CA1131092A - Detergent compositions - Google Patents

Abstract

DETERGENT COMPOSITIONS

Abstract Described axe detergent compositions containing a nonionic/cationic surfactant mixture and, as an improved builder mixture, a combination of aluminosilicate and polycarboxylate builder materials. These compositions contain little or no phosphate materials, yet deliver excellent particulate soil removal performance and greasy/
oily soil removal benefits, along with fabric softening, static control and other fabric care benefit.

Description

DETERGENT COMPOSITTO~S
Victor F. Rodriguez and Brandon H. Wiers 5Technical Field .
This in~ention relates to detergent compositions containing a nonionic/cationic surfactant mixture and, as an impro~7ed builder mixture, a combination of alumino-silicate and polycarboxylate builder materials. These com-10 positions deliver excellent particula~e soil removal perfor-mance and greasy/oily soil xemoval benefits, along with - fabric softening, static control, color fidelity and dye transfer inhibition benefits. Compositions which utilize mixtures of selected nonionic and cationic surfactants, 15 but without the particular builders describe~ herein, are defined in U.S. Patent No. 4,222,905 of Cockrell, issued September 16, 1980; U.S. Patent No. 4,259,217 of A.P. Murphy, issued March 31, 1981; and Canadian Patent Application No.
323,240, A.P. Murphy, filed March 12, 1979.
E~ackground Art _ The property possessed by bui]der materials c~f improving detergency levels of soaps and synt:~etic detergents is lcnown. Such builders permit the at:tainment Oe better cleaning 25 per Eor~nance than is possible when so-called unbuilt compo-~;itions are used. ~Iowever, the behavior and mechanisms by which builders perfonn their function are only partially understood. It i~ known that good builders must be able to sequestex most of the calcium and/or magnesium ions in 30 the wash water since these ions are detrimental to the detergency process. However, it is difficult to predict which compounds possess useful combinations o~ builder properties because of the complex nature of detergency and the countless factors which con-35 tribute both to overall perEormance results and therequirements of environmental acceptability~
Sodium tripolyphosphate (STP) has been found to be a highly efficient cleaning and detergent builder and this compound has been widely used for decades in cleaning and .. . ~ r~

.

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- 2 -detergent formu]ati s. However, because of the recent emphasis on removing phosphates from detergent and cleaning compositions, suitable replacements for phosphate builders, which would deliver effective cleaning performance and be environmentally acceptable, are being sought. Inorganic builders other than STP are generally not satisfactsry for use as a builder in detergent formulations because of their poor build6r ~roperties. Sodium aluminosilicates, commonly known as zeolites, have been proposed for use in detergent formulations since they are able to soften water by removing calcium ions; but they are not very effective in removing magnesium ions from water.
It has also xecently been taught that by combining ~pecific types of cationic surfactants with a narrowly defined range of alcohol ethoxyla~e type nonionic sur-factants, within defined nonionic:cationic ratios, simple, unbuilt detergent compositions which deliver good _le~ning performance and fabric care benefits, can be formulated.
(See e.g., U.S. Patent 4,259,217, Murphy; U.S. Patent 4,222,905, Cockrell, and Canadian Patent Appl:ication No. 323,240, of A.P. Murphy, previously referred to). These unbuilt detergent compositions, although generally.~qui~alent to fully built phosphate compositions known in the art, still are capable of further improvement.
Thus, it-can be seen that there is a need for new detergent compositions with cleaning properties superior or equivalent to phosphate-built detergents, but which do not contain phosphates, and which achieve environmental accept-ability by being readily biodegradable. Now, according to the present invention, there is provided new detergsnt compositions with a cationic/nonionic surfactant mixture and, as an improved builder mixture, a combination of aluminosilicate and polycarboxylate builder materials.
These compositions provide cleaning performance superior to that of phosphate-built compositions and also provide other fabric care benefits, such as softening and sta-tic control~

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,. .

Summary of the_Invention The present invention encompasses a detergent compo-sition, which contains from 0 to about 5~ phosphate materials, comprising:
S (a) .from about 1% to about 95% of a suractant mixture consisting essentially of: -(i) a nonionic surfactan~ having an HLB of from about 5 to about 17; and (ii) a c~.tionic surfactant, having the formula ~ ~ ~LZ

wherein each R is an organic group contai.ning a straight or branched alkyl or alkenyl group optionally substituted with up to 3 phenyl or hydroxy groups and optionally interrupted by up to 4 structures selected from the group consisting of ~3 c o o c -C-N-, -N-C-, O H H O O O H H O
-C-N-, -N-C-, -O-, -O-C-0-, -O-C-N-,. -N-C-O-, and mixtures thereof~ each Rl containing from i about 8 to about 22 carbon atoms, and which may ~dditionally contain up to about 20 ~: . ethy~ene oxide groups; m is a number from 1 to 3; each R is an alkyl or hydroxy alkyl group containing from 1 to 4 earbon atoms or a benzyl group, with no more than one R in a molecule being benzyl; x is xom 0 to 11, the remainder of any carbon atom positions being filled by hydrogens; Y is selected from the group consisting of N~ , , " - Fr' 'l \/ I
M - C
(2) -C
~ N - C - , I+
: ~3) _p (~3 -S~ , - (5) -N~ , wherein p is from 1 to 1 (C2H4)pH

5C2H40) H
(6) -~ - , wherein each p is from 1 to 12, (C2H40) p (C H O) H
- - ~7) -N -(C2H40)pH, wherein each p is ~rom 1 ~o 12, )pH ;
C
\ ~ \"~ ' , ~8) C ~N -u C~ ~ C
C
~3 C
(9~ N
. ~C C , and N
(10) mixtures thereof;

L is 1 or 2, the Y groups being separated by a moiety selected from the group consisting of Rl and R2 . analogs having from one to about twenty-two carbon atoms and 2 free carbon single bonds when ~ is 2; Z is an anion in a number sufficient to yi~e electrical neutrality to the molecule, said cationic surfactant being at least water-disperslble in admixt~re with said r~
-, .

! - 5 -nonionic sufactant;
wherein the ratio of said nonionic surfactant to said cati-onic surfactant is from about 1:1 to about 100:1; and (b) from about 5gO to about 99% of a detergency builder mixture consisting essentially of:
~i3 a water-insoluble aluminosilicate material selected from the group consisting of:
(1) Zeolites A, X, or P~B), or mi~tures thereof, having a particle size diameter of from about 0.01 microns to about 25 microns and containing at least 10%
water of ~ydration;
(2) amorphous hydrated aluminosilicate material o the empirical ormula:
M (zAlO ySiO ) wherein M is sodium, potassium, ammon-i~um~ z is from about 0.5 to abou~ 2, y is 1, said material having a particle ~i size diameter of less than about 100 i - 20 -- microns, a magnesium ion exchange capacity of at least about 50 milligrams equivalents of CaCO3 hardness per gram - of anhydrous aluminosilicate, and a Mg exchange rate of at least about 1 grain/gallon/minute~gram/gallon; and - (3) mi~tures thereof; and (ii) a polycarboxylate builder material;
whexein the weight ratio of the aluminosilicate material to the polycarboxylate material is from about l:lQ to about 10:1.
D~sclosure of the Invention _ This invention comprises the discovery of an improved builder mixture ~or use in detergent compositions con-taining selected nonionic/cationic surfactant mixtures.
The builder mixture, a combination of aluminosilica~e and polycarboxylate builder materials, delivers excellent par-ticulate soil remo~al performance and greasy/oily soil removal benefits. These compositions also provide fabric softening, static control, color fidelity and dye transfer _._, ......................................... .~ r~'!

31 ~3~

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inhibition benefits. The detergent compositions are particulaxly good in 10-40C water, especially when the particle size diameter of the aluminosilicate material is from about 0.5 to about 2 microns.
The essential elements in the detergent composition of this invention are:a nonionic~cationic surfactant mixture, and a mixture of aluminosilicate and polycarboxylate builder materials.
Surfactant Mixture The compositions of the present invention comprise, by weight, from about 1 to about 95%, preferably from about 15 to about 60~, and most preferably from about 20 to about 50%, of a mixture of particularly defined nonionic and cationic surfactants, defined hereinafter, within ratios of nonionic to cationic surfactant of from about 1:1 to about 100:1, preferably from about 1:1 to about 50:1, and more preferably from about 3:1 to about 40:1. Optimum removal of greasy/oily soils is generally obtained with nonionic:cationic surfactant ratios of from about 5:1 to about 20:1; while optimum removal of particulate soils is obtained with compositions having nonionic:cationic sur-factant ratios of from about 2:1 to about 9:1, especially from about 3:1 to about 6.5:1, most especially rom about

3.5:1 to about 5.5:1, with these ratios being particularly effectiYe where the cationic surfactant used is of the di-long chain variety disclosed and claimed in Canadian Patent Application No. 323,240 of A.P. Murphy, filed March 12, 1979.

The compositions of the present inYentiOn are prefer-ably formulated so as to have a pH of at least about 7 in the laundry solution, at conventional usage concentrations, in order to optimi2e their o~erall cleaning performance, to aid in their manufacturina and pro~essing, and to minimize the possibility of washing machine corrosion. Alkalinity sources, such as potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydroxide, sodium carbonate, and sodium bicarbonate, may be included in the compositions for this purpose. So~e of the cationic/nonionic systems of .~33L~

the presen-t invention may attain optimum removal of greasy/
oily soils at higher pHs, while attaining optimum partic-ulate removal at relatively lower pHs. In these systems, overall performance may b~ enhanced by varying the pH of the 5 wash solution during the laundering proces~. Particularly preferred compositions have a pH of at least about 8 in the laundry solution in order to optimize the removal of greasy/
oily and body soils. In addition to the higher pH in the laundry solution, these preferred compositions should also 10 have the ability to maintain a pH in the laundry solution of from about 8 to 11 throughout the washing operation ~reserve c alkalinity). Such a reserve alkalinity may be obtained by incorporating compounds which buffer at pHs of from about 8 to 11, such as monoethanolamine, diethanolamine, and tri-15 ethanolamine.
Preferred compositions of the present invention are also essentially.free of oily hydrocarbon materials and solvents, such as mineral oil, para~fin oil and kerosene, since these materials, which are themselves oily by nature, 20 load the washing liquor with excessive oily material, thereby diminishing the clean.ing effèctiveness of the compositions themselves.
Nonionic Component -Nonionic surfactants, having H~Bs of from about 5 to ~5 about 17, preferably from about 8O5 to about 14, more pre~erably from about 10 to about 13.5, which are conven-tionally used in detergent compositions, may be used in the compositions of the present invention. Such surfactants include the condensation product of 1 mole of a saturated or 30 unsaturated, straight or branched chain carboxylic acid having from about 10 to about 18 carbon atoms with ~rom about 5 to about 50 moles of alkylene (particularly ethylere) oxide; the condensation product of 1 mole of saturated or unsaturated, straight or branched chain alcohol having from about 10 to about 24 carbon atoms with from about 5 to about 50 moles of alkylene (especially ethylene) oxide; poly-ethylene glycols having a molecular weight of from about 400 to about 30,000; and the condensation product of 1 mole of ., .. . ~, . .
~ r 7 ~3~

alkyl phenol wherein the alkyl chain contains from a~out 8 to a~out 18 carbon atoms with from about 4 to about 50 moles of alkylene (especially ethylene) oxide. Further disclosure of nonionic surfactants useful in the present invention is found in U.S. Patent 3,862,058, Nirschl and Gloss, issued January 21, 1975, Preferred nonionic surfactants for use in the composi-tions of the present invention, because of their excellent biodegradability and performance characteristics, have the formula RtoC2H4)noH, wherein R is a primaxy or secondary, straight or branched alkyl chain containing an average of from about 8 to about 22, preferably from about 10 to about 20, carbon atoms, and n is an average of from about 2 to about 12, preferably from a~out 2 to about 9, especially from about 2 to about 7. ~here di-long chain cationic m~terials are used in the compositions of the present invention, it is especially preferred that the R group in the nonionic surfactant contain from about 10 to about 16 carbon atoms. The nonionic suractants described herein have an ~LB (hydrophilic-lipop}lilic ba.lance) of from about 5 to ~bout 17, preerably from about 8.5 to about 14, and most preferably from about 10 to about 13.5. HLB, an indicator of a surfactants hydrophilic or lipophilic nature, is defined in detail in Non onic Surfactants, by Mo J~ Schick, Marcel Dekker, Inc., 1976, pp. 607,613.

Preferred nonionic surfac~an~s for use in the present invention include the condensation product of C10 alcoh~l with 3 moles of ethylene oxide, the condensation product o coconut : 3V alcohol with 5 or 7 moles of ethylene oxide, the co~densation product of tallow alcohol wi~h 6, 9, or 11 moles of ethylene oxide, the condensation product of.secondary C15 alcohol with 5 or 9 moles of ethylene oxide, the condensation product of C12_13 alcohol with 3, 4, 5, 6.5, or 9 moles of ethylene oxide, the condensation product of Cl~ 15 alcohol with 7 or 9 moles of ethylene oxide, the condensation product of C12 alcohol wit~ 5 moles of ethylene cxide, the condensation `. 3L~31$~

product of Cl4-15 alcohol with 3, 4, 5, 7, or 5 moles of ethylene oxide, and mixtures thereof.
A preferred class of surfactants utilizes alcohols which contain about 20% of 2-methyl branched isomers, and are commercially available under the trade mark "Neodol", from the Shell Chemical Company. Particularly preferred nonionic surfactants for use in the compositions of the present invention include the condensation p-oduct of ClO alcohol with 3 moles of ethylene oxide, the condensation product of Cl2 13 alcohol with about 3 moles of ethylene oxide, and the same product which is stripped to remove substantially all lower ethoxylate and nonethoxylated fractions, the conden-sation product of Cl4_l5 alcohol with 7 moles of ethylene oxide, the condensation product of Cl~ 13 alcohol with 6~5 moles of ethylene oxide, the condensation product of Cl2 alcohol with 5 moles of ethylene oxide, the condensation product of coconut alcohol with 5 moles of ethylene oxide, the condensatiQn ~x~ct of C12_13 alcoho:Lwith 9 moles of ethylene oxide, the condensation product of Cl4 15 alcohol with 3 moles of ethylene oxide, the condensation product of Cl~ 15 alcohol with 4 moles o ethylene oxide, the condensation product of C14 15 alcohol with 9 moles of ethylene oxide, : and mixtures thereofO
~ Where optimum particulate soil removal performance is ; 25 sought, it is preferred ~hat cationic surfactants used are of the di-lon~ chain variety and that the nonionic sur-factant be selected from the group consisting of the con~
densation product of Cl4 15 alcohol with 2.25 moles of ethylene oxide, the condensation product of Cl4 15 alcohol - 30 with 7 moles of ethylene oxide, the condensation product of Cl2 15 alcohol with 7 moles of ethylene oxide, the con-densation product of C12 15 alcohol with 9 moles of ethylene oxide, the condensation product of Cl2_l3 alcohol wi moles of ethylene oxide, and the same product which is stripped so as to remove lower ethoxylate and nonethoxylated fractions, the condensation product o Cg 11 alcohol with 8 moles of ethylene ~oxide, which is stripped so as to remove _............................................................ . r-.

9~

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lower ethoxylate and nonethoxylated fractions, the con-densation product of coconut alcohol with 5 moles of ethylene oxide, the condensation product of coconut alcohol with 6 moles of ethylene oxide, -the condensation produc~ of tallow alcohol with 9 moles of ethylene oxide, and mixtures thereof.
The compositions of the present invention may contain mixtures of nonionic surfactants falling within the above preferred nonicnic surfactant,deinition, such as a mixture of the condensation product of C12 13 alcohol with 6.5 moles of ethylene oxide with the condensation product of C14 15 alcohol with 7 moles of ethylene oxide, in a ratio o~ from i about 4:1 to about 1:4. The present invention may also contain mixtures of nonionic surfactants r some o~ which do I not fall within the above preferred nonionic surfactant definition (such as alcohol ethoxylates having an average of greater than about 12 ethylene oxide groups per molecule), ~ and in such mixtures it i5 preferred that at leas~ one of - the nonionic surfactants contained in the mixture falls ' ' within'the above preferred nonionic surfactant definition and that this preferred nonionic surfactant (or mixture of surfactants) be included in an amount such that it falls i within the nonionic/cationic ratio range required herein.
- - ~here the nonionic surfactant mixture contains a non}onic surfactant (or surfactants) which falls outside of the above preferred nonionic surfactant definition, it is preferable that the ratio of the surfactant (or surfactants) within the definition to those outside the definition be within the - xange of from about 1:1 to about 10:1.
In addition to the required nonionic surfactant, preferred nonionic surfactant mixtures also contain alkyl glyceryl ethers. Particularly preferred are glyceryl ethers having the formulae: .

R-0CH2CH-CH2OH and R-O(CH2CH2O)ncH2cHcH2OH
QH OH
wherein R is an alkyl or alkenyl group of from about 8 to 35 about 18, preferably from about 8 to 12~ carbon atoms or an alkaryl group having from about 5 to 14 carbon atoms in the alkyl chain, and n is from 1 to about 6. These compounds may be used together with the nonionic surfactant component of the present invention, in a ratio o nonionic surfactant to glyceryl ether of from about 1:1 to abou~ 4:1, partic-S ularly about 7:3. Glyceryl ethers of the type useful in thepresent invention are disclosed in U.S. Patent 4,09~,713, Jones, issued July 4, 1978, and U.S. Patent No. 4,206,070 of Jones, granted June 3, 1980.

Another preferred group of nonionic surfactants useful herein comprises a mixture of "surfactant" and "co-sur-factant", containing at least one nonionic surfactant ~alling within the definition of the nonionic surfactants preferred herein, as described in Canadian Patent No.
1,059,865 of Jerome H. Collins, granted August 7, 1979.

Cationic Component The cationic surfactants used in the compositions of ~ the present in~ention have the formula RlR2~LZ wherein each R is an oxganic group containing ZL $traight or branched aIkyl or alkenyl group optionally substituted with up to three phenyl or hydroxyl groups, and optionally interrupted by up to four structures selected from the group consisting of:
O O O R~ R2O
Il 1~ 11 1 1 ~ :.
~t c o o c -C-N-, -N-C-, O H H O O g H H O
Il ~ i 11 11 11 1 1 11 -C-N-, -N-C-, -O-, -O-C-O-, -O-C-N-. -N-C-O-, and mixtures thereof~ and which contains from about 8 to 22 carbon atoms, and which may additionally contain up to 20 ethylene oxide groups, and m is a number from 1 to 3~ R2 is an alkyl or hydroxy alkyl group containiny from 1 to 4 carbon atoms, or a benzyl group with no more than one R2 in ~ 12 -a molecule being benzyl, and x is a number from 0 to 11, preferably from 0 to 6. The remainder of any carbon positions on the ~ group are ~illed by hydrogens. Y is selected from the group consisting of:

(l) -N+- , ~ N - C-(2) -C~
N - C -I

(3) -p~_ ~4) -S -.

(5) -N+- , wherein p is from 1 to 12, (C2H~O)pH

(C~H40)pH
~6) -N - , wherein each p is from l to 12, (~2H40) H
. .
C~H40~pH
(7) -N -(C2H40)pH, wherein each p is from l to 12, (C2~40)pH
C \ /

~8) ~C
C

C
/ ~/
(9) N +N t and C C
N

~,, i ~3~

~10) mixtures t~ereof;

; L is 1 or 2~ with the Y groups being separated by a moiety selected from the group consisting of Rl and R2 analogs (preferably alkylene or alkenylene~ having from one to about twenty-two calbon atoms and 2 ~ree carbon single bonds when L is 2. Z is a water-soluble anion such as halide, methyl ! sulfate, sulfate, or nitrate anion, particularly preferre~ I
! anions being chloride, bromide, iodide, sulfate, or methyl sulfate, in a number to give electrical neutrality of the j 10 cationic component.
~ The particular cationic component to be included in a ! given system depends to a large extent upon the particular ¦ nonionic componen-t to be used; it is selected such that it is at least water-dispersible when mixed with the nonionic 1 15 surfactant. The cationic surfactant is chosen, in light of t the paxticulax nonionic surfactant used, in order to satisfy the cloud point requirements of the detergent composition, discussed below. Mixtures of these cationic materials may also be used in the compositions of the present invention.
20 Preferred cationic surfactants are those having critical micelle concentrations of less than about 500 ppm, especially less than about 100 ppm.
In preferred cationic materials, L is equal to 1, p is from 1 to 12, pre~erably from 1 to 10, and Y is C ~ H4~)p~
- C ~C2H4)p~ (C2H4O)pH

or mixtures thereo~. However, L may be equal to two r thereby yielding cationic components containing two cationic charge cen-ters. An example of a di-cationic component is given below:

.

1~31L~9Z

Other cationic materials which are useful in the compo-sitions of the present invention include phosphonium and sulfonium materials.
Additional cationic surfactants useful in the compo-S sitions herein are disclosed in U.S. Paten~ No. 4,259,217 Murphy, issued March 31, 1981.

A particularly preferred type of cationic component, which is described in U.S. Patent No~ 4,260,529, Letton, granted April 7, 1981.

R2-(Zl)a~(R3)n-Z2-(CH2)m-N~-Rl X
Rl :

wherein Rl is Cl to C4 alkyl ox hydroxyalkyl; R2 is C5 to C30 straight or branched chain alkyl, alkenyl, alkylbenzyl or alkyl phenyl, or 1 + 1 X R - N-(CH2)s- ; wherein s is from ~ to 5;

R is Cl to C20 alkylene or alkenylene; a is 0 or 1, n is 0 or 1, and n is 1 when a is 1; m is from 1 to 5; Z and Z
are each selected from the group consisting of O O O O Q H H O O H H O
-C-, -C-O-, -O-C-, -O-, -O-C 0-, -C-N-, -N-C-, -O-~-W~, -N-C-O-, and wherein at least one of said zl or z2 groups i5 O O O H H O
-c-o, -o--, -C-N-, or -N-~-;
and X is an anion which makes the compound at least water-dispersible, preferably selected from the group consisting . . . j.

.

. ~

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- 15 - .
of halide, methyl sulfate, sul~ate, and nitrate, more ~' preferably chloride, bromide, iodide, methyl sulfate and sulfate.
Particularly preferred cationic surfactants o this t:
type are the choline ester derivatives having the following formula: ~
O CH ~-R2-C-O-CH2CH2-N~-CH3 X

~ J
as well as those compounds in which the -C-0- linkase in the ¦ above formula is replaced with O O H H O
1~ p t - t 11 --O-C, -C-N-, or -N-C-.
¦ Particularly preferred examples of this type of cat~
I ionic surfactant include stearoyl choline ester quaternary ¦ ammoni~um halides (R2 = C17 alkyl), palmitoyl choline ester . quaternary ammonium halides ~R = C15 alkyl), myristoyl choline ester quaternary ammonium halides ~R = Cll alkyl~, and tallowyl chGline ester quaternary ammonium halides tR~ =
C~-C17 alkyl).
Additional preferred cationic components of the choline ester variety are given by the structural formulas below, wherein p mày be fro~ 0 to 20.
O O CH
R -o-~-(cH2)p-c-o-cH2cH2-~-cH3 X

X CH3-~ -C~2-CH2-O-C-(CH2)p-C-O-C~-CH2-~ -CH3 X
~H3 C~3 . ... ~

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~ 1 6 -- , The preferred choline-derivative cationic substances, discussed above, may be prepared by the direct esterifi-cation of a fatty acid of the desired chain length with dimethylaminoethanol, in the presence of an acid catalyst.
The reaction product is then quaternized with a methyl halide, forming the desired cationic material. The choline-derived cationic materials may also be prepared by the direct esterification o~ a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material~ The reaction product is then used to quaternize trimethylamine, forming the desired cationic component.
Another type o~ novel, particularly prefexred cationic material, described in U.S. Patent No. 4,228,042, Letton, granted October 14, 1980 has the formula:

R Rl R3-o~(CH)no]y-(Zl)a~ R4)'t-Z2-(C~12)m-N -Rl X

In the abo~e formula, each Rl is a~ Ci to C4 alkyL or hydroxyalkyl group, preerably a m~st~yl group. Each R2 is either hydrogen or Cl to C3 al~yl, preferably hydrogen. R
is a C4 to C30 straight or branched chain alXyl or alkenyl, prefera~ly a C8 to C18 alkyl group, most prefera~ly a C12 alkyl group. R4 is a Cl to C10 alkylene or a~kenylene group. n is from 2 to 4, preferably 2; y is from 1 to 20, 2S preferably from about 1 to 10, most preferably about 7; a - may be 0 or 1, and t may be 0 or 1, but t is 1 when a is 1;
and m is from 1 to S, preferably 2. Z is selected from the group consisting o ~ IT p O H H o ~ ~
-O-C-, -C-O-, -C-, ~O-, -O-C-O-, -C-N-, -N~C-, -O-C-N-, u o O O H
-N C-O-; zl is -C- or -C-N-; and at least one of zl and z2 groups is selected from the group consisting of ~13 3 ~

- ~7 -O O O H H O
Il ~I 11 ~ l 11 -O-C-, -C-O~, -C-N-, -N-C-. X is an anion which makes the compound at least water dispersible, and is selected from the group consisting of halides, methyl sulfate, sulfate, and nitrate, particularly chloride, bromide iodide, methyl sulfate and sulfate. Mixtures of the above structures can also be used.
Where pa.ii~ulate soil removal is to be optimized, it is preferred that the cationic surfactants used are of the di-long chain quaternaxy D onium type, having two chains which contain an average o from about 12 to about 22, preferably from about 16 to about 18 carbon atoms. The remaining groups, if any, attach to the quaternary nitrogen atom, are preferably Cl to ~4 alkyl or hydroxyalkyl groups.
Although it is preferred that the long chains be alkyl groups, these chains may contain hetero atoms or other linkages, such as hydroxy groups, double or triple carbon-carbon bonds, and ester, amide, or ether linkages, as long as each chain falls with the preferred carbon atom ran~es given above. Cationic surfactants of this type are disclosed in Canadian Patent Application Serial No. 323,240 of A.P. Murphy, filed March 12, 1989. Preferred cationic surfactants are those having the formulae:

3 f~N - CH2 ~4 N+ R2 X~ or Rl-c ¦
R N - CH
R~ ~3 wherein the Rl and R2 groups contain an average of xom about 16 to about 22 carbon a~oms, preferably i5 alkyl groups, and most preferably contain an average of from about 16 to about 18 carbon atoms, R3 and R4 are Cl to C~ alkyl or hydroxyalkyl groups, and X is any ~ompatible anion~ partic-ularly one selected from the group consisting of halide,hydroxide, m~thyl sulfate, or acetate anions.

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Preferred cationic surfactants include ditallowalkyl-dimethyl (or diethyl or dihydroxyethylj ammonium chloride, ditallowalkyldimethylammonium methyl sulfate, dihexadecyl-alkyl (C16) (also known as distearyl), dimethyl (or diethyl, 5 or dihydroxyethyl) ammonium chloride, dioctadecylalkyl (C18) dimethylammonium chloride, dieicosylalkyl ~C20) dimethyl-ammonium chloride, methyl~ tallowalkylamiao ethyl (2) tallowalkylimidazolinium methyl sulfate (commercially available as ~;A~iso~t 475 from Ashland Chemical Company), or mixtures of those surfactants. Particularly preferred cationic surfactants are ditallowalkyldimethylammonium chloride, ditallowalkyldLmethylammonium methyl sulfate, methyl(l)tallowalkylamidoe~hyl(2)tallowalkylimidazolinium methyl sulfate, and mixtures o~ those sur~actants, with ditallowalkyldimethylammonium chloride being especially preferred.
Another particularly useful class of cationic sur-factant is that in which the two long chains of the cationic surfactant contain a significant amount of unsaturation, such as where at least about 20~, preferably at least about 30~, of the long chain contain at l~ast one double bondO
Compounds of this type have the fo~mula ..

R4_N+_R2 ~-Rl wherein Rl and R contain an average of Erom about 16 to about 22 (most preferably from about 16 to about 18) carbon atoms, and at least about 20% of these chains contain at least one double bond; R3 and R4 are Cl to C4 alkyl or hydroxyalkyl groups, and X is any compatible anion, partic-ularly one selected from the group consisting of halide, hydroxide, methyl sulfate, or acetate anions. Thus, for example, a preferred cationic surfactant is di-partially hydrogenated tallow dimethylammonium halide (especially chloride or methyl sulfate), which is also known as disoftered-tallowalkyldi.~nethylammonium halide. A commercially available *Trademark ..

..

compound of this type is Adogen ~70, sold by Ashland Chemical Company, wherein about 30% of the tallow chains are oleyl in character. Compositions made with these cationics showed several significant advantages over those made with more conventional cationics (such ditallowalkyldimethyl~nonium chloride), particularly those compositions show improved particulate soil removal, especially at low wash temperatures, improved static control, and remain in a stable single phase at temperature~ down to about 40F.
Utilizing the nonionic and cationic components, defined above, preferred compositions of the present invention may be formulated using the guidance provided by the reduced monomer concentration of the cationic component ~CR) in the laundry solution. Specifically, the selection of a CR value for a given nonionic and cationic surfactant pair will determine the ratio in which to combine those surfactants.
A given nonionic~cationic surfactant pair will ~ive its best particulate or grease~oil removal performance when it is formulated to have a CR value which falls within the ranges defined herein. The reduced monomer concentration of a surfactant is obtained by dividing th~e concentration of the surfactant monomer present in the laundr~ solution by the critical micelle concentration (CMC) of that sur~actant As used in this application, CMCs are aetermined at 105F in water containing 7 grains/gallon of mixed ~2 1; ~a M
hardness, unless otherwise stated.
The concept of reduced cationic monomer concentration is explained in detail in U.S. Patent No. 4,259,217, Murphy, granted March 31, 1981; Tamamushi and Tamaki, Proceedings o~ the Second International Congress of Surface Activity, III, 449, Academic Press, Inc. (1957); and Clint, J. Chem. Soc~ ~ar. Trans., I, 71, 1327 ~lg75) The reduced cationic monomer concentration of the nonionic/ cationic surfactant ~5 mixture is defined by equations (a) through (c), below~ In systems where grease/oil removal i5 to be optimized it is preferred that the CR value of the nonionic/cationic sur-: factant mixture be in the range of from about 0.002 to abou~

*Trademark _. . r-0.2, especially from about 0.002 to about 0.15/ most pre-ferably from about 0.002 to abou-t 0~08. In compositions wherein the particulate,soil removal capabilities are to be optimized, it is preferred that the nonionic/cationic surfactant mixture have a CR of from 0.005 to about 0.2, especially from about 0.008 to about 0.15, most preferably from about 0.01 to about 0.1. It is in the area of overlap (i.e., CR equals about 0.005 to about 0.2) of these CR
ranges that th~ compositions of the present invention yield bo~h optimum particulate and greasy/oily soil removal.
In the following equations these abbreviations are used:
Cl = critical micelle concentration o nonionic : surfactant (moles per liter~
15 C2 critical micelle concentration o cationic surfactant (moles per liter) = a-,constant based upon the heat of mixing = -2.8 e = base, of Napierian logarithm system 3 2.71828 x = mole fraction of the n~onionic surfactant in the micelle at concentration C
f = nonionic activit~2coeficient in the mixed ' ' 1 micelle = e~ X) f2 ~ cationic acti~ity coefficient in the mixed ' micelle = e ~ = f2C2 -flCl Ml = molecular weight of nonionic surfactant .~
M2 ~ molecular weight of cationic surfactant W - total analytical surfactant concentration in the solution (ppm) = sum of the cationic and nonionic concentrations Y - weight fraction of nonionic surfactant in the composition ~here a desired CR value or range is selected, and ~, Cl ~ C2 , Ml and M~ are known for given nonionic/cationic surfactant pair, the corresponding nonionic:cationic ratios(s) -: is calculated as follows:

,. ' ' I

~3 ~a) fox a given nonionic surfactant, cationic sur-factant, and for each end of the CR ran~e desired, solve for x using the equation x2 ~l-x~ R

by standard numerical iterative techniques to an error in x of less than OoO01;
~b) find the range of Y from the equation ---- -- = [X (X~
Ml M2 W

using 100 ppm and 10,000 ppm as the boundary values for W, for each end of the desixed C~
range;
(c) the nonionic/cationic ratio(s) (NCR) corresponding to the CR value or range selected is then obtained ~ by substituting the boundary values for Y into the ~ormula . NCR _ lYy In addition to these reduced cationic monomer concen-tration criteria, compositions which give the best per-formance on greasy/oily soils also satisfy specific cloud ~ 20 point requirements, given below, and detailed in U.S. Patent : No. 4,~59,217r Murphy, granted March 31, 1981.
Thus, these pxeferred compositions have nonionic/cationic mixtures which exhibit a cloud point between about 10C and 70C, more preferably - 25 between about 20C and 70C, especially between about 30~C
and!about 50~C. The compositions will exhibit their best grease/oil xemoval performance when the temperaturP of the wash solution in which they are used falls within about 20C, preferably within about 15C, and most prefexably within about 10C, of the cloud point of the nonionic/
cationic surfactant mixture .

~. . , r~

' ~ ~ 3~

As used herein, the term "cloud point" means -~he temperature at which a graph plotting the light scattering t intensity of the composition versus wash solution temper-ature begins to sharply increase to its maximum value, under 5 the following experimental conditions: j Il The light scattering intensity is measured using a j Model VM-12397 Photogoniodiffusometer, manufac~ure~ by Societe Francaise A I instruments de controle ek a 'analyses, France (the instrument being hereinafter referred to as 10 (SOFICA). The SOFICA sample cell and its lid are washed with hot acetone and allowed to dry. The surfactant mixture is made and put into solution with distilled water at a concentration of 1000 ppm. Approximately a 15 ml. sample of the solution is placed into the sample cell, using a syringe 15 with a 0.2~ nucleopore filter. The syringe needle passes through the sample cell lld, so that the cell interior is not expoc!ed to atmospheric dust. The sample is kept in a variable temperature bath, and both the bath and the sample are subject to constant stirring. The bath temperature is ~ heated using the SOFICA's heater and cooled by the addition ; of ice (heating rate 1C/minute); the temperature of the sample is determined by the t~peratuxe o~ the bath. The light scattering (90 angle intensity of the sample is then determined at various temperatures, using a green filter and 25 no polarizer in the SOFICA.
Builder Mixture The detergent compositlons herein contain from abou~ 5 to about 99%, preferably from about 20% to about 60%~ by weight of a detergency builder mixture. The builder mix~ure 3~ consists essentially of:
(i) a water-insoluble aluminosilicate material se-lected from the group consisting of (1~ Zeolites A, X, or P~B), or mixtures thereof, having a particle size diameter of from about On Ol microns to about 25 microns and contain-ing at least 10% water of hydration, and (2) amorphous h~drated aluminosilicàte makerial ~ T

~;3 of the empirical fonmulao Mz~zAlO2 ySiO2) wherein M is sodium, potassium, ammonium, z is from about n. 5 to about 2, y is 1, said material having a particle size dia~,eter of less than about 100 microns, a magnesium ion exchange capacity of a. least about 50 milligrams equivalents of CaC03 hardness per gram of anhydrous aluminosilica~e, and a Mg~t exchange rate of at least about 1 grain/
gallon/minute~gram~gallon, and (3) mixture.~ thereof; and (ii) a polycarboxylate builder material;
wherein.the weight ratio of the aluminosilicate mater~
~al to the polycarboxylate materia~ is from about 1:10 to about 10~
Preferably, the weight ratio of the aluminosilicate material to the polycarboxylate material is from about 1:4 to about 4:1, more preferably from about 1:~ to about 2:1.
Preferably, the aluminosilicate materials for use herein are those commonly known as Zèolites A, X, and P(B~.
The zeolites should contain at least 10% water of hydration ~nd should have a particle siæe diameter of from abou~ 0.
microns to about 25 microns, preerably rom about 0~1 microns to about 10 microns, more prefexably from about 0.5 microns to about 2 microns. Aluminosilicate materials are more fully descri~ed in U.S. Patent 4,096,081, Phenicie et al~ issued June 20, 1978, The amor- .
phous aluminosilicate materials suitable or use herein are fully described in U.S. Patent No. 4,180,485, Llenado, granted December 25, 1979.

~xamples of suitable polycarboxylate builder materials for use herein are (1) water-soluble aminopolycarboxylates~

,, .

~13~9 -- 2~ --e.g., sodium and potassium ethylenediaminetetraacetates, (2 the water-soluble salts of phytic acid, e.g., sodium and potassium phyta~es, disclosed in U.S. Patent No. 2,739,942, Eckey, issued March 2~, 1956, (3j the polycarboxylate materials described in U.S. Patent 3,364,103; and (4) water-soluble salts of polycarboxylate polymers and copolymers as described in U.S.
Patent No. 3,308,067, Diehl, issued March 7, 1967, A useful detergent builder which may be employed in the present invention comprises a water-soluble salt of a polymeric aliphatic polycarboxylic acid having the following structural relationships as to the position of the carboxy-late groups and possessing the following prescribed physiGal charactexistics: (a3 a minimum molecular weight of about 350 calculated as to the acid form; (b1 an equivalent weight of about 50 ,o about 80 calculat~d as to acid form; (c) at least 45 mole percent o~ the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms; (d) the site of attachment of the polymer chain of any carboxyl-containing radical being separated by not more than three carbon atoms along the polymer chain from the site of attachment of the next carboxyl-containing radical. Spec:ific examples of the above-described builders include polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid and citraconic acid and copol~mers with themselves.
In addition, other builders which can be used satis-factorily include water-soluble salts, especially the sodium and potassium salts, of mellitic acid, citric acid, pyro-mellitic acid, benzene pentacarboxylic acid, oxydiacetic acid~ carboxymethyloxysuccini acid, carboxymethyloxymalonic acid, cis-cyclohexanehexacarboxylic acid9 cis-cyclopenta-netetracarboxylic acid and oxydisuccinic acid.
It is to be understood that while the alkali metalsalts of the foregoing inorganic and organic polyvalent anionic builder salts are preferred ~or use herein from an .. .

~31~9;2 economic standpoint, the ammonium, alkanolammonium, e.g., triethanolammonium, diethanolammonium, and the like, water-soluble salts of any of the foregoing builder anions are also useful herein.
Other suitable polycarboxylates for use herein are ~he polyacetal carboxylates fully described in U.S. Patent

4,144t226, issued March 13, 1979 to Crutchfield et al, and U.S. Patent 4,146,495, issued March 27, 1979 to Crutchfield et al, These polyacetal carboxylates can be prepared by bringing together under polymeriæation conditions an ester of glyoxylic acid ~nd a pol~merization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, cor.verted to the ccrresponding salt, and added to a surfactant. Copending Canadian Patent Application Serial No. 345,728, Rodriguez et al, filed February 15, 1980, ~0 discloses a builder system containing these polyacetal carboxylates along with aluminosilicate b~ilder materials, for use in detergent compositions, which preferably contain nonionic/cationic surfactants.
Preferred polycarboxylate builders for use in the present invention are sodium or potassium nitrilotriacetate or citrate, or mixtures thereof. The compositions of this invention contain from 0 to about 5% phosphate materials, and are preferably substantially free of phosphate materials.
~dditional Components In particularly pr~ferred embodiments oE the present invention, the detergent compositions additionally contain from about 2 to about 25%, preferably from about ~ 'o about 16~, and most preferably from about 2 to about 10% o~ A
~atty amide surfactant, such as ammonia amides (e.g., coconutalkyl ammonia amide, diethanol amides, and ethoxy-lated amides~. In relation to the nonionic/ cationic surfactant system, the ratio of the cationic/ nonionic mixture to the amide component in the composition is in the ~3~2 range of from about 5:1 to about 50:1, preferably from about 8:1 to about 25:1. The addition of the amide component results in a composition which exhibits improved anti-redeposition of both clay and greasy/oily soils. This development is described in greater detail in U.S. Patent No. 4,228,044, Cambre, granted October 14, 1980.
Preferred amides are C~-C20 monoethdnol amides, ~8-C20 diethanol amides, and amides having the formula O H
19 R-C-N-CH2C~20CH2CH2H ~
wherein R is a C8-C20 alkyl group, and mixtures thereof.
Particularly preferred amides are those where the alkyl group contains from about 10 to about 16 carbon atoms, such as coconut alkyl monoethanol or diethanol amide. Such compounds are commercially available under the trademarks '~uperamide GR,"from Onyx Chemical Co., Jersey City, N.J~, "Superamide F-3"from Ryco, Inc., Conshohocken, Pa., and "Gafamide CDD-518,"available from GAF Corp., New York, N.Y.
These amide components may also be added in small amountsr i.e., from about 2~ to about 5~, to act as suds modifiers. Specifically, they tend to boost the sudsing in an active system which exhibits reLatively low sudsing, an~
depress the sudsing in an active system which exhibits relatively high sudsing.
The compositions o~ the present inven~ion may also contain addi~ional ingredients generally found in laundry detergent compositions, at their conventional art-establi~hed levels, as long as these ingredients are compatible with the nonionic and cationic components required herein. For example, the compositions may contain up to about 15%, preferably up to about 5%, and most pre~erably rom about O.001 to about 2~, of a suds suppressor component. Typical suds suppressors useful in the compositions of the present invention include, but are not limited to, those described below.
Preferred silicone-type suds suppressing additives are described in U.S. Patent 3,933,672, issued January 20, 1976, ,.3~ ~3Z
-- 27 ~
Bartolotta et al. The silicone material can be represented by alkylated poly-siloxane materials such as silica aerogels and xerogels and hydrophobic silicas of various types. The silicone material can be described as a siloxane having the ~ormula:

~ ~'~ .
~ ~ )x ~ R'~

wherein x is from about 20 to about 2,000, and R and R' are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl. Polydimethylsiloxanes tR and R' are methyl, having a molecular weight within the range of from about 200 to about 200,000, and higher, are al:l useful as suds controlling agents. Ad~itional suitable silicone materials wherein the side chain g~oups R and R' are alkyl, aryl, ox mixed alkyl and aryl hydrocarbyl groups exhibit useful Suas controlling properties. Examples of suc~
ingredients include diethyl-, dipropyl~, dibutyl-, methyl-e~hyl- t phenylmethyl-polysiloxanes and the like. Additional useful silicone suds controlllng agents can be represented by a mixture of an alkyla~ed siloxane, as re~erred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica.
A preferred silicone suds controlling agent is represented by a hydrophobic silanated (most praferably trimethyl-silanated) silica having a particle size ~n the range from about 10 millimicrons to 20 millimicrons and a specific surface area above about 50 m2~gm intimately admixed with dimethyl silicone ~luid having a molecular weight in the range from about 5G0 to about 200,000 at a weight ratio of silicone to silanated silica of from about lY~l to about 1:2. The silicone suds suppressing agent is advantageously ~eleasably incorporated in a water~soluble or water~
dispersible, substantially non-surface-active, detergent-impermPable carrier.

.. . - r , 3~ 2 Particularly useful suds supp~essors are t~e self-emulsifying silicone suds suppressors, described in U.S.
Patent 4,075,118~ Gault et al, issued Februar~ 21, 197B, An example of such a compound is DB-544," commercially available from Pow Corning, which contains a siloxane/glycol copolymex together with solid silica and a siloxane resin.
Microc-ys alline waxes having a meltin~ point ~n the xange from 35C-115C and a saponification value of less than 100 represent additional examples of a prefer~ed suds regulating component for use in the subject compositions, and are described in detail in U.S. Patent ~0S6J481~ Tate, issued November 1, 1~77, The microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of or~anic sur-factants. Preferred microcrystalline waxes have a meltin~
. .
~` point from about 65C to 100C, a molecular ~eigh~ in the range ~rom 400-1,000; and a penetration value of at least 6, measured at 77F by ASTM-D1321. ',uitable examples of the above waxes include: microcrysta]line and oxidized micro-crystalline petrolatum waxes; Fischer-Tropsch an~ oxidized Fischer~Tropsch waxes; ozokerite; ceresin; montan wax;
; beeswax; candelilla; an~ carnauba wax.
- Alkyl phosphate esters rep~esent an addition~l pre-~5 ferred suds suppressant for use herein. These preferred phosphate esters are predominantly monostearyl p~osphate which, in addition thereto, can contain di- and tristearyl phosphates and mo~o-oleyl phosphates, which can contain di-and trioleyl phosphates.
The alkyl phosphate esters frequently contain some trialkyl phosphate. Accordingly, a preferred phosphate ester can contain, in addition to the monoalkyl ester, e.g.
monostearyl phosphate, up to about 50 ~o~e percen~ of dialkyl phosphate and up to about 5 mole percen~ o~ ~rialkyl phosphate Other adjunct components which may be included in the compositions of the present invention, in their con~entional art-established levels for use ~i.e., from about 0 to about *Trademark . _. - !

~..3~

~ 29 -40%), include semi-polar nonionic (such as amine oxides), anionic, zwitterlonic and ampholytic cosurfactants; deter-gency builders; bleaching a~ents; bleach activatoxs; soil release agents (particularly copolymers of ethylene tere-phthalate and polyethylene oxide terephthalate, such as "Milease r sold by ICI, United States, as disclosed in U.S.Patent 4,132,6~0, Nicol, issued ~anuary 2, 1979 soil suspending agents;
corrosion inhibitors; dyes; fillers; optical brighteners;
germicides; pH adjusting agents~ alkalinity sources; hydro-tropes; enzymes, enzyme-stabilizing agents; perfumes;
solvents; carriers; suds modifiers7 opaci~iers; and the like. However, because o~ the numerous and diverse per-~ormance advantages of the present inVention, certain conventional componentsl such as cosurfactants and other detergency builders, as well as fabric softening and static control agen~s, will not generally be necessary in a par~
ticulax foxmulatlon, giving the compositions of the present invention a potenti~l cost advantage over conventional detergent/ softener compositions. I~ fact, ~ecause tha compositions of the present invention give such outstanding ciay removal performance across the range of water hardness conditions, for environmental reasons the compositions of the present invention contain less than about 5% phosphate materials. Preferred compositions are substantially or totally free of such phosphate materials, without decreasing the perormance of the compositions. Preferred compositions of the present invention are also substantially free of carboxymethylcellulose in order to optimize the clay removal performance of the system. Finally~ while the compositions of the present invention may contain anionic materials, such as anionic surfactants and hydrotropes ~e.g., alkali metal toluene sulfonates), it is preferred that particular anionic materials be contained in amounts sufficiently small such that not more than about 10~, pre~erably not mor~ than about

5%, of the cationic surfactant, contained in the laundry solution, is complexed by the anionic material. Such a complexing of the anionic material with the cationic *Trademark r L3L3~ Z

surfactant, decreases the overall cleaning and fabric conditioning performance of the composition. Suitable anionic materials may be selected based on their strength of complexation with the cationic material included in the composition (as indicated by their dissociation constant).
Thus, when an anionic mat~rial has a dissociation constant of at least about l x 10 (such as sodium toluene sul-fonate), it may be contained in an amoun~ up to about 40%, by weight, of the cationic surfactant; where the anionic material has a dissociation constant of at least about l x 10 5, but less than about l x 10 3, it may be contained in an amount up to about 15~, b~ weight, of the cationic surfactant; and where the anionic material has a dissoci-ation constant of less than about l x lQ 5 (such as sodium Cll 8 linear alkylbenzene sulfonate), it may be contained only in amounts up to about 10%, by weight, of the cationic surfactant. Preferred compositions are subs`tantially free of such anionic materials.
Examples of cosurfactants and detergency builders which ; 20 may be used in the compositions of the present invention are found in U.S. Patent No. ~,717,630, Boo~h, issued February 20, 1973, and U.S. Patent No. 4,259,217 of A.P. Murphy, issued March 31, 1981. However, these components, partic-; 25 ularly the anionic surfactants, should be checked with the particular nonionic/cationic surfac~ant system chosen, and used in an amount, so as to be certain that they will be compatible with the nonionic/cationic surfac~ant system.
The compositions of the present invention may be produced in a variety of forms, includin~ liqui~, solid, granular, paste, powder or substrate compositions. ~re-ferred substrate articles may be formulated according to U.S. Patent No. 4,170,565 of Flesher et al granted October 9, 1979. In a particularly preferred embodiment, the compositions of the present invention are formulated as liquids and contain up to about 20~ of a lower alkyl (Cl to C4~ alcohol, partic-ularly ethanol. Liquid compositions containing lower levels ~ ., - ~

~31~9~

of such alcohols (i.e., about 7 to 12~) tend to exhibit less phase separation than compositions containing higher alcohol levels. Granular compositions herein may also contain up to ! about 15~ by weight of alkali metal silicates, especially sodium silicate (2.0 ratio), to increase flowability and physical stability of the granules.
¦ The compositions of the present invention are used in ¦ the laundering process ~y fonning an aqueous solution containing from about 0.01 (100 parts per million) to abou~
0.3~ (3,000 parts per million), preferably from about 0.02 to about 0.2%, and most preferably from about 0.03 to about 0.15%, of the detergent compositions defined herein, and agitating the soiled fabrics in that solution. The fabrics are then rinsed and dried. When used in this manner~ the compositions of the present invention yield outstanding particulate and greasy/oily soil removal, togethex with fabric softening, static control, colox fidelity, and dye ~ transfer inhibition benefits, without requiring the use of ; any of the other conventionally used fabric softening ; 20 and static control laundry additives~
; All percentages, parts, and ratios used herein are by weight unless otherwise specified.
The following nonlimiting examples illustrate the compositions of the present invention.

, EXAMoeLE _ Identical clay-soiled cotton, polyester~cotton, and polyester swatches were washed in aqueous solutions having dissolved therein: 500 parts per million (ppm) of a sur-factant mixture containing 4.5 parts of the nonionic sux-factant C12 13 E6 5 (condensation product o C12 13 alcohol with 6.5 mole~ of ethylene oxide, commercially available as Neodol 23-6.~'from Shell Chemical Company) and 1 part of the cationic surfactanttdihydrogenated tallowalkyl di-methylammonium chloride); 600 ppm of the builder or buildermixture listed below; and 87 ppm of monoethanol amine.
~he swatches were washed for lO'minutes in a miniature , agitator containing 1-1/2 gallons of washing liquor at 100F and artificial water hardness (2 moles Ca~ to 1 mole Mg~+) at levels of 2, 7 and 1~ grains per gallon.
The swatches comprised approximate:Ly 4% by weight of the washing liquor. After washing, the swatches were spun ary and rinsed with 1-1/2 gallons of water, at lOO~F, having the same water hardness as that of the water they were washed in. The swatches were then dried in a miniature electric dryer. A Hunter Reflectometer was used to obtain ` a~reflectance reading (in Hunter Whi'teness Units) for each of the laundered swatchesn A higher reflectance reading indicates greater cleaning effectiveness. The results were as foll`ows: , . ... .
Fabric Water''Hardness' Hunter Whiteness Units , .. . . .. . .
Solution_Containing 600 p;~ Sodium Citrate Cotton2 gr./gal. 20.37 ~ 2.69 ~ 7 gr./gal. 18.59 ~ 1.40 ..12 gr./gal. 11.50 ~ 1.19 Polycotton2 gr.~gal. 63.47 ~ 2.13 n 7 gr./gal. 62.17 ~ 0.31 "12 gr./gal. 55.85 ~ 0~59 Polyester2 gr./galO 74.35 -~ 1.05 ~ 7 gr.Jgal. 72.65 ~ 1.13 "12 gr./gal. 70.75 ~ 1.05 *Trademark 113~B$~2 Solution Containing 600 ppm Sodium Nitrilotriacetate Cot~on2 gr.~gal. 27.88 f 1,49 "7 gr.~gal. 24.71 + 1.26 "12 gr./gal. 15O84 ~ 1.68 Polycotton 2 gr./gal. 65.35 ~ 1.91 7 gr./gal. 63~55 _ 0.~2 "12 gr./gal. 58.35 + 0.84 Polyester 2 gx./gal. 81.14 1.34 "7 gr./gal. 80.38 ~ 0.48 "12 gr./gal. 75.95 ~ 1.17 Solution Containing 600 ppm Po-lyacetal Carboxylate*
Cotton2 gr./gal. 28.60 ~ 0.30 7 gx./gal. 24.98 ~ 0.69 "12 gr./gal. 15.94 ~ 0.96 15 Polyco~ton 2 gr~/gal. 59.86 ~ 1.34 gr./yal. 56.5~ + 3.07 "12 gr./gal. 50.08 + 3.12 Polyester 2 gr./gal. 70.06 ~ 0.83 "7 gr./gal. 61.55 + 0.81 ~ `12 gr./gal. 4~45 + 2.04 Solution Containing 600 ppm Sodium Mellitate Cotton2 gr./gal~ 21.82 ~ 0.39 "7 gr./gal. 16.2~ + 2.Ç3 "12 gr./gal. 14.72 ~ 1.17 25 pOlycotton 2 gr./gal. 62.43 0.37 n7 gr./gal. 56.50 ~ 0.67 " ~12 gr./gal. 59.41 + 1.00 Polyester 2 gr./gal. 74.00 ~ 1.84 . . n .7 gr./gal. 73.64 + 0.18 "12 gr./gal. 65.46 ~ 1.23 Solution Cont:aining 600 ppm Zeolite ~**
Cotton2 gr.~gal~ 17.35 ~ 2.51 -~
-7 gr./gal. 11.43 ~ 1~37 ~12 gr./gal. 7.57 ~ 1.90 * 1, CH3CH2 I -C - O CH-OCH2CH3;n = 86 (average) CH3 COONa ~ CH3 Hydrated, particle dîameter 1-10 microns ~same through-out this Example) r ~13~

Polycotton2 gr./gal. 55.54 ~ 1.34 7 gr./gal. 48.37 + 1.43 " 12 gr./gal. 57.94 ~ 0.75 Polyester2 gr./gal. 71.65 ~ 0.86 " 7 gr./gal. 71.~0 ~ 0.76 " 12 gr./gal. 69.17 ~ 1.53 .
~ S~lution Containing 600 ppm Zeolite X***
_.
Cotton2 gr.~gal. 19.02 ~ 1.50 " 7 gr./gal. 14.77 + 2.04 " 12 gr./gal. 14.29 ~ 1.21 Polycotton2 gr./gal, 54.73 ~ 1.09 " 7 gr./gal. 50.89 ~ 4~47 " 12 gr.~gal. 59.41 ~ 1.34 ~ ~ - - Polyester2 gr.~gal. 71.9~ ~ 0.98 ; 15 - 7 gr./gal. 71.32 ~ 1.36 n 12 gr./gal. 70.~9 ~ 0~72 Solution Containing 30-0 ppm Zeolite A and 300 ppm Sodium Nitrilotriace-tate ` i - Cotton2 gr.~gal. 31.82 + 0.96 ~` 20 " 7 gr./gal. 29.40 ~ 0.6~
12 gr./gal. 24.84 ~ 1.89 P~olycotton2 gr./gal. 67.24 t 0.47 '" 7 gr./gal. 66.85 + 1.57 " 12 gx./gal. ~2.88 + 1.07 - 2`5 Polyester -2 gr./gal. ~2.84 ~ 1.32 7 gr./gal. ~0.81 ~ 1~34 12 gr./gal. 77.67 ~ 0.58 Solution Containinq 300 ppm Zeolite A and 300 ppm Sodium Citrate Cotton 2 gr./gal. 27.66 ~ 0.80 ~ 7 gr./~al. 26.80 ~ 1.41 " ~ 12 gr./gal. 21.96 ~ 0.47 Polycotton 2 gr./gal. 64.~0 ~ 0.67 " 7 grO/gal. 52.68 ~ 0.37 " 12 gr./gal. 61.31 ~ 1 48 ***
Hydrated, particle diameter 1~10 microns .

_ .......

~3~
' -35 - -Polyester2 gr.jgal. 78.11 f 0.55 "7 gr./gal. 77.65 ~ 2.31 "12 gr./gal. 74.28 ~ 0.68 Solution Contain'ing 300 ppm Ze ~ ite A and ; 5 300 ppm Polyacetal Carboxylate Cotton2 gr./gal. 37.57 ~ 1.30 "7 gr./gal. 33.48 ~ 0.55 . n12 gr./gal. 25.66 ~ 1.37 Polycotton2 gr./gal. 67.09 + 1.20 ~7 gr./gal. 63.54 ~ 0.44 ' "12 gr./gal. 58.37 ~ 0.80 Polyester2 gr./gal. 70.09 ~ 1.52 "7 gr./gal. 68.89 ~ 1.32 "12 gr./gal. 64.87 ~ 1.23 . .....
15 ' Sol~tion Containing 300 ppm Zeolite' A and 300 'ppm ~Sod'ium Mëllitate Cotton 2 gr./gal. 28.04 ~ 2.07 . n. . 7 gr./gal. 27.26 ~ 0~58 " 12 gr./gal. 24.7% ~ 0.21 20Polycotton2 gr./gal. 63.74 ~ 0.84 " , , 7 gr./gal. 60.61 ~ 2.09 - ' " ' ' 12 gr./gal. 59.35 ~ 1~71 Polyester2 gr./gal. , 74.88 ~ 0.51 " 7 gr./gal. 71.34 ~ 1.75 25" 12 gr./gal. 66.S5 ~ 3O25 Solution Containing 150 ppm Zeolite A and - - 450 ppm Sodium Nitrilotriacetate ! Cotton 2 gr./gal. 30.91 ~ 1.49 ~ 7 gr./gal. 28.34 + 1.33 i 30 ~ gr.~gal. - 13.73 1~24 Polycot-ton -2 gr./gal. 67.80 ~ 0.35 , 7 gr./gal. 60.98 ~ 2 12 gr./gal. 55.23 ~ 1.22 Polyester 2 gr./gal. 84.22 ~ 0.98 " ' 7 gr./gal. 82.11 ~ 0~68 '~ 12 gr./gal. 77.47 -~ 0.43 .

_ . . ,_.. . . ..

~36 -j - Solution Containing 150 ppm Zeolite A and 450 ppm Sodlum Citrate Cotton 2 gr./gal. 25.22 ~ 3.07 " 7 gr./gal. 21.15 + 0.92 " 12 gr./gal. 15.56 ~ 2.12 Polycot~on 2 gr./gal. 63.63 + 1.31 " 7 gr./gal. 62.62 ~ 1.72 ~ r./gal. 57.27 + 2.42 Polyester 2 gr./gal. 81.75 ~ 0.86 ~ 7 gr./gal. 78.1} ~ 1.02 " 12 gr./gal. 71.82 ~ 1.33 Solution Containing 150 ppm Zeolite ~ and 450 ppm Polyacetal Carboxylate*
Cotton 2 gr./gal. 28.44 + 0.80 " 7 gr./gal. 25.25 + 0.08 " 12 gr./gal. 1~.31 + 1.18 I Polycotton 2 gr.~gal. 60.36 ~ 1,7~
i " 7 gr./~al. 57.30 ~ 0.~2 i - n ~ 12 gr./gal. S0.83 ~ 0.57 Polyester 2 gr./gal. 7?.51 -~ 1.26 7 gr./gal. 73.85 + 0.2~
~" 12 gr./gal. 67.35 ~ 1.05 Solution Containinq 150 ppm Zeolite A and 45-0 ppm Sodium l~lellitate Cotton -2 gr.fgal. 23.65 0.75 " 7 gr./gal. 17.28 ~ 1.15 ; ~ " 12 gr./gal. 14.52 + 2.64 Polycotton 2 gr./gal. 59.13 + l.g2 - " 7 gr./gal. 56.82 + 2.96 " 12 gr./gal. 54.92 + 1.66 Polyester 2 gr./gal. 76.37 + 1.48 gr./gal. 75.73 + 0.99 . . - n - l~ gr./gal. 76.80 + 0.~2 - These results clearly demonstrate that syner~istic cleaning perormance was provided by the combination of the aluminosilicate and polycarboxylate builder materials.
Substantially better overall cleaning was provided, at the . -37 -same total builder level in otherwise identical composi-tions, by the detergent.composition containing the builder mixture than was provided by the detergent compositions containing only the individual builders.
Substantially similar cleaning results are obtained when the cationic surfactant is replaced, in whole or in part, by ditallowalkyldimethylammo~lium methyl sulfa-~e, ditallow-alkyldimethylammonium iodide, dihexadecylalkyldimethyl-ammonium rhloride~ dihexadecylalkyldihydroxylethylammonium . 10 methyl sulfate, dioctadecylalkyldimethyla~monium chloride, dieicosylalkyl methyl ethyl ammonium chloride, dieicosyl-alkyl dimethylammonium bromide, methyl (1) tallowalkyl amido . ethyl (2) tallowalkyl imidazolinium methyl sulfate, or mixtures of these surfactants.
Substantially similar results are also obtained where the nonionic su-rfactant in Composition A i~ replacedj in whole or in part, by the condensation product o C14_15 alcohol with 2.25 moles of ethylene oxide; the condensation product of C14 15 alcohol with 7 moles of ethylene oxide;
the condensation product of C'12 15 alcohol with 9 moles of ethylene oxide; the condensation product of C12 13 alcohol with 6.5 moles of ethylene oxide, which is stripped so as to remove lower ethoxylate and nonethoxylated fractions; the ~ condensation product of coconut alcohol with 5 moles o~
. 25 ethylene oxide; the condensation product of coconut alcohol with 6 moles of e~hylene oxide; the condensation product of C12 15 alcohol with 7 moles of ethylene oxide; the conden- -sation product of tallow alcohol with 9 moles of ethylene oxide; a 1:1 by weight mixture of the condensation product of C12 15 alcohol with 7 moles of ethylene oxide and the condensation product of Cl~ 15 alcohol with 7 moles or ethylene oxide; and other mixtures of those surfactants.
Excellent cleaning results are also obtained where the ratio of nonionic surfactant to cationic sura~tant used is about 2:1, 3:1, 3.5:1, 5:1, 6:1 or 9:1.
Cleaning benefits are also obtained when the weight ratio of the aluminosilicate material to the polycarboxy-late material is from about 1:10 to about 10:1, especially ~ F -I

3~3~ Z

-~8 when from about 1:4 to about 4:1. At aluminosilicate/poly-carboxylate ratios above 1, the cleaning advantages are most readily apparent at high water hardness levels, such as above 7 grains/gallon.
Similar synergistic cleanin~ effects are obtained when the aluminosilicate material is any hydrated Zeolite A, X or PtB), having a particle size diameter of from about 0.01 microns to about 25 microns, especiall- Crom about 0.1 microns to about 10 microns.
5ubstantially similar cleaning performance is obtained when the number of segments (n) in the polyacetal carboxy-late builder averages at least 4, but especially when n averages between 10 and 200.
EXAMPLE II
The following detergent composition was produced:
Component Wt.f%
~ihydrogenated tallowalkyl7~65 dimethylammonium chloride ~12-13 E6 5 34.45 Monoethanol amine 7.3 Polyacetal carboxylate 25.25 Hydrated Zeolite A (particle - ~5.25 diametex 1-10 microns~
lCondensation product of ~12 13 alcohol with 6.5 moles of ethylene oxide, commercially available as Neodol 23-

6.5 from Shell Chemical Company.
This composition delivered excellent particulate soil removal perfarmance, as demonstrated in Example I. Further, the composition provided greasy/oily soil removal ~enefits.
EX~MPLE III
The following deteryent composition was produced~
Component ` Wt.~
Dihydrogenated tallowalkyl7.65 dimethylammonium chloride C12-13 E6 5 34~45 Monoethanol amine 7.3 Sodium nitrilotriacetate 25.2S
Hydrated Zeolite A (particle 25.25 diameter 1-10 microns) A
~ 9~

lCondensation product of C12 13 alcohol with 6.5 moles of ethylene oxide, commercially available as Neodol 23-6.5 from Shell Chemical Company.
This composition delivered excellent particulate soil removal performance, as demonstrated in Example I. Further, the composition provided greasy/oily soil removal benefits.
EX~MPLE IV
The following detergent composition is produced:
Component W~.~%
C12_13(EO)6.5 12.0 Cl~_ls(EO)7 0 12.0 Ditallow dimethylammonium 4.8 chloride - Ethanol lo o Polyacetal carboxylate 10.0 Hydrated Zeolite A 10.0 (particle diameter 1-10 microns) Miscellaneous (includes pcrfume, 0.37 brightener, dye) Water Balance .... . ..
EXAMPLE V
The following detergent composi~ion is produced;
Component Wt./%
C12_13(EO~6.5 12.0 C14_15(EO)6 5 12.0 , Ditallow-dimethylammonium 4.8 ' chloride Ethanol 10.0 Sodium nitrilotriacetate 10.0 Hydxated Zeolite A ~particle 10.
diameter 1-10 microns) Miscellaneous (include perfume, 0.37 brightener dye) Water Balance EXAMPLE VI
The following detergent composition is produced:
Component Wt.
C12_13(EO)6 5 12.0 C14_ls(EO)7 0 12.0 Ditallow dimethylammonium 4.8 chloride ~ ~3~

Ethanol 10.0 Sodium citrate . 1~.0 Hydrated Zeolite A 10.0 (particle diameter 1~10 microns) Miscellaneous (includes perfume, 0O37 brightener, dye) Water Balance EXA~LE VII
The following detergent composition is produced:
Component Wt.~%
C12-13 (E)6.5 Ditallow dimethylammonium chloride 7.0 Hydrated Zeolite A (particle 25~0 diameter 1-10 microns) .
Sodium nitrilotriacetate 25.0 Sodium silicate ~2.0 ratio) ~.0 Miscellaneous (includes perfwme r Balance brightener, dye! and moisture) ~ . -EXAMPL~. VIII
The following detergent composition is producea:
I Component Wt./6 _13(E)6.5 ~ 30.0 Ditallow dimethylammoniwm chloride 7.0 ~ Hydrated Zeolite B (particle 25.0 diameter 1-10 microns) Sodium citrate 25.0 Sodium silicate (2.0 ratio) 5.0 Miscellaneous (includes per~ume, Balance brightener, dye, and moisture) EXAMPLE IX
The followin~ detergent composition i5 produced:
Component Wt./~
C~2_13(Eo)6.5 30~0 Ditallow dimethylammonium chloride .7.0 Hydrated Zeolite B (particle 25.0 diameter 1-10 microns) Polyacetal carboxylate 25.0 Sodium silicate (2.0 ratio) 8~0 Miscellaneous (includes perfume, Balance brightener, dye, a~d moisture) . .~. ~ !

Claims (19)

WHAT IS CLAIMED IS:

1. A detergent composition, which contains from 0 to about 5% phosphate materials, comprising:
(a) from about 1% to about 95% of a surfactant mixture consisting essentially of:
(i) a nonionic surfactant having an HLB of from about 5 to about 17; and (ii) a cationic surfactant, having the formula wherein each R1 is an organic group containing a straight or branched alkyl or alkenyl group optionally substituted with up to 3 phenyl or hydroxy groups and optionally interrupted by up to 4 structures selected from the group consisting of , , , , , , , , , , , and mixtures thereof, each R1 containing from about 8 to about 22 carbon atoms, and which may additionally contain up to about 20 ethylene oxide groups; m is a number from 1 to 3; each R2 is an alkyl or hydroxy alkyl group containing from 1 to 4 carbon atoms or a benzyl group r with no more than one R2 in a molecule being benzyl; x is from 0 to 11, the remainder of any carbon atom positions being filled by hydrogens; Y is selected from the group consisting of (1) , (2) (3) , (4) , (5) , wherein p is from 1 to 12, (6) , wherein each p is from 1 to 12, (7) , wherein each p is from 1 to 12, (8) , (9) , and (10) mixtures thereof;

L is 1 or 2, the Y groups being separated by a moiety selected from the group consisting of R1 and R2 analogs having from one to about twenty-two carbon atoms and 2 free carbon single bonds when L is 2; Z is an anion in a number sufficient to give electrical neutrality to the molecule; said cationic surfactant being at least water-dispersible in admixture with said nonionic sufactant;
wherein the ratio of said nonionic surfactant to said cati-onic surfactant is from about 1:1 to about 100:1; and (b) from about 5% to about 99% of a detergency builder mixture consisting essentially of:
(i) a water-insoluble aluminosilicate material selected from the group consisting of:
(1) Zeolites A, X, or P(B), or mixtures thereof, having a particle size diameter of from about 0.01 microns to about 25 microns and containing at least 10%
water of hydration, (2) amorphous hydrated aluminosilicate material of the empirical formula:
Mz(zAlO2?ySiO2) wherein M is sodium, potassium, ammon-ium, z is from about 0.5 to about 2, y is 1, said material having a particle size diameter of less than about 100 microns, a magnesium ion exchange capacity of at least about 50 milligrams equivalents of CaCO3 hardness per gram of anhydrous aluminosilicate, and a Mg++
exchange rate of at least about 1 grain/gallon/minute/ gram/gallon, and (3) mixtures thereof; and (ii) a polycarboxylate builder material; wherein the weight ratio of the aluminosilicate material to the polycarboxylate material is from about 1:10 to about 10:1.

2. A composition according to Claim 1 comprising from about 20% to about 50% by weight of the builder mixture.

3. A composition according to Claim 1 wherein the weight ratio of the aluminosilicate material to the polycarboxylate builder material is from about 1:4 to about 4:1.

4. A composition according to Claim 3 wherein the weight ratio of the aluminosilicate material to the polycarboxylate builder material is from about 1:3 to about 2:1.

5. A composition according to Claim 1 wherein the poly-carboxylate builder material is selected from the group consisting of the water-soluble salts of nitrilotriacetic acid, ethylene diaminetetraacetic acid, mellitic acid, citric acid, pyromellitic acid, benzene pentacarboxylic acid, oxydiacetic acid, carboxymethyloxysuccinic acid, carboxymethyloxymalonic acid, cis-cyclohexanehexacarboxylic acid, cis-cyclopentanetetracarboxylic acid and oxydisuccinic acid or mixtures thereof.

6. A composition according to Claim 5 wherein the polycar-boxylate builder material is sodium or potassium nitrilo-triacetate or citrate, or mixtures thereof.

7. A composition according to Claim 1 wherein the alumino-silicate material is Zeolite A, X or P(B), or mixtures thereof.

8. A composition according to Claim 7 wherein the alumi-nosilicate material has a particle size diameter of from about 0.1 microns to about 10 microns.

9. A composition according to Claim 8 wherein the aluminosilicate material has a particle size diameter of from about 0.5 microns to about 2 microns.

10. A composition according to Claim 8 wherein the poly-carboxylate builder material is selected from the group consisting of the water-soluble salts of nitrilotriacetic acid, ethylene diaminetetraacetic acid, mellitic acid, citric acid, pyromellitic acid, benzene pentacarboxylic acid, oxydiacetic acid, carboxymethyloxysuccinic acid, carboxy-methyloxymalonic acid, cis-cyclohexanehexacarboxylic acid, cis-cyclopentanetetracarboxylic acid and oxydisuccinic acid or mixtures thereof.

11. A composition according to Claim 10 wherein the poly-carboxylate builder material is sodium or potassium nitril-otriacete or citrate, or mixtures thereof, and the weight ratio of the aluminosilicate material to the polycarboxylate builder material is from about 1:4 to about 4:1.

12. A composition according to Claim 11 wherein the weight ratio of the aluminosilicate material to the polycarboxylate builder material is from about 1:3 to about 2:1.

13. A composition according to Claim 11 which is substan-tially free of phosphate materials.

14. A composition according to Claim 11 wherein the ratio of said nonionic surfactant to said cationic surfactant is from about 1:1 to about 50:1.

15. A composition according to Claim 14 wherein the ratio of said nonionic surfactant to said cationic surfactant is from about 5:1 to about 20:1.

16. A composition according to Claim 11 wherein said non-ionic surfactant has the formula R(OC2H4)nOH wherein R is a primary or secondary alkyl chain of from about 8 to about 2 carbon atoms and n is an average of from about 2 to about 12.

17. A composition according to Claim 16 wherein the cat-ionic surfactant is selected from the group consisting of , , or mixtures thereof, wherein the R1 and R2 groups contain an average of from about 16 to about 22 carbon atoms, R3 and R are C1 to C4 alkyl or hydroxyalkyl groups, and X is an anion selected from the group consisting of halide, hydrox-ide, methyl sulfate, sulfate, or acetate.

18. A composition according to Claim 17 wherein the cat-ionic surfactant is selected from the group consisting of ditallowalkyldimethylammonium chloride, ditallowalkyldi-methylammonium methyl sulfate, dihexadecylalkyidimethyl-ammonium chloride, dioctadecylalkyldimethylammonium chlor-ide, dieicosylalkyldimethylammonium chloride, methyl (1) tallowalkyl amido ethyl (2) tallowalkyl imidazolinium methyl sulfate, and mixtures thereof.

19. A composition according to Claim 16 wherein the cat-ionic surfactant is selected from the group consisting of:

wherein R1 is C1 to C4 alkyl or hydroxyalkyl; R2 is C5 to C30 straight or branched chain alkyl, alkenyl, alkylbenzyl or alkyl phenyl, or wherein s is from 0 to 5; R3 is C1 to C20 alkylene or alkenylene; a is 0 or 1; n is 0 or 1, and n is 1 when a is 1; m is from 1 to 5; z1 and z2 are each selected from the group consisting of , , , , , , , , , and wherein at least one of said groups is , , , or ; and X is selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate anions;

(b) wherein each R1 is a C1 to C4 alkyl or hydroxy-alkyl group; each R2 is a hydrogen or C1 to C3 alkyl group; R3 is a C4 to C30 straight or branch-ed chain alkyl or alkenyl; R4 is a C1 to C10 alkylene or alkenylene group; n is from 2 to 4; y is from 1 to 20; a may be 0 or 1, and t may be 0 or 1, but t is 1 when a is 1; m is from 1 to 5; z2 is selected from the group consisting of , , , , , , , , ;

z1 is selected from the group consisting of:
or ;

and at least one of z1 or z2 is selected from the group consisting of , , , ;

and X is selected from the group consisting of halides, methyl sulfate, sulfate, and nitrate; and (c) mixtures thereof.