suds in the cylinder which is measured at one-minute intervals.

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` -- 7 --:~598~i7 DESCRIPTION OF THE PREFERRED EMBODIMENTS
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The compositions of the present inven~ion contain two essential components, namely the alkoxylated zwitter-ionic compound and a surfactant compound. The zwitterionic and surfactant may be present in a ratio of from 99:1 to 1:99 by weight, preferably 10:1 to 1:10 by weight, and most preferably 4:1 to 1:10 by weight depending on the nature of the zwitterionic compound and the type of product to be formulated.
For use as a main wash detergent, the level of ethoxylated zwitterionic compound in the product will lie in the range 5~-35% by weight, preferably 10%-25%, and most preferably 15~~20%, the level of the surfactant compound being 0.5%-15~, preferably 1%-10%, and most preferably 1%-5% by weight. Such a main wash detergent can be formulated as a conventional granule or as a liquid, ` `~
paste, flake, ribbon, noodle, pellet, or tablet. As ~ ~`
will be shown hereinafter, this formulation flexibility is due, at least in part, to the ability of the zwitterionic ~ -surfactants of the present invention to achieve satisfactory " : .
particulate soil removal performance equivalent to that of --commercial heavy duty laundry detergents when used in blends with other surfactants. ~ -ALKOXYLATED ZWITTERIONIC COMPOUNDS
- Alkoxylated zwitterionic compounds useful in the present invention may have one or other of the following .~$
~ formulae: ~ -- (i) mono alkoxylates ~
.~ .
, ` IR2 ~ :
(C2H40) y [C2H3 (CH3) O] Z-R4-x .,. R3 :, ~ ' :
.

5~3~36~7 The synthesis of these compounds can be achieved using readily available commercial starting materials in the followiny synthetic route. Sodium hydride and poly-glycol (2:1 molar ratio) are reacted over a period of 4~10 hours in an ice bath-cooled solution of tetrahydro-furan under an atmosphere of an inert gas, e.g., argon.
Commercial materials can be used as the glycol source, :. , e.g. PEG mixtures containing from 4-20 ethylene oxide groups and polyethylene glycol-polypropylene glycol copolymers available as Pluronics~ from Wyandotte Chemical Company. Where a polyethylene glycol is employed the :, , resultant product is the sodium salt represented by ( ) Na O (CH2CH2O)yCH2CH2O Na~
` wherein y can be, for example, 2,4,8, 15 or l9.
A stoichiometric amount of tosyl chloride dissolved ;
in tetrahydrofuran is then added slowly to reaction product , (I), cooled in an ice bath, and the resultant mixture is stirred for 12 to 20 houxs to form (II) CH3- ~ -So2-o(cH2cH2o)y~l 2 ~ 3 i.e., the polyethylene glycol ditosylate. Pyridene or other suitable base is added to the mixture, which is then poured into ice water, acidified with HCl and then extracted with chloroform. The extract is rinsed with water and ~`' dried over sodium sulfate to give purified polyethylene glycol ditosylate (II).
The ditosylate (II) is then reacted with a tertiary `~-` amine of the structure ~
....
II) RlR2R3N

wherein Rl R2 and R3 are as defined hereinbefore. The reaction is conveniently carried out neat, or in a suitable solvent such as N,N-dimethyl formamide or CH3CN at ::, .''., ~' ~
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temperatures of 80C to about 100C to produce a mixture of ; 2 (C2H4O)y+l o2S ~ ~ - CH

CH3 - ~ 3 ;~
and (V) dicationic ammonium byproducts It will be appreciated that reaction of the ditosylate (II) with a tertiary phosphine RlR2R3P will give the corresponding phosphonium compound.
The mixture of (IV) and (V) is then dissolved in methanol and refluxed from 20-40 hours with an aqueous `
~ solution of sodium sulfite. Unreacted (V) and other i ionic materials are removed by contacting the above solution ., with a mixed bed ion exchange resin, followed by filtration of the solution and evaporation of the solvent to give, as the predominant zwitterionic product, ~ ;

~ 20 (VI) Rl - ~ - tC2H40)y C2H4 3 : R

~ Compound (VI) can optionally be further purified using , the mlxed bed resin.
` ~ It will be appreciated that zwitterionic compounds ~
of the general formula (VI) can be prepared using any of ~ -a variety of tertiary amines (III). Moreover, zwitterionic compounds having any desired, specific degree of ethoxylation (y) can be prepared by fractionating the polyethylene glycol used in the reaction and using the desired fraction in the synthesis scheme. Alternatively, relatively narrowly defined distillation "cuts" of polyoxyethylene ' .

.' ' ` ~ ~ , ` ' ' ' ' , ' ' '' ~5~ 7 glycol having any desired average degree of ethoxylation, and containing individual compounds having differing degrees of ethoxylation within the desired range, can be used in the reaction.
Polyethylene glycol is a cheap and readily available material and for this reason, preferred compounds are obtained when R4 is ethylene and z is zero. However, -there are certain advantages in the compounds having a mixed oxyethylene/oxypropylene charge-separating moiety, especially when the compounds are mixed with builders or other surfactants.
In the compounds where both y and z are integers, any ratio of y:z may be selected and any order of ethylene oxide/propylene oxide (EO/PO) moieties in the charge-~` separating position may be chosen; thus there may be a ~1~ statistical distribution of EO/PO moieties or there may be ~ blocks or segments of EO and Po moieties in the charge-,~ separating group. It is preferred that the charge- -;~ separating moiety consists of a block of polypropylene oxide and a block of polyethylene oxide, the polypropylene . ~
` oxide block being adjacent to the positive center. ~
. ~
- It will be further understood that sodium salt (I) can be reacted with a variety of epoxy compounds te.g., ' ! butylene epoxide) or halohydrins (e.g., 6-chlorohexanol or 8-bromooctanol) to provide zwitterionics having various R4 -~` groups within the scope of this invention. ~ ~-" a) Short Chain Derivatives Although not the most preferred materials, deriva- ;
tives in which Rl, R2 and R3 are straight or branched chain Cl-C6 alkyl or alkenyl groups do provide zwitterionic compounds having particulate soil removal capability. In .

~L~5~8~6~

order to yivQ the required de~ree of hydrophobicity to the molecule, the alkoxylated portion -(C2H4O)y[C2H3 (C~3)O]z- should be completely or at least substantially composed of polypropylene oxide units.
An example of a compound of this type is diethyl methyl ammonio(polypropenoxy) propane sulfonate in which eight polypropylene oxide groups are contained in the charge separating moiety.

:;
b) Mono-long Chain Derivatives In these derivatives, Rl is a hydrocarbon moiety that can be a straight or branched chain Cl-C30 alkyl or alkenyl group, preferably C14~Cl~ alkyl, particularly C14-C16 alkyl or an alkaryl group in which the alkyl portion has 10-24 carbon atoms; R2 and R3 are Cl-C4 alkyl ; or hydroxyalkyl groups particularly Cl-C3 alkyl and C2-C3 ` hydroxyalkyl; R4 is a Cl-C8 alkylene, C3-C~ alkenylene i` or 2-hydroxy propylene or 2- or 3-hydroxy butylene group -, .
-~ or a Cl-C4 alkarylene group; X is a sulfonate, sulfate or carboxylate radical; and z and y can each have a value in the range 0-20, provided that z + y is at least 2.

Preferably z is 0 and y is 9-12. Where X is a carboxylate . .! :
-~ radical, it is preferred that R4 is methylene, as this leads to greater stability of the ammonio-carboxylate zwitterionic compound.
- c) Di-long Chain Derivatives ` In this derivative, both Rl and R2 are hydrocarbon ~ moieties that can be straight or branched chain C6-C
m~ alkyl or alkenyl groups; R3, R4, X and z are as in (i) (b) ~
- above and y has an average value in the range 6-20. ~-Preferably Rl and R2 are identical and comprise alkyl groups each having 10 to 16 carbon atoms, most preferably alkyl ';

~59~1~7 groups each having lO to 24 carbon atoms. Preferably also z is 0 and pre~erred values for y lie in the range 6 to 15, most preferably in the range 9 to 12. ~ ~, In this derivative, R1,R2, and R3 are all ~ -hydrocarbon moieties that can be straight or branched chain C6-C16 alkyl or alkenyl groups; R4, x and z are as in (1) (b) and (c) above and y has a value in the range 6-100. Preferably Rl, R~, and R3 are each identical and each comprise an alkyl group having 8-16 carbon atoms ~ -in the chain. Most preferably each chain contains 8-12 carbon atoms. Z is preferably 0 and y has a preferred value in the range 9~50 r most preferably in the range 'i 1 2 5 0 .
(ii) di alkoxylates ii) Rl ~ N ~ (C2H4O)y_l ~ CH2CH2X (I) , (12H40,XH
~` In this structure, Rl can be a linear or branched C8-C30 alkyl or alkenyl group, preferably a Cl6 18 alkyl or alkenyl group; R2 can also be a C8-C30 alkyl or alkenyl ,, , group or can be a Cl-C4 alkyl or hydroxyalkyl group, preferably a methyl group; and X can be a sulfonate or sulfate radical.
.
` The number of ethylene oxide groups in each chain can be from l to 100 but their sum should be greater than 10. Normally there will be approximately the same number :
in each chain, the sum of the groups in both chains preferably having a value in the range 12-50 and most ~ .
preferably in the range 12-25.

: . .
The preparation of zwitterionic compounds of this type is accomplished using commercially available starting materials. A typical starting material is '~ ' '~
marketed under the trademark Ethoquad, by the Armak Company of the Armour Company. Ethoquad is a mixture of quaternary ammonium compounds whose predominant component is a di-ethoxylate of the structure ( C 2 H 4 0 ~ yH
N , ~1 2 / ~ (C2H4)x wherein y and x are each non-zero integers whose average sum is, for example, 5, 10, 15, 50, depending on the "cut"
, nd Rl and R2 are C12-C18 alkyl and Cl-C3 alkyl respectively.
: , .
~j In general terms, the compounds herein are prepared ; by adding tosyl chloride in equimolar amounts to a solution ; of the ethoxylated queternary salt in pyridine at a ~ ~
temperature of about 0C, stirring for about 24 hours, - -water quenching the reaction mixture and acidifying to a ~ pH of 2-3 with HCl.
;', The acidified reaction mixture is then extracted - with chloroform and the extract is washed with sodium bicarbonate solution and then with water; before being dried over anhydrous sodium sulfate. Evaporation of the solvent leaves the mono-tosylate ester as an oily ; residue.
The tosylate ester is dissolved in methanol and refluxed for about 24 hours with about a 10 molar excess of aqueous sodium sulfite, the reaction mixture is cooled and excess sodium sulfite and sodium tosylate are removed by filtration. The filtrate is then subjected to ;~ , : ' :::
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, ~ ~ S~ ~3~

purification by one or more treatments with a mixed bed ~anion-cation) resin to remove substantially all traces of all cat.ionic and anionic impurities and evapora-tion of the solven~ leaves the mono-sulfonate corresponding -~ ;
to (I) above.
iii) disul~oxy dialkoxylates .
. R2 iii) R -N+ - (C2H4O)y_l~CH2cH2 (II) : (C2H4O)X_l-cH2cH2 where Rl, R2, and X are ac in (ii) and y and x each have a value in the range 1-100 provided that the sum of y + x > 10. Preferred values for the sum of y + x will lie in the range 12-50 and most preferably in the range 15-25. The cation ~ M can be alkali metal, ammonium, and alkanol-;;.l ammonium, e.g. ethanolammonium or methanolammonium `~, but is most preferably sodium.
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~S~;7 The disulfona-te (II) is prepared in the same : manner as the mono-sulfonate (I), but using excess tosyl chloride (about 3:1 mole ratio, or greater) in the first step and a larger excess of sodium sulfite (20:1 mole ratio) in the second step.

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~5~ 7 I~ will be appreciated that a variety of diethoxylated amino starting materials can be employed ; in which the Rl and R2 groups may be substituted, x and y may he different from each other and the cation M in the Type (II) compounds may be other than sodium.
.~ , Compounds wherein y and x are of approximately equal length, the sum of y and x being from about 12 to about 25, most preferably from 15 to about 25, are especially useful herein.
It should be appreciated that mixtures of any of these zwitterionic compounds in any proportions may ~` be used in the compositions of the present invention. Such mixtures may be produced intentionally by blending " .
~, individual species or may arise as a result of the choice of feedstocks or as a result of the processing steps ~.
involved.
~i The ethoxylated zwitterionic compounds useful .:
~ in the present invention desirably display appreciable ;~ solubility in aqueous media. A solubility in water at ~ -25C of at least 50 ppm, preferably more than 75 ppm appears to be necessary for satisfactory particulate , ~ soil removal performance, but the preferred materials have ::
~ solubilities in water of 10%-30% by weight.
. .
The second essential component of a composition in accordance with the present invention is an organic :: .
detergent. This can be present at a level of from 1%-99~ by weight of the composition, the actual level being dependent on the end use of the composition and its desired physical form.

.
A wide range of organic detergents can be mixed i.e. can be considered compatible with the ethoxylated "''~
.
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~17-~C~5~367 zwitterionic compounds to form compositions useul in the present invention. In the context of this invention "compatible" is defined as causing no appreciable decrease in the ability of the ethoxylated zwitterionic compound to remove and suspend particulate soil.
Classes of compatible detergents that can serve ; as cosurfactants include the nonionic, zwitterionic, and ampholytic surfactants which can be used in a broad range of proportions to the ethoxylated zwitterionic compound. In contrast, most anionic detergents do not enhance the particulate soil removal performance of the ethoxylated zwitterionic compounds to the same extent, especially on synthetic fibers, although delayed solubility of the anlonic surfactant improves the performance of the combination. Amongst the cationic surfactants, only ~; those having a polyoxyalkylene function are compatible with the ethoxylated zwitterionic compounds useful in the present invention.
Nonionic Synthetic Detergents Most commonly, nonionic surfactants are compounds -~ produced by the condensation of an alkylene o~ide (hydro- ~
philic in nature) with an organic hydrophobic compound -which is usually aliphatic or alkyl aromatic in nature. ~ ~
:; : ., The length of the hydrophilic or polyoxyalkylene moiety ~which is condensed with any particular hydrophobic compound can be readily adjusted to yield a water-soluble compound ~-~ having the desired degree of balance between hydrophilic and hydrophobic elements.
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:~S~7 Another variety o nonionic surfac-tant is the semi~polar nonionic typified by the amine oxides, phosphine oxides, and sulfoxides, Examples of suitable nonionic surfactants are dis-closed in Nirschl et al U.S. Patent 3,862,058, Column 9, line 38, through Column 11, line 51 inclusive. ~ , Preferred nonionic surfactants are the condensation ' products of primaxy and secondary aliphatic alcohols with ethylene oxide, including but not being limited to the Tergitol ~ secondary alcohol ethoxylates manufactured by Union Carbide Corporation and the Neodol ~ primary alcohol ethoxylates marketed by Shell Chemical Company. In a highly preferred nonionic surfactant Neodol 23-3 (a predominantly C12~C13 primary OXO alcohol condensed with three moles of ethylene oxide) is "stripped" to remove unethoxylated alcohol ~i~ and lower ethoxylates to give a surfactant having a mean level of ethoxylation of 4.9 moles per mole of alcohol. This ;~ surfactant has superior oil and grease removal performance and detergent compositions incorporating it from the su~ject .
`, 20 of copending Canadian application serlal No. 222,185, filed March 17, 1975.
Table 1 illustrates the clay soil removal performance of mixtures of an ethoxylated zwitterionic compound and var-ious nonionic surfactants- Experimental Run 1 shows that the C16 ethoxylated zwitterionic material alone at a level of 250 ppm in water closely approaches the cleaning performance of the ,, .
.' ' .

~r ~59~7 fully Eormulated control product A on polyester and poly-cotton fabrics and achieves a major proportion of the control product performance on cotton. Experimental Run 2 shows that an appreciable proportion of this performance is retained at 125 ppm and the addition of 125 ppm of several different nonionic cosurfactants enables the performance at 250 ppm to be approached and even exceeded. It can also be seen that the addition of sodium tripolyphosphate to these systems, while providing an additional benefit in one or ~; 10 two instances, does not give an overall advantage. While the reason for this is not fully understood, it is believed - that the lack of benefit is a function of the ability of the better ethoxylated zwitterionic compounds, of which the C16 compound is an example, to remove soil in the presence .
of free mineral hardness ion.
Similar data was obtained for the corresponding C
ethoxylated compound, although this material was less effective on its own that the C16 ethoxylated compound.
However, the performance of the C14 ethoxylated compound was found to be improved by the addition of various nonionic surfactants, the improvement being seen over all fabric ~ ~-types. Addition of sodium tripolyphosphate at 250 ppm led ;~
to a further performance improvement. ~ ;
Table IV is a presentation of the grease and oil removal performance achieved by detergent compositions of the present invention. Runs 4 and 5 show respectively combina-tions of 125 p.p.m. C16 ethoxylated zwitterionic compound of Table 1 with 125 ppm of Neodol ~ 45 E7 witll 125 ppm of C11_15 secondary alcohol ethoxylate (Tergitol ~ 15-S-9 marketed by Union Carbide Corporation).

Thus for compositions of nonionic surfactants with , ~ - 20 -,~ .

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~L~598~;7 ~
ethoxylated zwitterionic materials useful in the present invention, it can be seen that for ethoxylated zwitterionics having good particulate soil removal performance, nonionic : surfactants can be used to reduce the level of ethoxylated zwitterionic necessary to achieve a given level of perfor-mance. For ethoxylated zwitterionics not having such good particulate soil removal performance, the level of performance can be raised by the addition of nonionic surfactants`and builders.
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-Ampholytic_Synthetic Deter~Pnts Ampholytic synthetic detergents can be broadly clescribed as derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical may be straight chain or branched and - wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfato.
Examples of compounds falling within this definition are sodium-3-(dodecylamino)-propionate~ sodium 3-(dodecylamino)-propane-l-sulfonate, sodium 2-(dodecylamino)ethyl sulfate, sodium 2-(dimethylamino)octadecanoate, disodium 3-(N-carboxymethyldodecylamino)-propane-l-sulfonate, disodium octadecyl-iminodiacetate, sodium l-carboxymethyl-2-undecyl-; imidazole, and sodium N,N-bis(2-hydroxyethyl)-2-sulfato-3-dodeeoxypropylamine. Sodium 3-(dodecylamino)propane-l-sulfonate is preferred.
Zwitterionie Synthetie Detergents Zwitterionic surfaetants ean be broadly deseribed as 2Q derivatives of secondary and tertiary amines, derivatives of heteroeyclic secondary and ~ertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The cationic atom in the quaternary eompound can be part of a heterocyelic ring. In all of these compounds there is at least one aliphatic group, straight ehain or branehed, containing from about 3 to 18 earbon atoms and at least one aliphatic substituent eontaining an anionie water-solubilizing group, e.g., earboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples of various elasses of zwitterionic surfaetants operable herein are diselosed in Nirsehl, et al. U.S. Patent 3,862,058 at Column 12, line 5 "' .

~591~` r7 through Column l~, line 60 inclusive.
Of all the above-described types of zwitterionic surfactants, preferred compounds include 3(N,N dimethyl-N-alkylammonio)-propane-l-sulfonate and 3(N,N-dimethyl-N~
alkylammonio) 2-hydroxypropane-l-sulfonate wherein in both compounds the alkyl group averages 14.8 carbon atoms in ~ :
length; 3(N,N-dimethyl-N-hexadecylammonio)-propane-l-sulfonate; 3(N,M-dimethyl-N-hexadecylammonio)-2-hydroxy-propane l-sulfonate; 3-tN-dodecylbenzyl-N,N-dimethylammonio)-propane-l-sulfonate; 3-(N-dodecylbenzyl-N,N,dimethylammonio)-2-hydroxypropane-1-sulfonate; N-dodecylbenzyl-N,N-dimethyl-ammonio acetate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)-propionate; 6-(N-dodecylbenzyl- N,N-dimethylammonio)hexanoate;
and N,N-dimethyl-N-hexadecylammonio acetate.

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'' ' " ' ' ` ,, , ~ ~ . ' ~59~3167 Clay soil removal performance results for combinations of the ethoxylated zwitterionic compounds of the present invention with other æwitterionic surfactants are shown in Table II. Experimental Runs 1 and 2 reproduce the Table 1 results at 250 ppm and 125 ppm for the C14 ethoxylated zwitt~rionic compound on its own while Runs 3 and 10 provide the same data for the C16 material.
The data shows that for both C14 and C16 ethoxylated zwitterionics, combination with other zwitterionic cosurfactants re;sults in an improvement in performance which is further enhanced by the addition of a builder (sodium tripolyphosphate).
Grease and oil removal data for combinations of the ~ -C16 ethoxylated zwitterionic compounds with zwitterionic cosurfactants are shown in Tablerv~ Runs 6 and 7. Advantages are again apparent for the combinati~ns in removing both triglyceride and hydrocarbon stains from polyester fabrics althc~gh tho r^sults for poly~otton are more variable.

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Z, -27a-- ~IDSi98~6'7 Anionic Deter~ents Non-soap anionic detergents that can be utilized in the compositions of the invention are disclosed in Nirschl et al U.S~ Patent No. 3,862,058 at column 4, line 64 to column 9, line 11~
This class of detergents also includes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about eight to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms. Suitable fatty acids can be obtained from natural sources such as, for instance, from plant or animal esters (e.g., palm oil, coconut oil, babassu oil, soybean oil, caster oil, tallow~ whale and fish oils, . .
grease, lard, and mixtures thereof). The fatty acids also can be synthetically prepared (e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process). Resin acids are suitable such as rosin and those resin acids in tall oil~ Naphthenic acids are also suitable. Sodium and potassium soaps can be made i 20 by direct saponi~fication of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
In Table III, clay soil removal results are given for ,:
combinations of ethoxylated zwitterionic compounds and anionic surfactants. Experimental Runs 1 and 2 represent :. .. .
comparative results for the C16 ethoxylated zwitterionic compounds respectively at levels of 250 and 125 ppm.

Experimental Runs 3 14 inclusive also give comparative ~`
, :' ., ~. , -` ~135~!36~

results for various anionic surfactants and, with the exception oE the alkyl ether sulphate, these materials all show very poor clay soil removal when used alone in water.
Runs 15-3~ demonstrate the effect of various anionic cosurfactants on the performance of the C16 ethoxylated zwitterionic compound in the presence and absence of builder. Runs 15-32 show that, at 125 ppm each of C16 compound and anionic cosurfactant in the absence of builder, particulate soil removal performance of the ethoxylated zwitterionic compound is depressed. It is restored, in varying degrees, by either delaying the solution of the anionic cosurfactant (Runs 16, 19, 22, 25, 28, and 31) which produces a marked effeGt on the performance on polyester fabrics, or by adding builder to the system, which shows a benefit for the more hydrophilic cotton-containing fabrics.
~ s noted above, the results show that sequential dissolution of first the ethoxylated zwitterionic and then the anionic cosurfactant serves to minimize the adverse effect of the latter on the clay removal performance of the 20 former. Such sequential dissolution can be achieved by any -one of a number of known methods, e.g., by coating, --granulation, or agglomeration of the anionic with other conventional detergent components such as C12_20 ~atty acids, C12_18 fatty acid amides and alkanol amides, high molecular weight (iOe. MWt>1000) polyethylene glycols, hydratable inorganic builder salts such as alkali metal polyphosphates, and porous siliceous materials such as those ` sold under the Trade Mark "Zeosyl" by J. M. ~uber Corporation. -Conveniently, the diluent component is incorporated at a 30 level o~ 5~ to 50%, preferably 10% to 25%, by weight of the mixture of anionic surfactant plus diluent so as to effect a .. .

, ' ' ' ' , delay of at least 60 seconds in the complete dissolution or dispersion of the mixture in an aqueous medium at 100F.
Similarly, microencapsulation using, e.g., hydrolysed gelatin, agar, or polyvinyl alcohol wall materials can be employed where low levels of anionic material are desired.
Techniques for microencapsulating materials, including detergent components, are well known in the art. A typical disclosure of such techniques is given in Kirk-Othmer Encyclopedia of Chemical Technology, 2nd edition, 13, pp.
436-456, published in 1967 by John Wiley ~ Sons, Inc.

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Grease and oil rernoval data are shown in Table V for combinations of Cll 8 LAS and C16_18 Y 6 respectively with -the C1~ ethoxylated zwitterionic compound, and it can be seen that Cl1 8 LAS provides performance advantages relative to the control product. In contrast, the ethoxylated sulphate surfactant serves to inhibit grease and oil removal.
The effect of anionic cosurfactants on the sudsing characteristics of the ethoxylated zwitterionic compounds of the present invention is illustrated in the Figure in which the suds height developed by the Recirculating ;
Suds Generator (RSG) are plotted for different blends of C16 ethoxylated zwitterionic compound and sodium Cll 8 ;
linear alkyl benzene sulphonate over a 10-minute time interval. It can be seen that an appreciable fraction of the sudsing performance achieved by 100% Cll 8 LAS
is given by blends in which the level of Cll 8 LAS is as low as 5%, the sudsing performance increasing with increasing Cll 8 LAS level-Thus anionic surfactants can be incorpo~ated in detergent compositions in accordance with the present ., .
invention although they should not exceed 50% by weight of the ethoxylated zwitterionic-cosurfactant mixture if the desirable particulate soil removal properties of the ethoxylated zwitterionic compound are to be retained.
Alkali metal salts of aliphatic carboxylic acids can be incorporated at these levels without special formulation precautions but most anionic cosurfactant levels in excess of 20% of the mixture, more preferably in excess ~
of 10% of the mixture, require incorporation in a manner that will delay the cosurfactant solubility.
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Cationic Deter~ents Only those cationic detergents having a hydro-philic grouping with the molecule have been found to ke compatible with the ethoxylated zwitterionic compounds useful in the present invention.
Thus compounds of the class IR2 ' ~ $, Rl ~ N ~ (CH2CH20)pH X

can be employed wherein Rl is a C12-C18 linear or branched alkyl or alkenyl group R2 and R3 are Cl-C
alkyl or hydroxy alkyl groups, p has a value in the range 3-50, and X is a compatible anion. Analogous bis-ethoxy-lated quaternary ammonium salts can also be used.

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Optional Components .
In addition to the ethoxylated ~witterionic compound and the organic surfactant, the de-tergent ~:
compositions may also contain other ingredients convention- ~ .
ally employed in such products. The principal optional component is an inorganic or organic detergent builder -:.
to assist in mineral hardness control which may be used ;
at levels between 1% and 99% by weight of the detergent .~
composition, preferably between 10% and 75% and most ~ ::
preferably between 25% and 60%.
Suitable inorganic builders include the alkali metal polyphosphates (including the pyrophosphates and . glassy high polymeric phosphates) phosphonates, carbonates, , sesquicarbonates, bicarbonates, borates, silicates, ~ .
sulphates, and aluminosilicates.
Aluminosilicate buil.der salts found to be useful in the present invention have the general formula: ~ ;
Naz[(Alo2)z(sio2)y] x H2O
` wherein z and y are integers of at least 6, the molar ratio '! 20 of z to y is in the range from 1.0 to about 0.5 and x is an integer from about 15 to about 15 to about 264. Such alumino-silicates also should have a particle size diameter in the range 0.1 to 100 microns, a calcium ion exchange . capacity of at least ahout 200 milligram equivalent/gram ~-and a calcium ion exchange .,~, , .
., .

..

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: -35-; rate of a-t least about 2 grains/U.S. gallon/mlnute/gram.
Detergent compositions incorporating aluminosilicate builder salts o~ this type are disclosed in -the commonly assigned Belgian Patent No. 814,874 ~ssued November 12, 1974.
Suitable wat~r soluble detergent builders are disclosed in Nirschl U.S. Patent No. 3,862,058 at column 15, line 8 to column 16, line 18. Examples of organic builders ~ are set forth in Diehl U.S. Patent No. 3,308,067 and mixtures ; of certàin preferred organic and inorganic builders are dis-closed in Canadian Patent No. 755,038.
Another optional ingredient that may be incorporated : ~, is an enzyme or removal of protein-based or carbohydrate-based stains. Enzymes for xemoving protein-based stains are proteolytic in nature such as those sold under the trade marks "Alcalase" and "Esterase" b~r Novo Industries, A/S
Denmark or under the trade marks "Maxatase" and "AZ Protease"
.
by Gist-Brocades N.V. The Netherlands. These materials are normally incorporated at levels of up to 1% by weight, preferably 0.25% to 0.75~ by weight, and are preferably coated or prilled with inert additives to minimize dust formation - and improve storage stability. A wide range of enzyme mat-~ erials and means for their incorporation into synthetic - detergent granules is disclosed in U.S. P. 3,553,139 issued on January 5, 1971, to McCart~, Roald, DeOude, Blomeyer, and - Crac~o.
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~,' ' ' ' , ' ~ further ingredient that may be incorporated to improve product performance is a bleaching agent of the halogen or oxygen-containing type. ~xamples of the hypohalite bleach type include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanurates and ;~
N-chloro and N-hromo alkane sulphonamides. Such materials are normally added at 0.5%-10~ by weight of the finished product, preferably 1%-5% by weight.
Examples of oxygen-containing bleaches include sodium perborate, sodium percarbonate, and potassium non-opersulphate that are incorporated at levels of 5-30%, preferably 10-25% by weight of the final product. The ;
inclusion of organic bleach activators such as phthalic anhydride, tetra acetyl ethylene diamine, tetra acetyl ; methylene diamine or tetra acetyl glycouril lead to the in situ production during the washing process of the corres-ponding organic peroxy acids which have enhanced low temperature bleaching performance. Activators of this , type are normally used with sodium perborate, at usage i 20 levels of 5-15% by weight of the final product.
Materials to boost or modify the sudsing pattern of the compositions of the present invention may also be included. Examples of suds boosters include coconut and tallow mono- and di-alkanolamides, particularly ethanolamides and C12 15 alkyl di-lower alkyl amine oxides. Typical suds depressors include long chain fatty acids such as ; those disclosed in U.S~ Patent 2,95~,347 issued September 27, 1960, to Wayne St. John and combinations of certain :
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. , 59~6~
nonionlcs therewith as dlsclosed in U.S. Patent 2,954,348 issued Septe~lber ~7, 1960, to Eugene Schwoeppe.
Other optional ingredients in granular produets lnclude hydrotropes and anticaking additives such as salts of lower alkyaryl sulphonic acids~ salts of ~-sulphosuecinic acid, and ~-sulphobenzoic acid, and urea, normally utilized at levels of 0.5~ to 5% by weight oE the final product, preferably at levels of 1~-3% by weight. C12-C18 alkyl acid phosphates and their condensation products with ethylene oxide may also be incorporated at similar levels for control of crutcher mix viscosity. Antire-deposition agents such as glassy polymeric,- phosphates magnesium silicates, colloidal silicas, carboxymethyl cellulose, hydroxyethyl cellulose, and thei~r derivatives may also be incorporated. Preferred anti-redeposition agents are glassy phosphates containing more than ten phosphorous atoms per moleeule and colloidal silieas.
Anti-tarnish and anti-corrosion agents, perfume and colour may also be ineluded, the last ingredient being , 20 conveniently added either as a general colour or in the z form of a speckle appLied to a separate granule fraction of the entire formulation or to a granulate of one or more of the ingredients.
Anionic optical brightening agents or fluorescers such as the bis (triazinylamino) stilbene disulphonates can be included in the formulations of the present invention but their efficiency is not as high as in conventional formulations unless they are incorporated together with an anionie surfactant.
i :' ' .~ . ' ',.:

9~367 s discussed hereinbefore anion,ic surfactants can form part of the detergent compositions of the present invention but incorporation of most anionics at a ratio to the zwitterionic compound in excess of about 1:4 by weight leads to a fall~off in particulate soil removal performance. The only exceptions are the aliphatic carboxylates particularly those soaps having a carbon ' chain length approximately that of the hydrophilic chain ~ ,' of the zwitterionic compound.
Thus, good anionic fluorescer daposition togethar with acceptable particulate soil removal performance can be obtained by employment of a mixture of ethoxylated zwitterionic compound and water soluble soap in a ratio ;
of soap to zwitterionic within the range from about 1:3 to about 1:1. For the preferred C16-G18 ethoxylated zwitterionic compounds of the present invention the soap chain length should be in the stearic or tallow range.
The pH of detergent ~ormulations in accordance ; `~
with the present invention can lie anywhere within the 1 20 range 5-12 but is preferably chosen to fall within the ::, ' range 8.0-10.-S as this provides a slight particulate soil J removal benefit on synthatic fabrics. However, the use'of ~ ' ', specific optional components such as enzymes may require - the selection of a product pH that will permit optimum functioning of the component concerned.
Granular formulations embodyin~ the compositions ~' of the present invention may be formed by any of the ~`' conventional techniques i.e., by slurrying the indlvidual ', components in water and then atomizing and spray-drying ., ~
~, .
~, -39-: .' 36;7 the resultant mixture, or by pan or drum granulation of the components.
Liquid formulations embodying the compositions of the present invention may contain builders or may be unbuilt. If the compositions are unbuilt, they will conventionally contain approximately 30-50% Itotal surfactant, from 1-10% of an organic base such as mono, di, or tri-alkanolamine, a solubilization system such as alkali metal halide and a lower primary alcohol such as ethanol or isopropanol and approximately 30%-40% water. Such compositions will normally be homogeneous single phase liquids of low viscosity (approximately 100-150 centipoises at 75F).
Built liquid detergent compositions may also be single phase liquids provided that the builder can be solubilized in the mixture at its level of use. Such - liquids conventionally contain 10%-25% total surfactant, -~
10%-20% builder which may be organic or inorganic, 5%-10% of a hydrotrope system and 50%-60% of water. Liquids of this type also have low viscosity (100-150 c.p.s. at 75F). suilt liquid detergents incorporating components that form heterogeneous mixtures or levels of builder that cannot be completely dissolved can also embody the -~
compositions of the present invention. Such liquids . ~
conventionally employ viscosity modifiers to produce systems having plastic shear characteristics to maintain stable dispersions and to prevent phase separation or solid settlement.

~' - ~5~367 The following examples serve to illustra-te the present invention - EXAMPLE I: A granular detergent composition was made up having the following composition:
~-(N-octadecyl-N,N-dimethylammonio)-2-octaethenoxy-ethane-1-sulphonate 9.3%
3-(N-myristyl N,N-dimethylammonio)propane-l-sulphonate 9-3% ~
Na12(SiO2:AlO2)1215H2O 51.8% ' a2CO3 14.8%
~- Sodium Silicate (SiO2:Na2O=3.2:1) 14.8% ;~
,; 100.0% '~ :
- The composition was dissolved in water having a mineral hardness of 7 grains/U.S. gallon (Ca:Mg = 2:1) to give a 0.12% solution and was then used in a Tergotometer to give a 10 minute wash at 105~F to a mixture of cotton, polycotton, and polyester cloth swatches, employing the .
Test Procedure previously described. A similar wash using Control Product A at a level of 1400 ppm in solution was ~ , . 20 also carried out, and the particulate soil removal given by the composition expressed as a percentage of the performance of the control product was:
Cotton PolycottonPolyester 110 102 108 ~-, :

;~, ~ ~.

.

~59~i7 EXAMPL~ I,iquid laundry detergellts were made up having the following compositions:
P Q R S
C14_15 alcohol with 7 moles ethylene oxide 33.0 33,0 33.0 33.0 33.0 Cll 8 linear alkyl benzene sulphonate 23.0 23.0 -~
riethanolamine 3.0 3.0 3.0 3.0 3.0 KCL 2.5 2.5 --Ethanol 5.0 15.0 15.0 15.0 15.0 N-octadecyl N,N-dimethyl ammonio-2- -- -- -- 2.0 5.0 octaethenoxy-ethane-l-sulphonate Water to 100----> to 100 ---> --->
Each composition was used to pretreat a 5" square knitted polyester swatch presoiled with a clay solution - ~:
:.
prior to the latter being washed. In each pretreatment, : ~ :
, ,.:
`, three drops of the composition were applied to a 1" square cut out from the swatch, and this cut out and the remainder , of the swatch were then given a 10 minute wash at 105F
in a Tergotometer using wa-ter having 7 grains/gallon hardness (Ca/Mg = 2~

~' ~

: , .
~ .

. .

~5~

The wasil, rlnse, and dry cycles were as hereinbefore described in the standard procedure. , The swatches and cut ou-ts were then graded visually for particulate soil removal. Compositions P and Q showed no pretreatment benefit on the respective cut outs and little if any clay soil removal from the swatches. Composition R achieved discernible clay removal from the swatch and a visible benefit for pretreatment. Compositions S and T also showed some . . .
clay removal from the swatches but the areas of the cut outs which had been pretreated were restored to their original condition before clay soiling.

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Claims (25)

1. A detergent composition comprising A) 1% to 99% by weight of the composition of a zwitterionic compound having a formula selected from the group consisting of (i) wherein R1 and R2 are independently selected from the group consisting of straight and branched chain C1-C30 alkyl and alkenyl moieties, alkaryl moieties in which the alkyl group has 1-24 carbon atoms and C4-C6 heteroring entities in which two R moieties are joined with Y, R3 is selected from the group consisting of straight and branched chain C1-C21 alkyl and alkenyl moieties, alkaryl moieties in which the alkyl group has 1-16 carbon atoms, C4-C6 heteroring entities in which two R moieties are joined with Y and -(C2H4O)XH wherein x has a value of 3-20; R4 is selected from the group consisting of C1-C4 alkylene, C3-C8 alkenylene, 2-hydroxy propylene, 2- and 3-hydroxy butylene moieties and C1-C4 alkarylene moieties provided that where R3 is -(C2H4O)XH then R4 is -CH2-CH2-;
Y is nitrogen or phosphorus; X is an anion selected from the group consisting of sulfate, sulfonate and carboxylate radicals; and y and z independently have a value in the range of 0-20 provided that y + z is an integer from 2-20 and provided that where R3 is -(C2H4O)XH then z = 0 and x + y ? 10;

and ii) wherein R1 is selected from the group consisting of linear and branched C8-C30 alkyl and alkenyl radicals; R2 is selected from the group consisting of linear and branched C8-C30 alkyl and alkenyl radicals and C1-C4 alkyl and hydroxyalkyl radicals;
X- is selected from the group consisting of sulfate and sulfonate; y and x have values in the range of 2-100 provided that y + x ? 12;
M is a cation selected from the group consisting of alkali metal, ammonium and alkanolammonium ions; and B) 99% to 1% by weight of the composition of an organic detergent.

2. A detergent composition according to Claim 1 wherein the zwitterionic compound has the formula wherein R1 is selected from the group consisting of straight and branched chain C16-C22 alkyl and alkenyl moieties, R2 is a C1-C3 alkyl group and x + y has a value in the range of 14-50.

3. A detergent composition according to Claim 2 wherein R1 is selected from the group consisting of straight and branched chain C16-C18 alkyl and alkenyl moieties and x + y has a value in the range of 15-25.

4. A detergent composition according to Claim 1 wherein RI, R2, and R3 are each selected from the group consisting of branched and straight chain C6-C16 alkyl and alkenyl radicals; R4 is selected from the group consisting of C1-4 alkylene and 2-hydroxy propylene and 2- and 3-hydroxy butylene moieties and alkarylene moieties in which the alkyl group contains from 1-4 carbon atoms; X is sulfate or sulfonate; z is zero and y has an average value in the range of 6 to 20.

5. A detergent composition according to Claim 4 wherein y has a value of at least 9.

6. A detergent composition according to Claim 1 wherein R1 and R2 are each selected from the group consisting of branched and straight chain C6-C21 alkyl and alkenyl radicals; R3 is selected from the group consisting of C1-C4 alkyl and hydroxyalkyl moieties; R4 is selected from the group consisting of C1-C4 alkylene and 2-hydroxy propylene and 2- and 3-hydroxy butylene moieties, and alkarylene moieties in which the alkyl group contains 1-4 carbon atoms; X- is sulfate or sulfonate; z is zero and y has an average value in the range of 6 to 20.

7. A detergent composition according to Claim 1 where R1 is selected from the group consisting of branched and straight chain C8-C30 alkyl and alkenyl radicals; R2 and R3 are each selected from the group consisting of C1-C4 alkyl and hydroxyalkyl moieties; R4 is selected from the group consisting of C1-C4 alkylene and 2-hydroxy propylene and 2- and 3-hydroxy butylene radicals and alkyarylene moieties in which the alkylene group has 1 to 4 carbon atoms; and (y + z) has a value of from about 6 to about 20.

8. A detergent composition according to Claim 7 wherein R1 is a C12-C18 alkyl moiety; R2 and R3 are independently selected from C1-C3 alkyl and hydroxyalkyl moieties; z is zero and y has a value from about 6 to about 12.

9. A detergent composition according to claim 1 incor-porating 99% - 50% by weight of the ethoxylated zwitterionic compound and 1% - 50% by weight of an anionic surfactant as the organic detergent.

10. A detergent composition according to claim 9 wherein the anionic surfactant is a C12-C18 linear aliphatic carboxylic acid or water soluble salt thereof.

11. A detergent composition according to claim 10 wherein the linear aliphatic carboxylic acid or water soluble salt thereof has the same number of carbon atoms in the alkyl chain as the group R1 of the ethoxylated zwitterionic compound and wherein the composition further includes from 0.05% to 0.5% by weight of an anionic optical brightening agent.

12. A detergent composition according to claim 9 wherein the anionic detergent is selected from the group consisting of alkali and alkaline earth metal, ammonium and alkanol ammonium linear and branched C10-C14 alkyl benzene sulfonates, C10-C20 alpha-sulfo carboxylic acid salts and esters in which the alkyl group has 1-8 carbon atoms, C10-C20 alkane sulfonates, C14-C18 olefin sulfonates, C10-C18 alkyl sulfates and con-densation products thereof with 1-20 moles of ethylene oxide, and mixtures thereof.

13. A detergent composition according to claim 12 wherein the anionic surfactant is incorporated in an intimate mixture with 5% to 50% by weight of the mixture of a material requiring more than 60 seconds for substantially complete dissolution or dispersion in an aqueous medium at 100°F.

14. A detergent composition according to claim 13 wherein the material is an organic material selected from the group consisting of polyethylene glycols of molecular weight greater than 1000, C12-C18 fatty acid amides, C12-C18 fatty acid alkanolamides, C12-C20 fatty acids and mixtures thereof.

15. A detergent composition according to claim 13 wherein the material is an inorganic hydratable salt.

16. A detergent composition according to claim 15 wherein the hydratable salt is an alkali metal polyphosphate.

17. A detergent composition according to claim 13 wherein the anionic surfactant has a coating of a material requiring more than 60 seconds for substantially complete dissolution or dispersion in an aqueous medium at 100°F.

18. A detergent composition according to claim 17 wherein the material is selected from the group consisting of polyethylene glycols of MWt > 1000.

19. A detergent composition according to claim 1 wherein the organic detergent is a nonionic detergent selected from the group consisting of ethylene oxide condensates of C8-C20 branched and linear aliphatic primary and secondary alcohols, alkyl phenols wherein the alkyl group contains 6-12 carbon atoms and ethylene oxide-propylene oxide condensates.

20. A detergent composition according to claim 19 wherein the nonionic detergent is a primary alcohol ethoxylate of the formula R1 - R2 - O(CH2CH2O)nH
wherein R1 is a linear alkyl residue and R2 has the formula CHR3CH2-; R3 being selected from the group consisting of hydrogen and mixtures thereof with not more than 40% by weight of C1-4 alkyl groups, wherein R1 and R2 together form an alkyl residue having a mean chain length in the range of 8-15 carbon atoms at least 65% by weight of said residue having a chain length within ? 1 carbon atoms of the mean, wherein the average value of n lies between 3.5 and 6.5 provided that the total amount by weight of components in which n = 0 shall be not greater than 5% and the total amount by weight of components in which n = 2-7 inclusive shall be not less than 63%, based on the total weight of the ethoxylate and wherein the HLB of the ethoxylate lies in the range of 9.5-11.5.

21. A detergent composition according to claim 1 wherein the nonionic surfactant is a C10-15 alkyl, di-lower alkyl, or hydroxy lower alkyl amine oxide.

22. A detergent composition according to claim 1 wherein the organic detergent is a zwitterionic surfactant selected from the group consisting of 3-(N-C10-l6alkyl N,N-dimethylammonio)propane-1-sulfonate, 3-(N-C10-16alkyl N,N-dimethylammonio)2-hydroxypropane-1-sulfonate, 3-(N-C10-15 alkyl benzyl, N,N-dimethylammonio3-2-hydroxypropane-1-sulfonate.

23. A detergent composition according to claim 1 further including a detergent builder salt in an amount such that the ratio of builder salt to ethoxylated zwitterionic compound plus organic detergent lies in the range 1:20 to 20:1.

24. A detergent composition according to Claim 23 wherein the detergent builder is in an inorganic builder selected from the group consisting of ammonium and alkali metal polyphosphates, phosphonates, carbonates, bicarbonates, silicates, alumino silicates, and sulfates.

25. A detergent composition according to Claim 24 wherein the detergent builder is an organic builder selected from the group consisting of alkali metal nitrilotriacetates, citrates, oxydisuccinates, carboxylmethoxysuccinates, poly-maleates, and copolymers of maleic anhydride with methyl vinyl ether or ethylene.