CA1111060A - Biodegradable cationic surface-active agents - Google Patents

Abstract

ABSTRACT
Novel, biodegradable cationic surface-active agents are disclosed. These compounds, when used in laundry detergent compositions together with selected nonionic surfactants, provide excellent removal of particulate and greasy/oily soils, as well as providing fabric softening, static control, and dye transfer inhibition benefits to the laundered fabrics. The novel biodegradable cationic surface active agents have the formula wherein each R1 is C1 to C4 alkyl or hydroxyalkyl; each R2 is either hydrogen or C1 to C3 alkyl; R3 is C4 to C30 straight or branched chain alkyl or alkenyl:
R4 is C1 to C10 alkylene or alkenylene; n is from 2 to 4;
y is from 1 to 20; a is 0 or 1, and t is 0 or 1, but t must be 1 when a is 1; m is from 1 to 5; Z2 is selected from the group consisting of , , , -O-, , , , , ;
Z1 is selected from the group consisting of , , , , ;

said selections being made so that is an alkyl or alkenyl group which can be interrupted by only structures selected from the group consisting of:

, , , , -O-, , , and

Description

Technical Field .
; This invention relates to laundry detergent compo-sitions containing no or low levels of phosphate materials, which exhibit highly improved particulate soil removal capabilities. ~hese detergent compositions p~rovide sur-. prisingly effective clay soiI removal performance even in the absence of detergency builders. Similar compositions which utilize mixtures of selected nonionic surfactants and selected cationic surfactants and which give unexpectedly . 10 good removal of greasy/oily and body soils are defined in .. Canadian Patent Application Serial No. 306,474, Murphy, ... filed June 29, 1978.
.. Background Art :` Nonionic surfactants are generally used in laundry . ., ` 15 detergent compositions for their ability to remove greasy and oily soils. Cationic surfactants have also been used in detergent compositions, primarily to provide adjunct . fabric care benefits, and not for the purpose of cleaning.
Certain cationic surfactants have been included in detergent . 20 compositions for the purpose of yielding a germicidal or - sanitization benefit to washed surfaces see, for example, U.S. Patent 2,742,434, Kopp, issued April 17, 1956; U.S.
Patent 3,539,520, Cantor et al, issued November 10, 1970;
: and U.S. Patent 3,965,026, Lancz, issued June 22, 1976.
Other cationic surfactants, such as ditallowalkyldimethyl-` ammonium chloride, are included in detergent compositions for the purpose of yielding a fabric-softening benefit, as disclosed in U.S. Patent 3,607,763, Salmen et al, issued

-2~

September 21, 1971; and U.S. Patent 3,644,203, La~berti et al, issued February 22, 1972. Such components are also used to control static, as well as soften laundered fabrics as, for example, in U.S. Patent 3,951,879, Wixon, issued April 20, 1976; and U.S. Patent 3,959,157, Inamorato, issued May 25, 1976. However, none of t:hese patents indicate that by the careful selection and combination of certain nonionic and cationic surfactants, to achieve specific nonionic:
cationic surfactant ratios and reduced cationic monomer con-centrations, outstanding removal of particulate soils maybe obtained.
The compositions of the present invention have out-standing cleaning capabilities. In laundry tests, these compositions,not containing any builder components, have been shown to remove clay soils at least as well, and in some cases dramatically better, than fully-built conven-tional laundry detergent compositions. In addition, the compositions inhibit the transfer of dyes, soften and control static through the washing and drying operations. Further, by selecting the preferred cationic components defined in :~ this application, the compositions additionally provide biodegradability and excellent removal of greasy and oily soils, while also providing, in a single detergent product, particulate soil removal, fabric softening, static control and dye transfer inhibition benefits to the laundered fabrics.
The cleaning performance, which is superior to that previously demonstrated, is the result of a heretofore unrecognized cleaning potential of certain selected cationic surfactants ~.

.
.
~` ' ~ , , . ., , . : . :
, ' ` when used in the presence of certain selected nonionic sur-factants under the conditions specified herein.
It is an object of this invention to provide laundry detergent compositions which yield outstanding particulate soil removal, and which also provide fabric softening, static control and dye transfer inhibition benefits.
It is another object of this invention to provide laundry detergent compositions, yielding excellent particu-late soil rèmoval, which may be used in a vaxiety of physi-cal forms, such as liquid, solid, paste, granular, powder, ; or in conjunction with a carrier such as a substrate.
It is a further more specific object of this inventionto provide specific detergent compositions which yield excellent particulate soil removal and which are biodegradable.
It is a still further specific object of this invention to define specific novel cationic surfactants which are bio-degradable and which yield excellent particulate and greasy and oils soil removal performance, as well as fabric softening and static control, in the cationic/nonionic surfactant systems of the present invention.
It is another specific object of this invention to provide amide-containing cationic/nonionic surfactant-containing compositions which yield both excellent particu-late soil removal and anti-redeposition properties.
It is yet another object of this invention to provide a process for laundering fabrics which yields especially good particulate soil removal, using cationic and nonionic sur-factant-containing detergent compositions.

., . '~

:~~

Disclosure of the Invention The present invention re:Lates to novel biodegradable ` cationic surface-active agents, having the formula .' R2 1_ R3-o[ (CH)no]y~(Zl)a~(R4)t~Z2~(CH2)m~M -Rl X

Rl wherein each Rl is Cl to C4 alkyl or hydroxyalkyl; each R2 is either hydrogen of Cl to C3 alkyl; R3 is C4 to C30 : straight or branched chain alkyl or alkenyl;
- 10 R4 is Cl to C10 alkylene or alkenylene; n is from 2 to 4;
y is from 1 to 20; a is 0 or 1, and t is 0 or 1, but t must - be 1 when a is 1; m is from 1 to 5; Z is selected from the group consisting of

3 3 3 ~ T I 11 3 1 -O- -, - -O-, - -, -O-, -O- -O , -C-N-, -N-C-, -O- -N-, H ~
-- -- --O--Z is selecte~ from the group consisting of 2 0 ~O~~~ O~ r ~~~ r ~~ ~~;
said selections being made so that R

R ~O[(~H)nO]y~(Z )a~(R4)t-Z2-(CH2)m-is an alkyl or alkenyl group which can be interrupted by only structures se:Lected from the group consisting of:

-~-O-, -O-~ -N-, -N-~-, : . , , :

-O-, -O-~-O-, -O-~-N-, and -~-~-O-- and wherein at least one of said zl and z2 groups is selected - from the group consisting of ester, reverse ester, amide, ; 5 and reverse amide; and X is an anion which makes the surfactant at least water-dispersible.
These compounds, when used in laundry detergent compositions together with selected alcohol polyethoxylate nonionic surfactants, in ratios of nonionic surfactant to cationic surfactant of from about 1:1 to about 100:1, provide ; excellent removal of both particulate and greasy~oily soils.
~- The compositions also provide fabric care benefits, such as " fabric softening, static control, and dye transfer inhibition benefits to fabrics laundered with them.
The compositions of the present invention comprise, by weight, from about 5 to about 100%, particularly from about 10 to about 95%, and most preferably from about 20 to about 90%, of a mixture of the particularly defined cationic and nonionic surfactants in the ratios stated. It is preferred that the detergent compositions contain at least about 1%
of the cationic component; otherwise, sufficient cationic surfactant may not be present in the wash solution to provide the desired cleaning results. In addition, preferred compo-sitions contain less than about 10% of the cationic component, due to commercial availability and cost considerations.
The compositions of the present invention may be formulated so as to have a pH of at least about 6 in the laundry solution at conventional usage concentrations in order to optimize cleaning performance; preferably they are alkaline in nature when placed in the laundry solution and have a pH of greater than about 7. At pH lower than about 6, the particulate soil removal capabilities of the compositions tend to decrease. Particularly preferred compositions have a pH of at least about 8 in the laundry solution, in order to improve the removal of body soil.
The compositions may also be free of oily hydrocarbon .
materials, such as mineral oil, paraffin oil, dry cleaning solvents and kerosene, because these materials (which are ' themselves oily in nature), load the washing li~uor with ; excessive oily material, thereby diminishing the cleaning effectiveness of the compositions.
Nonionic Component The nonionic surfactants used in the compositions of the present invention are biodegradable and have the formula R(OC2H4)nOH
wherein R is a primary or secondary alkyl chain of from about 8 to about 22, preferably from about 10 to 18, carbon atoms and n is an average of from about 2 to about 12, preferably from about 2 to about 9, most preferably from about 2 to about 7, and especially from about 4 to about 7.
The nonionic surfactants included within the present inven-tion include branched alcohol ethoxylates. The nonionics have an HLB (hydrophilic-lipophilic balance) of from about 5 from about 17, preferably from about 6 to about 14, and especially 10 to about 13.5. These nonionic surfactants are preferably combined with less soluble cationic materials ~ .

.:
.' ', ', ' ` , ' ~', .

:' ' :; . ~ , .... `:

:`
(such as those having 2 or 3 long alkyl chains). Where more soluble cationic materials are used, nonionic surfactants of lower HLB may be equally as beneficial. HLB is defined in detail in Nonionic Surfactants, by M. J. Schick, Marcel Dekker, Inc., 1966, pp. 607-613.
Particularly preferred nonionic surfactants for use in the compositions of the present invention include the condensation product of C10 alcohol with 3 moles of ethylene oxide, the condensation product of coconut al,cohol with 5 moles of ethylene oxide, the condensation product of C12 13 alcohol with 6.5 moles of ethylene oxide, the condensation ` product of C12 13 alcohol with 3 moles of ethylene oxide, and the same product which is stripped so as to remove the lower ethoxylate and nonethoxylated fractions, the con-densation product of C14 15 alcohol with 7 moles of ethylene oxide, the condensation product of C12 alcohol with 5 moles of ethylene oxide, the condensation product of C12 13 alcohol with 9 moles of ethylene oxide, the condensation product of C14 15 alcohol with 3 moles of ethylene oxide, the condensation product of C14 15 alcohol with 4 moles of ethylene oxide, and the condensation product of C14 15 alcohol with 9 moles of ethylene oxide. A preferred class of such surfactants are made from substantially linear alcohols, such as those which utilize oxoalcohols containing about 20% 2-methyl branched isomers, commercially available under the traclemark "Neodol" from Shell Chemical Company.
The compositions of the present invention may also contain mixtures of nonionic surfactants falling within the ..

36~

above nonionic surfactant definition, or mixtures of non-ionic surfactants, some of which do not fall within the above nonionic surfactant definition, as long as at least - one of the nonionic surfactants contained in the mixture falls within the above definition of the nonionic surfactants : and the ratio of that nonionic surfactant to the cationic surfactant falls within the required nonionict~cationic ratio. Where the nonionic surfactant mixture contains a nonionic surfactant (or surfactants) which falls outside of the above nonionic definition, the ratio of the surfactant (or surfactants) within the above definition to that which does not fall within the definition is preferably within the range of from about 1:1 to about 5:1. Specific examples of surfactant mixtures include a mixture of the condensation product of C14 15 alcohol with 3 moles of ethylene oxide ("Neodol 45_3")1 and the condensation product of C14 15 alcohol with 14 moles of ethylene oxide("Neodol 45-14")2 in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 3:1; a mixture of the 20 condensation product of C10 alcohol with 3 moles of ethylene oxide together with the condensation product of a secondary C15 alcohol with 9 moles of ethylene oxide ("Tergitol 15-S-9")*, in a ratio of lower ethoxylate nonionic to higher : ethoxylate nonionic of from about 1:1 to about 4:1; and a 25 mixture of "Neodol 45-3" and "Tergitol 15-S-9", in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of *Trademark 2 "

,' : ' ' " ' ~

9~
;~
fro~ about 1:1 to about 3:1~
Preferred nonionic surfactant mixtures contain alkyl glyceryl ether compounds in add:ition to the required non-ionic surfactant. Particularly preferred are glyceryl ethers having the formulae -OCH2-~H-CH2OH and R-o(cH2cH2o)ncH2lHcH2oH
H OH
wherein R is an alkyl or alkenyl group of from about 8 to 10 about 18, preferably about 8 to 12 carbon atcms or an alkaryl group having from about 5 to 14 carbons in the alkyl chain, and n is from 1 to about 6, together with the non-ionic surfactant component of the present invention, in a ratio of nonionic surfactant to glyceryl ether of from about 15 1:1 to about 4:1, particularly about 7:3. Glyceryl ethers of the type useful in the present invention are disclosed in U.S. Patent No. 4,098,713, Jones, granted July 4, 1978; and Canadian Patent No. 1,081,574, K.L. Jones, granted July 15, 1980.
- Other biodegradable nonionic surfactants well known in the detergency arts may be used, in combination with one or more of the nonionic surfactants falling within the defin-ition of nonionic surfactants required in the present invention, to form useful nonionic surfactant mixtures.
Examples of such surfactants are listed in U.S. Patent 3,717,630, Booth, issued February 20, 1973, and U.S. Patent ; 3,332,880, Kessler et al, issued July 25, 1967.
Nonlimiting examples of suitable nonionic surfactants . , which may be used in conjunction with the required nonionic surfactants include the condensation products of aliphatic alcohols with from about 13 to about 25 moles of ethylene oxide. mhe alkyl chain of the ~liphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 13 moles of ethylene oxide per mole of alcohol; and the condensation product of about 14 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from 10 to 14 carbon atoms).
A preferred group of nonionic surfactants useful herein comprises a mixture of l'surfactant" and"cosurfactant", containing at least one nonionic surfactant falling within the definition of nonionic surfactants useful in the present invention, as described in Canadian Patent No. 1,059,865, Collins, granted August 7, 1979.
Cationic Component : 20 The cationic surfactants used in the compositions of the present invention have the formula R mR2xYLZ

wherein each Rl is an organic group containing a straight or branched alkyl or alkenyl group optionally substituted with up to three phenyl or hydroxy groups and optionally inter-rupted by up to four structures selected from the following group: .

;
.

, .

.

~ O O O R2 R20 - ~ 3 , -c - o-, - o-c - , --C-N-, -N-~-, - I H IH 1l 1l I H IH 11 - -N-, -N-C-, -O-, -O-C-O-,. -O-C-N-, -N-C-O , and mixtures thereof, and which contains fro~ about 8 to 22 ;~ carbon atoms. The Rl groups may additionally contain up to 12 ethoxy groups. m is a number from 1 to 3. No more than one Rl group in a molecule can have 16 or more carbon atoms when m is 2 or more than 12 carbon atoms when m is 3. Each R2 is an alkyl or hydroxyalkyl group containing from 1 to 4 - carbon atoms or a benzyl group with no more than one R2 in a molecule being benzyl, and x is a number from 0 to 11, preferably from 0 to 6. The remainder of any carbon atom positions on the Y group are filled by hydrogens. Y is selected from the group consisting of:
(1) -N - , \ /
~ -- C -(2) -C

(3) -p _

(4) -S -~ I+
~; (5) N - , wherein p is from 1 to 12, ~C2H4O)pH
` ~f2H40)pH
(6) --N - , wherein each p is from 1 to 12 ,. I
(C2H4)pH

I
(7) IC ~IN
, , /C~C~

C
~C +l , and / \ N ~ \
(9) mixtures thereof;
L is 1 or 2, with the Y groups being separated by a moiety selected from Rl and R2 analogs (preferably alkylene or alkenylene) having from 1 to about 22 carbon atoms and two free carbon single bonds when L is 2. Z is a water-soluble anion, such as a halide, sulfate, methylsulfate, hydroxide, or nitrate anion, particularly preferred being chloride, 1~ bromide, iodide, sulfate or methyl sulfate anions, in a ` number to give electrical neutrality of the cationic com-ponent. The specific cationic component to be included in a given system depends to a large extent upon the particular nonionic component to be included in the system, and is :`
selected such that it is at least water-dispersible, or preferably water-soluble, when mixed with said nonionic surfactant. The term "water-dispersible" means that the cationic and nonionic surfactants, as well as the anions discussed hereinafter, remain dispersed throughout the laundry solution during the washing process. Mixtures of the above-defined cationic materials may also be used in the compositions of the present invention. Small amounts of other cationic materials can be tolerated in such mixtures.

.

, " ' '~
- , .

. .

. ~ . ~ . - . : . :

v When used in combination with nonionic surfactants, within the specific ratios and the preferred reduced cat-ionic monomer concentrations, defined hereinafter, these cationic components provide excellent soil removal charac-teristics, confer static control and fabric softeningbenefits to the laundered fabrics, and inhibit the transfer of certain dyes among the laundered fabrics in the wash solution. Preferred cationic surfactants are those which have critical micelle concentrations less than about 500 ppm.
In preferred cationic materials, L is equal to 1 and Y
is \ ~ I

-N - ~ ~ - C -or mixtures thereof. However, L may be 2 and, in that case, the cationic component contains 2 cationic charge centers.
Other cationic materials which are useful in the compositions of the present invention include phosphonium and sulfonium materials.
Where m is equal to 1, it is preferred that x is equal to 3 and R2 is a methyl group. Preferred composi-tions of this mono-long chain type include those in which Rl is a C10 to C18 alkyl group. Particularly preferred compositions of this class include C12 alkyl trimethyl-ammonium halide~ C14 alkyl trimethylammonium halide, coconutalkyl trimethylammonium halide, tallowalkyl tri-.

methylammonium halide, and C16 alkyl trimethylamm~nium halide.
- In order to be sufficiently water-soluble or water-dispersible, the cationic surfactant must satisfy the following chain-length criteria. Where m is equal to 2, only one of the Rl chains can be longer than 16 carbon atoms. Thus, ditallowdimethylammonium chloride and di-stearyldimethylammonium chloride, which are used conven-tionally as fabric softeners and static control agents in detergent compositions, are not included within the definition of the cationic components used in the present ` invention. Preferred di-long chain cationics of this type include those in which x is equal to 2 and R2 is a methyl group. In this instance it is also preferred that Rl is . . .
a C10 to C14 alkyl group. Particularly preferred cationic materials of this class include di-Clo alkyldimethyl-ammonium halide, di-C12 alkyldimethylammonium halide materials, and dicoconutalkyl dimethylammonium halide.
Where m is equal to 3, only one of the Rl chains can r' 20 be greater than 12 carbon atoms in length. In this instance, it is preferred that x is equal to 1 and that R2 is a methyl group. In these compositions it is preferred that Rl is a C8 to C12 alkyl group. Particularly preferred tri-long chain cationics include trioctylalkyl-methylammonium halide, and tridecylalkylmethylammonium halide.
Another type of preferred cationic surfactant for use in the compositions of the present invention are the alkoxylated alkyl quaternaries. Examples of ethoxylated `. ~
'`

.:

.

compounds are given below:

fH3 IH3 Z R- l-(C2H4)pH E[(OC H ) N+ (C H O) H Z~

wherein each p is from 1 to 12, preferably from 1 to 10, most preferably from 1 to 7, with the total ethylene oxide groups in a molecule not exceeding about 12. Each ~ is a C10 to C20 alkyl group.
The compositions of the present invention are formu-lated so as to be substantially free of ethoxylated cationicsurfactants which contain an average of about 13 or more, and especially more than about 10, moles of ethylene oxide per mole of surfactant. These compounds tend to be rela-tively nonbiodegradable, do not enhance the cleaning or fabric conditioning benefits provided by the compositions and may, in some circumstances, decrease the overall laun-dering performance provided by them.
The following formulations have been found to be especially suitable for removing particulate soils, and providing fabric softening, static control and dye transfer inhibition benefits, in a conventional home laundering operation.

(a) Tallowalkyltrimethylammonium halide or methyl-sulfate, such as chloride, together with a nonionic surfac-tant selected from the condensation product of C12-C13 alcohol with 2 to 4 moles of ethylene oxide, the condensation product of C14 15 alcohol with 3 to 6 moles of ethylene oxide, such as the condensation product of C12 13 alcohol with 3 moles of ethylene oxide, the condensation product of C14 15 alcohol with 4 moles of ethylene oxide, or mixtures thereof, in a non-ionic:cationic ratio of from 5':1 to about 5:3.
(b) Tallowalkyltrimethylammonium halide or methylsul-fate, such as chloride, together with a nonionic surfactantselected from the condensation product of C12-C13 alcohol with 5 to 7 moles of ethylene oxide and the condensation product of C14-C15 alcohol with 5 to 8 moles of ethylene oxide, such as the condensation product of C12 alcohol with

5 moles of ethylene oxide, the condensation product of . C12 13 alcohol with 6.5 moles of ethylene oxide, the con-- densation product of C14 15 alcohol with 7 moles of ethylene oxide, or mixtures thereof, in a nonionic:cationic ratio of from 5:1 to about 1:1, especially from 5:1 to about 4:1.
Compositions which exhibit both excellent particulate and greasy~oily soil removal may be formulated by combining this cationic material with the condensation product of C12-C13 alcohol with 4 to 10 moles of ethylene oxide or the con-densation product of C14-C15 alcohol with 6 to 10 moles of ethylene oxide, in nonionic:cationic ratios of from 5:1 to about 1:1.
(c) Coconutalkyltrimethylammonium halide or methyl-sulfate, such as chloride, together with a nonionic surfac-tant selected from the condensation product of C12-C13 alcohol with 2 to 4 moles of ethylene oxide and the con-densation product of C14-C15 alo~hol ~ith 3 to 6 moles of ethylene oxide, such as the condensation product of C12 13 alcohol with 3 moles o~ ethylene oxide, the condensation product of C14 15 alcohol with 4 moles of ethylene oxide, or mixtures thereof in a nonionic:cationic ratio of from 5:1 to about 1:1.
(d) Coconutalkyltrimethylammonium halide or methyl-sulfate, such as chloride, together with a nonionic surfac-: 5 tant selected from the condensation product of C12-C13 alcohol with 5 to 7 moles of ethylene oxide and the conden-sation product of C14-C15 alcohol with 5 to 8 moles of ethylene oxide, such as the condensation product of C12 alcohol with 5 moles of ethylene oxide, the condensation product of C12_13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C14 15 alcohol with 7 moles of ethylene oxide, or mixtures thereof, in a nonionic: cationic ratio of from 5:1 to about 1:1, especially about 3:1. Compositions which exhibit both excellent particulate and greasy/oily soil removal may be formulated by combining this cationic material with the condensation product of C12-C13 alcohol with 4 to 10 moles of ethylene oxide or the condensation product of C14-C15 alcohol with 6 to 10 moles of ethylene oxide, in nonionic:
cationic ratios of from 5:1 to about 1:1.
(e) A cationic surfactant of the formula Rl-N+-CH2- ~ Z , wherein Rl, R2 and Z
R2 are as defined above, together with a nonionic surfactant selected from the con-densation proclucts of C12-C15 alcohols with 2 to 4 moles of ethylene oxide, such as the condensation product of C12 13 ', ~i ~$~
~18-alcohol with 3 moles of ethylene oxide, the condensation product of C14_15 alcohol with 4 moles of ethylene oxide, or mixtures thereof, in a nonionic:cationic ratio of from about 3:1 to about 1:1.
(f) A cationic surfactant of the formula R -~ -CH2- ~ Z , wherein Rl, R and Z are R - as defined above, together with a nonionic surfactant selected from the con-. 10 densation products of C12-C15 alcohols with 5 to 10 moles of ethylene oxide, such as the condensation product of C12 alcohol with 5 moles of ethylene oxide, the condensation product of C12 13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C14 15 alcohol with 7 moles of ethylene oxide, or mixtures thereof, in a nonionic:cationic ratio of from 5:1 to about 1:1.
(g) Dicoconutalkyldimethylammonium halide, or methyl-sulfate such as chloride, together with a nonionic surfac-tant selected from the condensation product of C12-C13 alcohol with 4 to 8 moles of ethylene oxide or the conden-sation product of C14-C15 alcohol with 4 to 8 moles of ethylene oxide, such as the condensation product of C12 alcohol with 5 moles of ethylene oxide, the condensation product of C12 13 alcohol with 6.5 moles of ethylene oxide, 25 the condensation product of C14 15 alcohol with 7 moles of ethylene oxide, or mixtures thereof, in a nonionic:cationic ratio of from 5:1 to about 1:1, especially from about 4:1 to about 2:1. Compositions which give both excellent particulate ~1 .. . .
, ~v ~`
and greasy~oily soil removal can be obtained by combining this . cationic surfactant with the condensation product of C12-C13 alco~ol with 6 to 10 moles of ethylene oxide in nonionic:cationic ~: ratios of from 5:1 to about 4:1.
. 5 (h) Tri-C12alkylmethylammonium halide or methylsul-fate, such as chloride, together with a nonionic surfactant selected from the condensation product of C12-C13 alcohol with 6 to 10 moles of ethylene oxide and the condensation . .
product of C14-C15 alcohol with 6 to 10 m~les of ethylene oxide, such as the condensation product of C12 13 alcohol `: with 6.5 moles of ethylene oxide, the condensation product . of C12 13 alcohol with 9 moles of ethylene oxide, the con-densation product of C14 15 alcohol with 7 moles of ethylene oxide, the condensation product of C14 15 alcohol with 9 : 15 moles of ethylene oxide, or mixtures thereof, in a nonionic:
cationic ratio of from 5:1 to about 1:1, especially from 5:1 to about 5:3.
(i) Tri-C8 1Oalkylmethylammonium halide or methyl-sulfate, such as chloride, together with a nonionic surfac-tant selected from the condensation product of C12-C13 : alcohol with 5 to 10 moles of ethylene oxide, and the con-densation product of C14-C15 alcohol with 6 to 10 moles of ethylene oxide, such as the condensation product of C12 . alcohol with 5 moles of ethylene oxide, the condensation :: 25 product of C12 13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C12 13 alcohol with 9 moles of ethylene oxide, the condensation product of C14 15 alcohol with 7 moles of ethylene oxide, the condensation product of ~'., . . , C14 15 alcohol with 9 moles of ethylene oxide, or mixtures thereof, ~n a nonionic:cationic ratio of from about 3:1 to : abou~ 1:1.
. . .
A particularly pre~erred type of cationic component, which is described in Canadian Patent Application 306,517, Letton, filed June 29, 1978, has the formula .
. R2-(Zl)a~(R3)n-Z2-(CH2)m-N -Rl X
Rl 10 wherein Rl is Cl to C4 alkyl or hydroxyalkyl; R2 is C5 to .` C30 straight or branched chain alkyl or alkenyl, alkyl phenyl, or Rl ~- X Rl- N-(CH2)S- ; wherein s is from 0 to 5;

R
R3 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; zl and z2 are each selected from the group consisting of ~'' 11 11 11 11 1 1 11 11 1 1 11 : -C-O-, -O-C-, -O-, -O-C-O-, -C-N-, -N-C-, -O-C-N-, -N-C-O-~- 20 and wherein at least one of said groups is an ester, reverse ester, amide or reverse amide; and X is an anion which makes the compound at least water-dispersible, `; preferably selected from the group consisting of halide, methyl sulfate, and nitrate, preferably chloride, bromide, iodide, sulfate, or methyl sulfate.
In addition to the advantages of the other cationic surfactants disclosed herein, this particular cationic component is environmentally desirable, since it is .

biodeyradable, yielding environmentally acceptable compounds, both in terms of its long alkyl fragment and its ` nitrogen-containing fragment. These preferred cationic components are useful in nonionic/cationic surfactant mixtures which have a ratio of nonionic to cationic of from about 1:1 to about 100:1. However, when used in the composi-tions of the present invention, they are used in surfactant mixtures which have nonionic to cationic ratios of from S:l to about 1:1, more preferably from 5:1 to about 5:3, particularly 10 from about 10:3 to about 10:5, most preferably about 10:4.
In preferred compositions, the ratios are selected such that the compositions have reduced cationic monomer concentrations as specified herein. These preferred cationic surfactants may also be used in the detergent systems defined in Canadian Patent Application Serial No. 306,474, Murphy, filed June 29, 1978, in nonionic to cationic ratios of 5.1:1 to about 100:1, pre-ferably from 5.1 to about 50:1, particularly from about 6:1 to about 40:1 and most particularly from about 6:1 to about 20:1. In formulating such compositions, the nonionic/
cationic surfactant mixture should have a cloud point of from about 0 to about 95C, preferably from about 10 to about 65C, most preferably from about 20 to about 65C, and in preferred compositions, the surfactant mixture has a reduced cationic monomer concentration of from about 0.002 to about 0.2, especi-ally from about 0.002 to about 0.15, particularly from about 0.002 to about 0.08.
Where this type of biodegradable cationic surfactant is used, it is preferred that the detergent compositions have a pH of not greater than about 11, preferably less than about ,~ ~

--22- ~ L~
. .
10, in the laundry solution, in order to minimize hydrolysis of the cationic surfactant.
~ Particularly preferred cationic surfactants of this type are the choline ester derivatives having the following formula:

` 2 ~ f 3 , R - -O-CH2CH2-1 -CH3 X

as well as those wherein the ester linkage in the above formula is replaced with a reverse ester, amide or reverse amide linkage.
Particularly preferred examples of this type of cationic surfactant include stearoyl choline ester quaternary ammonium halides (R2 = C17 al~yl~, palmitoyl choline ester - 15 quaternary ammonium halides (R2 = C15 alkyl), myristoyl choline ester quaternary ammonium halides (R2 = C13 alkyl), lauroyl choline ester ammonium halides ~R2 = C11 alkyl), and tallowyl `; choline ester quaternary ammonium halides (R2 = C15-C17 alkyl).
`Additional preferred cationic components of the choline ester variety are given by the structural formulas below, wherein p may be from 0 to 20.

2 R I f+
R -O-C-(CH2) C-O-CH CH2-N -CH X

+F 1 ~ FH3 ;X CH3- 1-CH2-CH2-O-C-(CH2)p- -O-CH2-CH2-N -CH3 X

' .. . . ......... .
"' : ' ' ' $g~
~ -23-.
The preferred choline-derivative cationic substances, discussed above, may be prepared by the direct esterification of a-fatty acid of the desired chain length with dimethylamino-ethanol, in the presence of an acid catalyst. The reaction pro-duct is then quaternized with a methyl halide, forming thedesired cationic material. The choline-derived cationic materials may also be prepared by the direct esterification of 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.
The novel, particularly preferred cationic materials of the present invention have the formula R2 Rl R3-o[(cH)no]y-(zl)a-(R4)t-z2-(cH2)m-N -R X

Rl In the formula, each Rl is a Cl to C4 alkyl or hydroxyalkyl group, preferably a methyl group. Each R2 is either hydrogen or Cl to C3 alkyl, preferably hydrogen. R3 is a C4 to C30 straight or branched chain alkyl, alkenyl, alkyl phenyl, or alkyl benzyl group, preferably a C8 to C18 alkyl group, most prefer-ably a C12 alkyl group. R4 is a Cl to C10 alkylene or alkeny-lene group. n is from 2 to 4, preferably 2; y is from 1 to 20, 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 must be 1 when a is 1;
and m is from 1 to 5, preferably 2. z2 is selected from the group consisting of:

, ~ .

., O O O O H H O O H H O

-C-O-, -C-, -O-, -O-C-O-, -C-N-, -N-~-, -O-C-N-, -N-C-O-zl is selected from the group consisting of :

` O O O H H O H O
B o c -~-N-, ~ B -N-~-O-and wherein at least one of saicl zl and z2 groups is selected from the group consisting of ester, reverse ester, amide and reverse amide. X is an anion which will make the compound at least water-dispersible, and is s~elected from the group consisting of halides, methyl sulfate, and nitrate, - particularly chloride, bromide, iodide, sulfate, and methyl sulfate. Mixtures of the above structures can also be used.
These novel cationic surfactants may be used in non-ionic/cationic surfactant mixtures in a ratio of nonionic component to cationic component of from about 1:1 to about 100:1. When these surfactants are used in the composi-tions of the present invention they are used in nonionic to ;- cationic ratios of from 5:1 to about 1:1, more preferably from 5:1 to about 5:3, particularly from about 10:3 to about 10:5, especially about 10:4, and preferably have ratios which yield reduced cationic monomer concentrations within the range given herein. They may be also used in the nonionic/cationic surfac-; tant mixtures disclosed in Canadian Application Serial No.
306,474, Murphy, filed June 29, 1978, wherein the ratio of nonionic component to cationic component would be from 5.1:1to about lOO::L, preferably from 5.1:1 to about 50:1, particularly from about 6::L to about 40:1, and most particularly from about

6:1 to about :20:1. In formulating such compositions, the ., ~
'. ,, ~ '' ~
.; ,, ' - .

.

nonionic/cationic surfactant mixture should have a cloud point of from about 0 to about 95C, preferably from about 10 to about 65C~ most preferably from about 20 to about 65C, and the surfactant mixture preferably has a reduced cationic monomer concentration of from about 0.002 to about 0.2, especially from about 0.002 to about 0.15, particularly from about 0.002 to about 0.08.
These surfactants, when used in the compositions of the present invention, yield excellent particulate soil, body soil, and grease and oil soil removal. In addition, the detergent compositions control static and soften the fabrics laundered therewith, and inhibit the transfer of ; certain dyes in the washing solution. Further, these novel cationic surfactants are environmentally desirable, since both their long chain alkyl fragments and their nitrogen fragments are biodegradable, in that they degrade to yield environmentally acceptable compounds. Where this type of biodegradable cationic surfactant is used, it is preferred that the detergent compositions have a pH of not greater than about 11, preferably less than about 10, in the laundry solution, in order to minimize hydrolysis of the cationic surfactant.
Preferred embodiments of this type of cationic component are the esters in which Rl is a methyl group and z2 is an ester or reverse ester group, particular formulas of which are given below, in which t is 0 or 1 and y is from 1 to 20.

-:

' ~' ~' ~ . ' ' ' .

O CH

2CH2~ y (-CH2 ~ t-C-O-CH2-CH2_~_CH3X-R3--o(C~ 2CH20)~.--C--C~2-- -C~:3 X

1 3 1l CH3 R --O (CHCH20) y~C~CH2 I CH3 - R3--O(C:~CH20)y~(CH2)t~C~0 CH2 CH21 3 2 2)y C (cH2)t-~-o-cH2cH2-N+-cH3 X~

: O H H O CH
R3-o(CH2CH2o)y~C~C=C~C~O~CH2CH2~N _CH3 X

CH
3-O(CH2CH2CH2CH2O)Y-C-CH2-N -CH3 X

25 R3-O(CH2CH2CH2CH2O)Y-(CU2) t C O CH2C 2 3 . H3 The preferred derivatives, described above, may be pre-pared by the reaction of a long chain alkyl polyalkoxy (preferably ~,. .

, :., - ~ . , ,, '' : ~

- -27- ~ h~ ~

polyethoxy) carboxylate, having an alkyl chain of desired length, with oxalyl chloride, to form the corresponding acid chloride. The acid chloride is then reacted with dimethylamino-ethanol to form the appropriate amine ester, which is then quaternized with a methyl halide to form the desired choline - ester compound. Another way of preparing these compounds is ` by the direct esterification of the appropriate long chain ethoxylated carboxylic acid together with 2-haloethanol or di-methyl aminoethanol, in the presence of heat and an acid catalyst.
The reaction product formed is then quaterniz~ed with methyl-halide or used to quaternize trimethylamine to form the desired choline ester compound.
As a guide in formulating compositions which deliver ` excellent particulate soil removal, the reduced cationic monomer concentration may be used. Thus, the nonionic and cationic components, defined above, may be combined into a surfactant ` mixture which has a ratio corresponding to a reduced cationic monomer concentration (CR) of from about 0.005 to about 0.2, preferably from about 0.008 to about 0.15, particularly from about 0.01 to about 0.1. A CR value within this range will yield a composition which exhibits optimum particulate soil removal performance. Where the nonionic and cationic components used are pure, the more narrow CR ranges are preferred.
In a preferred method of preparing the compositions of the present invention, the nonionic and cationic surfactants are intimately and completely mixed together prior to the addition of any addi-tional components to the mixture. This intimate premixing of the nonionic and cationic components enhances performance of the compositions.
:, : : : `
~ ` `' ~ ` : ' .

An approximation of the CR of a surfactant mixture is obtained by dividing the concentration of the cationic surfactant monomer in the laundry solution by the critical micelle concentration (CMC) of the surfactant. As used in this application, CMC's are detlermined at lOO~F in water con-taining 7 grains/gallon of mixed hardness, unless otherwise stated. For purposes of this application, CR is calculated according to the equations given below.
The concept of reduced monomer concentration, in a ; 10 single component system, as a quantity which normalizes the extent of adsorption of a surfactant onto a fabric surface (the critical element in the removal of greasy/oily soils) is discussed in Tamamushi and Tamaki, Proceedings of the Second International Con~ress of Surface Activity, III, 449, Academic .
`; 15 Press, Inc- (1957). The equations below extend this concept of reduced monomer concentration to multi-component systems, utilizing surfactant monomer concentrations. The concept of surfactant monomer concentration is derived from the discussion - in Clint, J. Chem. Soc. Far. Trans., I, 71, 1327 (1975), in the context of an ideal solution, and is based on the following ` quadratic equation (equation (11) in Clint):
. *
(Clm)2[c2* - 1] + Clm(C-c2 +Cl) -~ Ccl = O

wherein in the above and the following equations;
C = total analytical surfactant concentration in the solution (moles/l.) = sum of the cationic and nonionic concentrations = Cl + C2 (wherein "1"
denotes nonionic surfactant and "2" dPnotes cationic surfactant) :
:
, :; *
cl = critical micelle concentration (CMC) of nonionic surfactant (moles/l,) ~ C2 = critical micelle concentration of cationic surfactant (moles~:L.) ~ = total mole fraction of nonionic surfactant in the solution = Cl/(Cl + C2) = a constant based upon the heat of mixing =
. -2.8 CmL = nonionic monomer concentration . 10 c2m = cationic monomer concentration e = base of Napierian logarithm system = 2.71828 x = mole fraction of the nonionic surfactant in : the micelle at concentration C
: 15 fl = nonionic activity coefficient in the mixed micelle = e~(l-x)2 f2 = cationic..activity coefficient in the mixed micelle = e~x f2C2 ~
- CR = reduced cationic monomer concentration 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 (ppm) = Wl+W2 (wherein "1" denotes nonionic surfactant and "2" denotes cationic surfactant) Y = weight fraction of nonionic surfactant in the ~ .

. .
.
. ' ' . . '' , . ' .

, .

composition.
` The above equation is solvecl for the nonionic monomer concentration by taking its posi.tive root (equation (12) in Clint).

clm = ~-(C-(c2 -cl)) +- [(C-(C2-cl))2 ~ 4aC(c2-Cl)~l/2}

-` 2( 2 -l) .': Cl ; By modifying this equation based on the assumptions - l~ of a regular, rather than an ideal, solution, the CR range for optimum performance was derived from the following equation:

-(C-Q) + ~(C A)2 + 4aCQ
- 2Q (l) For a given cleaning test for a nonionic/cationic system, x was found by inserting the values known from the test (i.e., cl, c2, a, C and ~) into equation (l) and solving iteratively for x, such that the error in x is~less than 0.001. This pro-cedure was repeated for a large number of such tests, over vary . ing usage conditions. The x values obtained were then used to solve for the cationic monomer concentrations using the ~; following equation:
c2m = (l-x)f2c2 (2) The CR value was then calculated using equation (3).

CR = c2/c2 (3) '` The CR va:lues obtained cover a large number of combina-tions and ratios of various nonionic and cationic surfactants, .
, , .' - ' , at various concentrations and temperatures, ~hich have been evaluated for their ab~lity to clean greasy/oily soils. The examination of the resulting data revealed that for a given system the optimum cleaning of greasy/oily soils was found at a CR value of from about 0.002 to about 0.2.
This range of CR (i.e., 0.002 to 0.2) can then be used to determine the range of optimum nonionic/cationic ratios for any given combination of nonionic surfactant and cationic surfactant, for the desired wash concentration within the overall wash concentration range of from 100 parts per million (ppm) to 10,000 ppm of surfactant. This calculation * *
is carried out in the following manner, where ~, CR, cl c2, Ml and M2 are known for a given nonionic/cationic surfactant pair:
(a) for a given nonionic surfactant, cationic sur-factant, and for each end of the CR range, solve for x using the equation (l-x) e~X = C
by standard numerical iterative techniques to an error in x of less than 0.001;
(b) find the range of Y from the equation y(l--x) _ x(l--Y) = 1000 [x(x~

usins 100 ppm and 10,000 ppm as the boundary values for W, for each end of the CR range;
(c) the nonionic/cationic ratio lNCR) range for optimum performance is then within the range ,,~,~`

.
` , ~ ~ '.` .`

' obtained by substituting the boundary values for Y into the formula .' - Y

NCR = 1 ~l - 5 Put another way, steps (b) and (c) may be combined into a single equation which may be solved directly for ~ the NCR.
.' 1 ; Y - (1000/W)~+ M2(x-1) - NCR =
l-Y (1000/W)~+
xMl The above procedure is relevant only to wash solution concentrations above the critical micelle concentration of the nonionic/cationic mixture. For concentrations which are as high as about five times the critical micelle concen-tration, CR is essentially independent of concentration.
This means that for conventional laundry usage concentrations (e.g., 100 ppm to 10,000 ppm, and especially from about 250 ppm to aboùt 3,000 ppm), the CR of most commercial cationic/
nonionic surfactant mixtures (wherein the cationic component 20 has a CMC of less than about 100 ppm, measured at 105F
water containing 7 grain/gallon of mixed calcium and magnesium hardness) will be independent of the actual usage concentration, so that using a concentration of about 1,000 ppm in the above calculation will be a satisfactory approxi-mation for the entire range. As used herein, if a concen-tration range is not specified, the 1,000 ppm CR is meant.
By way of example, the optimum ratio for grease/
oil removal for Composition A of Example I, herein, given .
.
, ,. , ~ .
~ `' ' ; -' ' ' - . : : . ' "
' ~
- , CR, is calculated below. For this system, the following values are either known or selected as indicated:
W = 1,000 ppm (selected as representative of usage conditions) cl = 1.967 x 10 ppm C2 = 2.1875 x 10 ppm ~ = -2.8 Ml = 406.7 M2 = 320 CR = 0.0073 (selected for optimum greasy~oily soil removal performance, but could be any value between 0.002 and 0.2) Substituting the values for ~ and CR into equation (a):
(1 x)e~2 8x2= 0 0073 ; Solving iteratively for x, it is found that x =
0.922.
~; Using this value for x, it is found that fl = 0.983 f2 = 0.0925 ~ = (0.0925) (2.1875 x 10 5) - (0.983) (1.967 x 10 5) = -1.73 x 10 5 Substituting these values into equation (b), it is found that:

Y(l-o 922) - 0 922(1-Y) = 11 (0.922) (0.922-1) (-1-73X10 Y = 0.938 Substitut:ing this value for Y into equation (c~, the i~`'.~.

' - - ` :
' ' .

_34_ nonionic/cationic ratio is determined.

NCR = - -- = 15.1 1-0.938 It will be noted that this ratio corresponds to the ; 5 ratio actually found in Example I, Composition A.
In addition to these reduced cationic monomer criteria, the nonionic/cationic surfactant mixture may also satisfy the specific cloud point requirements, given ~ below. In addition to outstanding particulate soil deter-,~ 10 gencyr these preferred compositions will be optimized for the removal of greasy/oily soils. Thus, in preferred compositions, the cloud point of the nonionic/cationic mixture ( and in preferred embodiments the nonionic/ cationic mixture plus any electrolytes present in the composition) falls between about 0 and about 95C, preferably between about 10 and about 65C, more preferably between about 20 ; and about 65C, especially between about 30 and about 50C.
; For cold water detergency, the surfactant mixture should have ` a cloud point between about 0 and about 25C. The fact that a composition has a cloud point within these temperature ranges assures that the composition can be utilized under laundry temperature conditions to achieve outstanding removal of greasy~oily soils. If a composition does not have a cloud point within the temperature range specified, it will not yield the outstanding cleaning of the present invention.
The compositions will exhibit their best grease/oil removal performance when the temperature of the wash solution in which they are used falls within about 20C, preferably ' .

within about 15C, and most preferably within about 10C, of the cloud point of the nonionic/cationic surfactant mixture.
Put another way, the laundry solution temperature range in which the preferred compositions deliver optimum grease~oil removal lies between the cloud point temperature of the system in the absence of the cationic component, and about 30C, preferably aboul: 25C, most preferably about 20C, above that cloud point temperature.
As used herein, the term "cloud point" means the temperature at which a graph which plots the light scattering intensity of the composition versus wash solution temperature begins to sharply increase to its maximum value, under the following experimental conditions:
The light scattering intensity is measured using a 15 Model V~-12397 Photogoniodiffusometer, manufactured by Societe Francaise d'instruments de controle et d'analyses, France (the instrument being hereinafter referred to as (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 with a 0.2~ nucleopore filter. The syringe needle passes through the sample cell lid, so that the cell interior is not exposed 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 t:he SOFICA~s heater and cooled by the addition ~1 :

'' of ice (heating rate 1C/minute); the temperature of the sample is determined by the temperature of the bath. The light scattering intensity of the sample is then determined ` at various temperatures, using a green filter and no polarizer in the SOFICA.
Fatty Amide Component In particular preferred embodiments of the present ` invention the nonionic surfactant/cationic surfactant mixture additionally contains from about 2 to about 25%, preferably : 10 from about 2 to about 16%, and most preferably from about ~ 3 to about 10%r of a fatty amide surfactant. Any nonionic - surfactant conventionally used in detergent compositions;
however, preferred compositions contain the nonionic surfac-tants defined above, in order to maximize the cleaning benefit obtained. These amide surfactants may be used in nonionic/
cationic surfactant mixtures having nonionic:cationic ratios of from about 1:1 to about 100:1. When they are used in ` the compositions of the present invention, the mixtures ` have nonionic:cationic ratios of from 5:1 to about 1:1, preferably from 5:1 to about 5:3, more preferably about 10:3 to about 10:5, particularly about 10:4. In non-ionic/cationic systems, the ratio of the total cationic and nonionic components to the amide component in the composition is in the range of from 5:1 to about 50:1, preferably from about 8:1 to 25:1. When these compositions are formulated in accordance with the ratio and the preferred reduced cationic monomer concentration limits given herein, they result in excellent particulate soil removal performance, as ' ~1 ~',`'`
well as improved soil anti-redeposition characteristics, and the development is described in Canadian Patent Application Serial No. 306,559, Cambre, filed June 29, 1978.
Amides useful in these preferred compositions include, but are not limited to, carboxylic acid amides, sulfonic acid amides, phosphonic acid amides, and boronic acid amides.
Preferred amides include those having the formulae:

Rl_~_N Rl--$-N /
.'-' R2 l'~
~herein R is a C8-C20 alkyl, alkenyl, alkyl phenyl or alkyl benzyl group, prefèrably C10-Cl8 alkyl, and most preferably Cll alkyl; and each R2 is hydrogen, or Cl-C8 alkyl or hydroxyalkyl, preferably hydrogen. Specific examples of `~ 15 these compositions include a mixture of stearoyl choline bromide (present in the washing solution at 120 parts per million), the condensation product of coconut alcohol with 5 moles of ethylene oxide (present in the wash solution at about 357 parts per million), and a mid-cut coconut alkyl ammonia amide (Rl=coconut alkyl and R2 is hydrogen; present in the wash solution at about 50 parts per million~; and a mixture of stearoyl choline bromide (100 ppm), the con-densation product of coconut alcohol with 5 moles of ethyl-ene oxide (357 ppm), and lauramide (Rl = Cll and R2 is hydrogen; at 45 ppm). These amides may also be used in the surfactant mixtures described in Canadian Patent Application Serial No. 306,517, Murphy, filed June 29, 1978 which have nonionic:cationic ratios of from 5.1:1 to about 100:1, ~, ' .

, ' ' , " ,:' preferably from 5.1:1 to about 50:1, particularly from about 6:1 to about 40:1, and most particularly from about 6:1 to about 20:1. In forming such compositions, which are optimized for the removal of greasy~oily soils, the nonionic/
cationic surfactant mixture should have a cloud point of from about 0 to about 95C, preferably from about lO to about 65C, especially from about 20 to about 65C, and the surfactant ~"
mixture preferably has a ratio which correspc)nds to a reduced cationic monomer concentration of from about 0.002 to about 0.2, especially from about 0.002 to about 0.15, particularly from about 0.002 to about 0.08.
, Additional Components While the compositions of the present invention may contain additive materials conventionally used in detergent compo-sitions, the amount of anion-producing materials, and hence ` anions, which will make the particular cationic surfactant " used in the compositions non-water dispersible should be minimized. Whether a particular anion constitutes an "interfering anion" depends upon the physical and chemical properties (such as structure and dissociation constant) of the particular anions and cationic surfactants used in a given composition. It is preferred that anionic materials - be contained :in amounts sufficiently small such that not more than about lO molar percent, preferably not more than about 5 molar percent, 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 surfactant decreases the overall cleaning and fabric , ~ `

.
: .

P~

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 tas indicated by their dissoci-ation constant). Thus, when an anionic material has a dissociation constant of at least about lxlO 3 (such as -sodium toluene sulfonate), it may be contained in an amount up to about 40%, by weight, of thè cationic surfactant;
where the anionic material has a dissociation constant of at least about lxlO 5, but less than about lxlO 3, it may be contained in an amount up to about 15%, by weight, of the cationic surfactant; and where the anionic material has a dissociation constant of less than about lxlO 5, ( such as sodium Cll 8 linear alkylbenzene sulfonate), it should be contained only in amounts up to about 10%, by weight, of the cationic surfactant.
It is preferred, in order to minimize the effects of interfering anions, that the compositions of the present invantion be substantially free of phosphate, polyphosphate, silicate, and polycarboxylate builder anions, carboxymethyl cellulose, and anionic surfactants; particularly preferred are those which are substantially free of phosphate, poly-phosphate, and carboxymethyl cellulose materials. The compositions of the present invention contain from 0 to about 20% of phosphate materials; and, even though they contain no or low levels of phosphate materials, exhibit an outstanding level of particulate soil removal. It is preferred that the compositions be substantially free of ~.

- ,' ' ~ '' .

phosphate materials both for performance and environmental reasons.
The compositions of the present invention may also contain additional ingredients generally found in laundry detergent compositions, consistent with the restrictions on interfering anions, stated above, at their conventional art-established levels. Very low levels (i.e., from about 1 to about 15%) of electrolytes, such as perborates, phosphates, polyphosphonates, carbonates or sulfates, may have a bene-ficial effect on cleaning performance.
The compositions of the present invention may containup to about 15~, preferably up to about 5%, and most pre-ferably from about .1 to 2%, of a suds suppressor component.
Typical suds suppressors include long chain fatty acids, such as those described in U.S. Patent 2,954,347, issued September 27, 1960, St. John, and combinations of certain nonionics therewith, as disclosed in U.S. Patent 2,954,348 issued September 27, 1960, Schwoeppe. Other suds suppressor components useful in the compositions of the present inven-tion include, but are not limited to, those described below.
Preferred suds suppressing additives are described in U.S. Patent 3,933,672, issued January 20, 1976, Bartolotta et al., relative to a silicone suds controlling agent. The silicone material can be represented by alkylated polysiloxane materials such as silica aerogels and xerogels and hydrophobic silicas of various types, The silicone material can be described as a siloxane having the formula:

.:

R
I~;io ~ I J x 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 The polydimethyl-siloxanes (R and R' are methyl) having a molecular weight within the range of from about 200 to about 200,000, and higher, are all useful as suds controlling agents. Additional suitable silicone materials wherein the side chain groups R and R' are alkyl, aryl, or mixed alkyl and aryl hydrocarbyl groups exhibit useful suds controlling properties. Examples of the like ingredients include diethyl-, dipropyl-, dibutyl-, methyl-ethyl-, phenylmethyl-polysiloxanes and the like.
Additional useful silicone suds controlling agents can be represented by a mixture of an alkylated siloxane, as re-ferred 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 ` 20 is represented by a hydrophobic silanated (most preferably trimethylsilanated silica having a particle size in the range from about 10 millimicrons to 20 millimicrons and a specific surface are above about 50 m2/gm. intimately admixed with ` dimethyl silicone fluid having a molecular weight in the 25 range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 19:1 to about 1:2. The silicone suds suppressing agent is advantageously releasably incorporated in a water-soluble or water-dispersible, `: : : :`. : .

substantially non-surface-active detergent-impermeable ~- carrier.
Particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in U.S.
Patent No. 4,136,045, Gault et al, issued January 23, 1979.
An example of such a compound is "DB-544"* commercially available from Dow Corning, which contains a siloxane/glycol copolymer together with solid silica and a siloxane resin.
Microcrystalline waxes having a melting point in the ; 10 range from 35C - 115C and a saponification value of less than 100 represent additional examples of a preferred suds regulating component for use inthe subject compositions, such waxes are described in U.S. Patent 4,056,481, Tate, issued November 1, 1977. The microcrystalline waxes are substantially water~insoluble, but are water-dispersible in the presence of organic surfactants. Preferred microcrystal-line waxes have a melting point from about 65C to 100C, a molecular weight in the range from 400-1,000; and a pene-tration value of at least 6, measured at 77F by ASTM-D1321.
Suitable examples of the above waxes include: microcrystalline ` and oxidized microcrystalline petrolatum waxes; Fischer-Tropsch and oxidized Fisher-Tropsch waxes; ozokerite; ceresin;
montan wax; beeswax; candelilla; and carnauba wax.
Alkyl phosphate esters represent an additional prefer-red suds suppressant for use herein. These preferred phos-phate esters are predominantly monostearyl phosphate which, * Trademark in addition thereto, can contain di- and tristearyl phosphates and monooleyl phosphates, which can contain di- and trioleyl phospha~es.
The alkyl phosphate esters frequently contain some tri-alkyl phosphate. Accordingly, a preferred phosphate estercan contain, in addition to the monoalkyl ester, e.g., monostearyl phosphate, up to about 50 mole percent of dialkyl phosphate and up to about 5 mole percent of trialkyl phosphate.
Other compatible adjunct components which may be included in the compositions of the present invention, in their conventional art-established levels of use, include bleaching agents, bleach activators, soil suspending agents, corrosion inhibitors, dyes, fillers, optical brighteners, germicides, pH adjusting agents, enzymes, enzyme stabilizing agents, perfumes, fabric softening components, static control agents, and the like. However, because of the numerous and diverse performance advantages of the compositions of the present invention, many components, such as static control agents, fabric softening agents and germicides, will not usually be necessary.
The compositions of the present invention may be manu-factured and used in a variety of physical forms, such as solid, powder, granular, paste, or liquid. The compositions are particularly well-suited for incorporation into substrate articles for ~use in the home laundering process. Examples of such articles are described in U.S. Patent No. 4,170,565, Flesher et al, issued October 9, 1979; U.S. Patent No.
4,095,946, Jones et al, issued June 20, 1978; U.S. Patent .

, .

.~
No. 4,118,525 granted October 3, 1978; and U.S. Patent No.
4,113,630, Hagner et al, granted September 12, 1978.
~ hese articles consist of a water-insoluble substrate which releasably incorporates an effective amount, prefer-ably from about 3 to 120 grams, particularly from about 20to 80 grams, of the detergent compositions of the present invention. A particularly preferred substrate article in-corporates a bleaching component and a bleach activator on the substrate, together with the nonionic/cationic surfactant mixture.
In a particularly preferred method of making the detergent compositions of the present invention, the specifically defined nonionic and cationic surfactants, present in ratios from about 1:1 to about 100:1, are intimately and completely mixed at a temperature of from about 25C to about 95C, preferably from about 40C to about 90C, prior to the addition of any additional components. By using this process, the components are taken from their original liquid or powder form and are made into a thick paste, which is ideally suited for use in the substrate articles, described above.
When this process is used to m-ake the compositions of the present invention, the components are present in non-ionic:cationic ratios of from 5:1 to about 1:1, preferably from 5:1 to about 5:3, and more preferably from about 10:3 to about 10:5, and are formed into mixtures which satisfy the reduced cationic monomer concentration requirements, herein. In one particularly preferred embodiment of this process, the components are intimately mixed together at a temperature of about 25C. In this embodiment, it is pre-ferred that the anion contained in the cationic surfactant be bromide. Thus, when stearoyl choline bromide, a powder having the following formula, 17H3s C O-CH2CHz-EI -CB3 Br is intimately mixed at a temperature of about 25C
with the condensation product of C12 alcohol with 5 moles of ethylene oxide, a liquid, at a nonionic:
cationic ratio of about 10:4, a thick paste product is formed. Substantially similar results are obtained when the nonionic surfactant is the condensation product of coco-nut alcohol with 5 moles of ethylene oxide.
In another particularly preferred embodiment of this process, the components are intimately mixed together at a temperature of at least about 65C. In this embodiment, it is preferred that the anion contained in the cationic surfactant be chloride. Thus, when stearoyl choline chloride, a powder, is intimately mixed at a temperature of about 80C with the condensation product of C12 alcohol with 5 moles of ethylene oxide, a liquid, at a nonionic:cationic ratio of about 10:4, a thick paste product is formed. If the same components are mixed together at about 25C, the mixture remains a liquid, which is much less desirable for use in making substrate articles. Substantially similar ; results are obtained when the nonionic surfactant is the condensation product of coconut alcohol with 5 moles of ~; :

' , ~ ' ` '.~

- -46~

ethylene oxide. Where this process is used in making the compositions described in concurrently filed Canadian Patent Application Serial No. 306,474, Murphy, nonionic:cationic ratios of from 5.1:1 to about 100:1, preferably from 5.1:1 - 5 to about 50:1, more preferably from about 6:1 to about 40:1, and most preferably from about 6:1 to about 20:1, are used, in accordance with the cloud point and the pre-ferred reduced cationic monomer concentration definitions, stated therein, The compositions of the present invention are used in the laundering process by forming an aqueous solution (pre-ferably one having a temperature of from about 10 to about 50C) containing from about 0.01 (100 parts per million) to 0.3% (3,000 ppm), preferably from about 0.02 to 0.2~
` 15 and most preferably from about 0.03 to about 0.15~, of the nonionic/cationic detergent mixture, 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 exceptionally good particulate soil removal performance. Further, the compositions also provide fabric softening, static control, and dye transfer inhibition benefits to the fabrics laundered therewith.
Although not intending to be bound by theory, it is believed that the clay removal mechanism is as follows.
At the optimum nonionic:cationic ratio, as defined by the reduced cationic monomer concentration, the cationic sur-factant adsorbs onto the clay soil (negatively-charged) in a mono-layer, neutralizing the charge. This neutralized charge , results in a hydrophobic surface which increases the adsorption of the nonionic surfactant onto the clay surface. The clay soil-is then easily removed by the agitation.
It has been found that when the nonionic/cationic com-positions of the present invention are used in a laundrysolution, a threshhold eoncentration of at least about 50, preferably about 100, most preferably about 150, parts per million on the eationic component must be present in the laundry solution in order to give the partieulate soil removal benefit. Under conventional United States laundry conditions, which generally utilize from about 150 to 1500 parts per million of a detergent composition in the laundry '!" solution, nonionic surfactant to cationic surfactant ratios of from 5:1 to about 1:1 are necessary in order to provide this threshhold concentration in the laundry solution. In washing processes which utilize higher concentrations of detergent composition, such as European washing proeesses, it is possible to use higher nonionic surfactant to cationic surfactant ratios, while still attaining the necessary cationic threshhold concentration. Under these European washing conditions it is possible to obtain excellent partic-ulate soil removal, in addition to outstanding greasy and oily soil and body soil removal, using the nonionic sur-factant to cationic surfactant ratios of from 5.1:1 to about 100:1 defined in coneurrently filed Canadian Patent Applieation Serial No. 306,474, Murphy.
All percentages, parts, and ratios used herein are by weight unless otherwise speeified.

. ~ .

-48~

The following nonlimiting examples illustrate the compositions and the method of the present invention.
EXAMPLE I
Identical cotton, polyester~cotton, and polyester swatches were stained with a clay-in-water suspension and - three stained swatches oE each :Eabric type were washed in a one gallon washing machine, which simulates the action of - a commercial washing machine, using two different detergent compositions. ~ne set of swatches was laundered using the commercially available built, brightener-containing laundry detergent "Tide",* marketed by The Procter & Gamble Company, at the equivalent of its recommended 1-1/4 cup usage level.
The second set oE swatches was laundered in a detergent com-position of the present invention, having the following formulation:
Component % by Weight Dicoconutalkyl dimethyl-ammonium bromide 19 Condensation product of C14_15 alcohol with 7 moles of ethylene oxide ("~eodol 45-7")** 48 HLB=11.5 Sodium chloride 33 CR=0.0815 This detergent composition, having a nonionic:cationic ratio of about 10:4, was used in the aqueous laundering solution at a concentration oE about 500 ppm, and had a * Trademark ** ,-pH in the laundry solution of about 6.5. The wash water contained 7 grains per gallon of mixed calcium and magnesium hardness, and the laundering operation lasted for 10 minutes at 100F (38C). A Hunter Reflectometer was then used to obtain a reflectance reading for each of the laundered swatches. The cleaning effectiveness of the particular treatment was determined by averaging the reflectance readings of the individual swatches. A higher reflectance reading indicates greater cleaning effectiveness.
This procedure was repeated twice for each of the two detergent compositions and the reflectance readings were averaged for the two runs. The conventional built phosphate granular detergent yielded fabrics having an average of 63.1 Hunter Whiteness Units, while the detergent composition of the present invention yielded fabrics having a value of 62.0 Hunter Whiteness Units. These data demonstrate the outstanding clay soil removal performance of the unbuilt compositions of the present invention which e~ualed the performance provided by the conventional built, brightener-containing detergent composition.
Substantially similar cleaning results are obtainedwhere the detergent composition of the present invention does not contain the sodium chloride component, indicating that for the particular detergent composition defined above, sodium chloride does not contribute "interfering anions"
to the laundry solution of the disclosed detergent compositions.
Substantially similar results are also obtained where the cationic surfactant used in the above composition is ~ !
:

.
replaced by C12 alkyl trimethylammonium chloride, C14 alkyl trimethylammonium bromide, di-Clo alkyl dimethylammonium chlorlde, di-C12 alkyl dimethylammonium chloride, tri-C8 alkyl methylammonium bromide, tri-C10 alkyl methylammonium chloride, or the cationic surfactants listed below:

CH
:.: 1 3 HOH4C2_N _C2H4OH C1 ,'"

C12H25 C \ l Cl N~-CH2 C18H37-N CH2 ~ Cl 1 f+
C16H33-C-O-cH2cH2 iN CH3 Br O O CH
~ 3 C H -o-c-cH2cH2-c-o-cH2c 2 1 3 Br : -51-:, CH
~ 3 CloH2l-o(cH2cH2o)lo C 2 C 3 Cl . ClH3 Substantially similar clean:;ng results are also obtained where the cationic surfactant used above is replaced by a : mixture of dicoconutalkyl dimethylammonium bromide (A) . together with C12 alkyl trimethylammonium chloride (B) in a ratio of A:B of about 4:1, 3 1 2:1, 1:1, 1:2, or 1:4; a ' 10 mixture of 17 35 C O CH2CH2-1 -CH3 Br (C) together with di-Clo alkyl dimethylammonium chloride 15 (D) in a ratio of C:D of about 5:1, 3:1, 1:1, 1:3 or 1:5; or a mixture of C, above, together with h' fH3 Cl2H25-(cH2cH2o)7-cH2-c-o-cH2cH2-N -CH3 Cl (E) 20 in a ratio of C:E of about 7:1, 3:1, 2:1, 1:1, 1:2, 1:3, .` 1:4, or 1:7.
Essentially similar results are also obtained where the nonionic component of the above composition is replaced with the condensation product of C10 alcohol with 3 moles of ethylene oxide (HLB=9), the condensation product of coconut alcohol with 5 moles of the ethylene oxide, the condensation product of coconut alcohol with 7 moles of ethylene oxide .

.
' ., ' . .
.

`: -52-- (HLB=12.8), the condensation product of C12 13 alcohol with 6.5 moles of ethylene oxide (HLB=12), the condensation product of C12 13 alcohol with 3 moles of ethylene oxide (HLB=7.9), and the same product which is stripped so as to remove unethoxylated and lower ~ethoxylate fractions, the condensation product of C12 alcohol with 5 moles of ethylene ; oxide, the condensation product of C12_13 alcohol with 9 moles of ethylene oxide, and the condensation product of C14 15 alcohol with 3,4 or 9 moles of ethylene oxide. A mixture of the condensation product of C14 15 alcohol with 3 moles of ethylene oxide together with the condensation product of C14 15 alcohol with 7 moles of ethylene oxide in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of about 2:1, or the mixture of the condensation product of coconut alcohol with 5 moles of ethylene oxide together with an alkyl glyceryl ether having the structural formula:

C12H25-0CH2fH CH2 OH

in a ratio of alcohol ethoxylate to glyceryl ether of about ` } 20 7:3.

Results substantially equivalent to those obtained above are also obtained where the detergent composition has a ratio of nonionic surfactant to cationic surfactant of 1:1, 10:3, 5:3, 10:5, or 5:1.
Substantially similar results are also obtained where :~ the detergent composition is formulated, such as by the addition of monoethanolamine, to have a pH in the laundry .

.:

solution of about 7, 8, 8.5, 9 or 10.
EXAMPLE II
tdentical cotton, polyester/cottonr and polyester swatches were stained with bacon grease and dirty motor oil and were aged for about 24 hours. The swatches were then washed in a one gallon washing machine, which simulates the action of a commercial washing machine, using two different detergent compositions. The first group of swatches was washed using a heavy-duty liquid laundry detergent composil:ion, optimi2ed for grease and oil removal, having the formulation given below, at its recommended usage level.
Component % by Weight "Neodol 45-7"* 15.0 Mg Linear alkyl ben~ene 31. 3 sulfonate Triethanolamine 3.5 Ethanol 6.5 Coconut alkyl fatty acid 1.0 Water 41.8 Brightener and minors Balance to 100 (brighteners, perfume, etc.) The second group of swatches was washed in a laundry detergent composition of the present invention having the following formulation:
Component O fH3 ~ by Weight 25 C12H25-(CH2CH2)7-CH2-C- CH2CH2 IN 328.6 * Trademark ~ .

Condensation product of C12_13 alcohol with 3 moles of 71 4 ethylene oxide, stripped to remove lower ethoxylate and unethoxylated fractions ("Neodol 23-3T")**
The detergent composition of the present invention had a ratio of nonionic surfactant to cationic surfactant of about 10:4 and was used in the aqueous laundering solution at a concentration of about 500 ppm, having a pH in the laundry solution of about 6.5. The fabrics were washed for about 10 minutes in water having a temperature of about 100F
(38C), containing 7 grains per gallon of mixed calcium and magnesium hardness. The percentage stain removal for each swatch was calculated using light reflectance readings, ob-tained on a Gardner color measurement device, taken before and after the washing process. The average percent stain removal for each of the detergent compositions tested is ` summarized in the table below:

Average % Stain Removal (across ; 3 fabric types) Bacon Dirty ~- 20 Grease Motor Oil Liquid laundry composition 58.2 45.5 Nonionic/cationic mixture 58.8 57.5 These data demonstrate the effective grea~se and oil removal obtained using the preferred cationic components in the detergent compositions of the present invention.
The detergent composition of the present invention, as formulated above, also yields excellent particulate soil ** Trademark ~, .
:
.. . . . .:
:, , ' ' .': - - , removal performance, and given fabric softening, static con-trol and dye transfer inhibition benefits to fabrics laundered . ther~with.
Substantially similar results are obtained where the nonionic component of the above composition is replaced by the condensation product of C10 alcohol with 3 moles of ethylene oxide, the condensation product of C'12 alcohol with 5 moles of ethylene oxide (HLB=ll), the condensation product of coconut alcohol with 5 moles of ethylene oxide, the conden-sation product of coconut alcohol with 7 moles of ethyleneoxide, the condensation product of C12_13 alcohol with 6-5 moles of ethylene oxide, or the condensation product of C14_15 alcohol with 7 moles of ethylene oxide.
Substantially similar results are also obtained when the ratio of nonionic surfactant to cationic surfactant used ; in the above composition is 10:3, 20:7, 10:5, 20:11, 5:3, . 5:4, or 1:1.
Similar results are also obtained where the cationic surfactant, used above, is replaced by one of the following surfactants:

l 1 ~
C H -(CH2cH2O)7-cH2-c-o CH2 2 1 3 Br ` CH3 fH3 Cl2H25-(cH2cH2Q)9-cH2~c-o-cH2cH2~ cH3 Br ., . .
' ~

. .

. : - . , -- .
- , :, - . : , - . ~ :
..

:

lOH21 (CH2cH2o)lo-~-cH2-N -CH3 Cl : 5 13 27 (CH2CH2O)8 C-C=C-C-O-CH2CH2-N -CH3 Cl-: CH3 O CH

CllH23-(CH2CH2CH2CH2O)7 C CH2 1 3 EXAMPLE III
A detergent composition of the present invention was formulated by combining the condensation product of coconut alcohol with 5 moles of ethylene oxide (HLB=10.5) together with one of the preferred cationic surfactants of the present invention having the formula:

in a ratio of nonionic surfactant to cationic surfactant 20 of about 10:4 CR=0.071. This detergent composition had a pH in the wash solution of about 8.5, and was used in the washing solution at a concentration of about 500 ppm.
A second detergent composition of the present invention was formulatecl by combining the same nonionic and cationic surfactants in the same ratio as above. The composition also containecl monoethanolamine as an alkalinity source, in an amount such that the monoethanolamine was present L'?~
:
:;. , `, ` , , ` , - ` `::
" , ` , ,. ` ' ~ : : :-., ri~

at about 30 ppm in the washing solution when the entire composition was used at a concentration of about 530 ppm.
The pH of the second detergent composition in the laundry solution was about 9.3.
Identical polyester/cotton blend swatches were stained with a mixture of soil collected from air conditioning filters and a mineral oil/olive oil/oleic acid blend. The stained swatches were then washed using each of the above - two detergent compositions in a one gallon ~washing machine which simulates the action of a commercial washing machine.
The washing operation was carried out for 10 minutes using water having a temperature of about 100F (38C) and con-taining 7 grains per gallon of mixed calcium and magnesium hardness.
The soil removal performance was calculated by using the weight removal percentage, averaged across the three stained swatches washed in each composition. Both compositions gave -~ excellent soil removal performance. However, the cationic/
nonionic mixture containing monoethanolamine and having the higher alkalinity had a soil removal of about 73~, while the . . .
lower pH cationic/nonionic mixture had a soil removal of .
about 50%. These data demonstrate that improved soil removal performance is obtained by the use of cationic/nonionic detergent compositions having a higher alkalinity such as that obtained by the inclusion of monoethanolamine.
Substantially similar results are obtained when other sources of alkalinity, such as sodium hydroxide, sodium carbonate, triethanolamine, and sodium silicate, are used, ~ "
'., ~

- .

~ ' ` . : :

in comparable amounts, in place of or in combination with the monoethanolamine.
Similar results are also obtained where the nonionic component used above is replacecl by the condensation product 5 of C10 alcohol with 3 moles of ethylene oxide, the conden-sation product of coconut alcohol with 6 moles of ethylene oxide, the condensation product of coconut alcohol with 7 moles of ethylene oxide, the condensation product of C12 13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C14 15 alcohol with 7 moles of ethylene oxide, or the conaensatlon product of C12 13 alcohol with 3 moles of etnylene oxide stripped so as to remove the lower ethoxylate ana unethoxylated fractions.
Excellent cleaning results are also obtained where the . 15 detergent compositlons used contain nonionic to cationic surfactant ratios of about 5:1, 4:1, 10:3, 20:7, 20:9, 2:1, 5:3, or 1:1.
Excellent cleaning results are also obtained where the nonionic component is replaced by a mixture of the conden-sation product of C14_15 alcohol with 3 moles of ethylene oxide together with the condensation product of C14 15 alcohol with 7 moles of ethylene oxide, in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of about 2:1; or a mixture of the condensation product of coconut alcohol with 5 moles of ethylene oxide together with an alkylglyceryl ether having the formula:

bH

:
' ` '' ~
'': ' ~ ' . : .
~: :

,, .: : :

: -59-: in a ratio of alcohol ethoxylate to glyceryl ether of about

7:3.
~ ubstantially similar cleaning results are also obtained where the cationic component is replaced by C12 alkyl tri-methylammonium chloride, C14 alkYl trimethylammonium bromide,di-Clo alkyl dimethylammonium bromide, di-C12 alkyl dimethyl-ammonium chloride, tri-C8 alkyl methylammonium bromide, tri-C10 alkyl methylammonium chloride, or cationi.c components having the formulae given below:
. 10 N - CH2 14 29 C \ ¦ Br / \

:, 11 1+
.. C16~33_C_O_CH2CH2_N -CH3 C1 ~ 1l fH3 12 25 C CH2CH2-C-O-CH2CH2-N -CH Cl : 20 1H
. 3 Br~ CH3-+N-CH2CH2-O-C-(CH2)12 C O CH2CH2 1 3 ` 11 1 : lOH21 O(cH2cH2o)lo-c-cH2-N+-cH3 Cl . CH3 ,. ~

EXA~PLE IV
A detergent composition of the present invention was formulated by combining the condensation product of coconut alcohol with 5 moles of ethylenle oxide together with the cationic surfactant having the formula:
~ CH3 C17H35- -~CH2cH2 I CH3 Cl such that the ratio of nonionic surfactant tc) cationic surfactant was about 10:4. The detergent coll~position was used in the laundry solution at a concentration of about 500 ppm. A second detergent composition of the present - invention was formulated so as to contain the same nonionic and cationic components in the same ratio, but which addition-ally contained a C12_16 alkyl fatty acid ammonia amide, present in an amount such that the amide component would be present in the washing solution at a concentration of 50 ppm when the composition was used at a concentration of 500 ppm. This composition had a pH in the laundry solution of about 8.4. Nine swatches (3 cotton, 3 polyester and 3 polyester/cotton blend), were stained with a clay-in-water - suspension and were washed in a one gallon washing machine . ~
which simulates the action of a commercial washing machine, using each of the above two detergent compositions. Two 11" x 11" 100% cotton terry cloths, with loop construction, were added to each washing machine as redeposition sites for the soil removed from the stained swatchas. The washing process was carried out for 10 minutes in water of about .
,, "' "' ~, , '~':

-61~

100F (38C), containing 6.5 grains per gallon of mixed cal-cium and magnesium hardness. After washing the cloths in the respective test treatments and subsequently drying them, the reflectance of the terry cloths were read using a Hunter Reflectometer. The cleaning performance of both detergent compositions on the stained swatches was excellent. In addition, the first composition, containing o~ly the nonionic ; and cationic components, yieldecl terry cloths having a reflectance of 53 Hunter Whiteness Units, while the second composition, which additionally contained the amide component, yielded terry cloths having a reflectance of 71 Hunter Whiteness Units. These data demonstrate the improved soil antiredeposition properties which are obtained by the inclusion of an amide component in the cationic/nonionic detergent compositions of the present invention.
Substantially similar results are obtained where the amide component is present in such an amount such that the concentration of amide in the washing solution is about 80 ppm, 75 ppm, 65 ppm, 55ppm, 40ppm, or 30 ppm. Similar results are also obtained where the amide component used above is replaced by amides having the formula: -Rl-~-N or Rl-S-N
R /`
wherein Rl is C8 alkyl, C10 alkyl, C12 alkyl, C13 alkylr C15 alkyl or C17 alkyl, and R is hydrogen, methyl, ethyl, propyl, or hydroxymethyl.
Excellent results are also obtained where the nonionic .

.

surfactant used above is replaced by the condensation pro-duct of C10 alcohol ~ith 3 moles of ethylene oxide, the condensation product of coconut alcohol w~th 6 moles of ethylene oxide, the condensation product of coconut alcohol with 7 moles of ethylen~ oxide, the condensation product of C12 13 alcohol with 6.5 moles of ethylene oxide, the conden-sation product of C14 15 alcohol with 7 moles of ethylene oxide, or the condensation product of C12 13 alcohol with 3 moles of ethylene oxide stripped so as to remove nonethoxylated and lower ethoxylate fractions. Excellent results are also obtained wherein the nonionic component is xeplaced by a mixture of the condensation product of C10 alcohol with 3 moles of ethylene oxide together with the condensation pro-duct of a secondary C15 alcohol with 9 moles of ethylene oxide, in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of about 3:1; or the mixture of the condensation product of coconut alcohol with 5 moles of ethylene oxide together with an aIkyl glyceryl ether having the formula:

OH
; wherein the ratio of nonionic surfactant to glyceryl ether is about 3:1.
Substantially similar results are also obtained wherein the ratio of nonionic surfactant to cationic surfactant in 25 the above compositions is 5:1, 10:3, 20:7, 20:9, 2:1, 5:3, or 1:1.
Excellent results are also obtained where the cationic component of t~e above compositions is replaced by C12 alkyl .

.
' ~ ' ' ~ '. ' :

., . . . ~ : .

'.
` trimethylammonium chloride, C14 alkyl trimethylammonium chlo-- ride, di-Clo alkyl dimethylammonium bromide, di-C12 alkyl dimethylammonium bromide, tri-C8 alkyl methylammonium chloride, or tri-C10 alkyl methylammonium bromide.
` 5 EXAMPLE V
A substrate article, for use in the automatic laundering operation, is made by coating one side of an 8" x 11" sheet ; of a Scott 8050 Industrial Towel, having an air permeability of about 130 cu. ft./min./sq. ft., a basis weight of about 77.5 grams per sq. yd., and a thickness of 44 mils, with about 50 grams of a composition having the formulation given below.
The composition is made by intimately mixing the nonionic and cationic surfactants together, at a temperature of about 80C, to form a thick paste, and then adding the remaining ` 15 components.
Component Weight O fH3 C17H35-C-O-cH2cH2-l-`cH3 Cl 24.6 Condensation product of - coconut alcohol with 5 61.6 moles of ethylene oxide - C12_16 alkyl fatty acid ammonia amide 8.6 Monoethanolamine 5.2 CR-0.057 An identical sheet of the paper towel is placed on top of the coated original sheet, and the edges are sewn together so as to enclose the composition. This article has a pH

` ' '. : - , .

.
in the laundry solution of about 9.5, and provides a con-venient method for introducing the compositions of the present invention into the laundering solution, as well as providing excellent cleaning performance.
1 5 A substrate article may also be made by coating one side ` of an 11" x 11" sheet of melt-blown poly-propylene, having a thickness of about 29 mils, a basis weight of about 58.5 grams per sq. yd., and an air permeability of about 66 cu.ft./min./sq. ft., with about 60 grams of the detergent composition described above, placing an identical substrate sheet over the coated sheet, and heat-sealing together the edges of the two substrates, enclosing the detergent com-position within the article.
Similar articles may be manufactured wherein the cationic surfactant is stearoyl choline bromide. In this case, the cationic and nonionic surfactants are intimately mixed at a temperature of about 25C, to form a thick paste, and the remaining components are added.
EXAMPLE VI
A heavy-duty liquid laundry detergent composition, having the formula given below, is formulated by mixing together the following components in the stated proportions.
Component Weight %

1l fH3 25 C12H25-(CH2CH2)7-CH2-C- CH2CH2 1 314.3 Condensat:ion product of coconut alcohol with 5 moles of 35.7 ethylene oxide ~`
Monoethanolamine 45.0 : Lauramide 4.0 Minors tsuds suppressor, perfume brightener, etc.~ 1.0 CR=0.026 This product, when used in an automatic laundering operation at a concentration of about .05~, :has a pH of .
- about 9.5 and provides excellent removal of both particulate ` and greasy/oily soils, as~well as exhibiting good antire-deposition properties.

EXAMPLE VII

A solid particulate deterg~nt composition of the :-~ present invention, having the formulation given below, is ~ made by mixing together the following components.
i. .
Component Weight Dicoconut alkyl dimethylammonium 14.3 bromide Condensation product of coconut 35.7 alcohol with 5 moles of ethylene oxide Sodium bicarbonate 45.0 C12-16 alkyl fatty acid ammonia 4.0 i amide : Minors ~suds suppressor, perfume, 1.0 ` etc.~
CR=0.0466 This product, when used in an automatic laundering operation, at conventional usage concentrations, has a pH of about 10, and provides excellent particulate soil removal.
It is to be noted that as to the detergent composit~on, defined above, bicarbonate anions do not constitute .
. ' ' ' , `' ' .
~ .
:

6~) "interfering anions" (i.e., excellent performance is obtained even when such anions are present in the laundry solution).
EXAMPLE VIII
A cationic surfactant having the formula given below is prepared as follows.
- O CH

Cl2H25-(cH2cH2o~7-cH2-c-o CH2CH2 IN 3 44 Grams of an anhydrous sodium alkyl ethoxy acetate, having the formula given below and prepared by the azeotropic removal of water from "Sandopan DTC Gel"*(Sandoz Chemical), were dissolved in 100 ml. of methylene chloride at room temperature.

fl O

C12H25-O~cH2cH2o)7cH2 Na 18.R Grams of oxalyl chloride were added rapidly to the solution and the reaction mixture was left standing overnight. The solvent and the excess oxalyl chloride were then removed from the mixture by vacuum distillation, yielding the acid chloride corresponding to the sodium alkyl ethoxy acetate shown above.
40 Grams of the acid chloride product were then dissolved in 100 ml. of methylene chloride, in a two neck reaction vessel, equipped with a reflux condenser and dropping funnel. 12.2 Grams of N,N-dimethylaminoethanol were then added dropwise from the dropping funnel into the reaction *Trademark - . ' . ~ ~, , , ~ :
. ' . :~ ' ' ' :' , ' .:

.

mixture, at a rate such that the reaction heated to a boil.
The reaction was stirred at reflux during the addition step, and was allowed to stir overnight at ambient temperature.
The methyl chloride solut~on was then washed with an aqueous base solution, followed by two water washes. The separated organic layer was dried over sodium sulfate, and then stripped under vacuum to yield about 39 grams of amine ester corresponding to the sodium alkyl ethoxy acetate .~
` compound described above.

~` 10 37 Grams of this amine ester compound were then placed in a round bottom flask, equipped with a reflux condenser and a dropping funnel. An excess of iodomethane was added rapidly to the amine ester, causing the reaction mixture to boil during the addition. After the reaction subsided, the mixture was left standing overnight and was then stripped under vacuum, yielding 43 grams of the desired choline ester cationic surfactant having the formula given above.
This cationic surfactant, when used in the detergent compositions described herein, yields outstanding particulate soil removal, as well as excellent greasy and oily soil and body soil removal, in addition to providing static control, fabric softening, and dye transfer inhibition benefits to fabrics laundered with the compositions.
EXAMPLE IX

A stearic acid choline ester cationic surfactant, having the formula given below, was prepared in the following manner.

', ~
:

,~

6a~

O CH
ll 1 3 C17H3s-C~O-CH2CH2 -I -CH3 Cl 200 Grams of stearic acid, 138 grams of N,N-dimethyl-aminoethanol, 6 grams of concentrated sulfuric acid and 2000 ml. of benzene were combined in a flask equipped with a Dean-Stark water trap and a reflux condenser. The mixture was stirred at reflux, through the water trap, for four - days, during which time the theoretical amount of water had collected. The reaction mixture was cooled to room temperature and then washed with a dilute calcium hydroxide solution, followed by three water washes. The solution was then dried over sodium sulfate and stripped under ;- vacuum, yielding an amine ester.
The reaction product formed above was dissolved in 1000 ml. of 80/20 acetone/methylene chloride solvent.
Methyl chloride was bubbled into the solution, which thickened as the quaternary ammonium ester began to precip-itate out of solution. The reaction mixture was saturated with methyl chloride and then allowed to stand overnight.
The white, crystalline solid product was isolated by vacuum filtration, washed with acetone, and then dried in a vacuum oven, yielding 185 grams of the desired stearoyl choline ester cationic surfactant.
This b~odegradable cationic surfactant, when used in the detergent compositions defined herein, yields excellent particulate soil removal performance, as well as fabric softening, static control and dye transfer inhibition bene~its to fabrics laundered with those compositions.
:' - :: .

:' '' . , ~ ~ .

Claims (49)

1. A compound having the formula wherein each R1 is C1 to C4 alkyl or hydroxyalkyl; each R2 is either hydrogen or C1 to C3 alkyl; R3 is C4 to C30 straight or branched chain alkyl or alkenyl;
R4 is C1 to C10 alkylene or alkenylene; n is from 2 to 4;
y is from 1 to 20; a is 0 or 1, and t is 0 or 1, but t must be 1 when a is 1; m is from 1 to 5; Z2 is selected from the group consisting of , , , -O-, , , , , ;
Z1 is selected from the group consisting of , , , , ;

said selections being made so that is an alkyl or alkenyl group which can be interrupted by only structures selected from the group consisting of:

, , , , -69a--O-, , , and and wherein at least one of said Z1 and Z2 groups is selected from the group consisting of ester, reverse ester, amide, and reverse amide; and X is an anion which makes the surfactant at least water-dispersible.

2. The compound of Claim 1 wherein Z2 is selected from the group consisting of ester, reverse ester, amide and reverse amide.

3. The compound of Claim 2 wherein Z2 is selected from the group consisting of ester and reverse ester.

4. The compound of Claim 2 wherein Z2 is selected from the group consisting of amide and reverse amide.

5. The compound of Claim 2 wherein n is 4 and R2 is hydrogen.

6. The compound of Claim 2 wherein n is 2 and the R2 groups are CH3 and hydrogen respectively.

7. The compound of Claim 2 wherein n is 2 and R2 is hydrogen.

8. The compound of Claim 7 wherein y is from 1 to 10.

9. The compound of Claim 8 wherein R3 is C8 to C18 alkyl.

10. The compound of Claim 7 wherein a is 1 and Z1 is -C- .

11. The compound of Claim 10 wherein t is 1 and R4 is C2 alkylene.

12. The compound of Claim 7 wherein a is n.

13. The compound of Claim 12 wherein m is 2.

14. The compound of Claim 13 wherein t is 1 and R4 is methylene.

15. The compound of Claim 14 wherein Z2 is .

16. The compound of Claim 15 wherein y is from 1 to 10.

17. The compound of Claim 16 wherein R3 is C8 to C18 alkyl.

18. The compound of Claim 17 wherein R1 is CH .

19. The compound of Claim 18 wherein X is selected from the group consisting of halides, methyl sulfate, sulfate, and nitrate.

20. The compound of Claim 19 wherein X is selected from the group consisting of chloride, bromide, iodide, sulfate and methyl sulfate.

21. The compound of Claim 20 wherein y is 7.

22. The compound of Claim 21 wherein R3 is C12 alkyl.

23. The compound of Claim 7 wherein Z2 is .

24. The compound of Claim 23 wherein y is from 1 to 10.

25. The compound of Claim 24 wherein R3 is C8 to C18 alkyl.

26. A detergent composition containing from 0 to about 20% of phosphate materials, and having a pH in the laundry solution of not greater than about 11, comprising from about 5 to about 100% of a surfactant mixture consisting essentially of (a) a biodegradable nonionic surfactant having the formula R(OC2H4)nOH wherein R is a primary or secondary alkyl chain of from about 8 to about 22 carbon atoms and n is an average of from about 2 to about 12, having an HLB of from about 5 to about 17; and (b) the cationic surfactant of Claim 1;
said composition having a pH of at least about 6.5 in the aqueous laundry solution, and wherein the ratio of said nonionic to said cationic component is in the range of from about 1:1 to about 100:1.

27. The composition of claim 26 wherein, in the cationic surfactant, Z2 is selected from the group consisting of ester, reverse ester, amide, and reverse amide.

28. The composition of Claim 27 wherein the nonionic surfactant is selected from the group consisting of the condensation product of C10 alcohol with 3 moles of ethylene oxide, the condensation product of coconut alcohol with 5 moles of ethylene oxide, the condensation product of C12 alcohol with 5 moles of ethylene oxide, the condensation product of C12-13 alcohol with 3 moles of ethylene oxide, and the same product which is stripped to remove substantially all lower ethoxylate and nonethoxylate fractions, the con-densation product of C12-13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C12-13 alcohol with 9 moles of ethylene oxide, the condensation product of C14-15 alcohol with 3 moles of ethylene oxide, the condensation product of C14-15 alcohol with 4 moles of ethylene oxide, the condensation product of C14-15 alcohol with 7 moles of ethylene oxide, the condensation product of C14-15 alcohol with 9 moles of ethylene oxide, and mixtures thereof.

29. The composition of Claim 27 wherein, in the cationic surfactant, Z2 is .

30. The composition of Claim 29 wherein, in the cationic surfactant, n is equal to 2 and R2 is hydrogen.

31. The composition of Claim 30, wherein, in the cationic surfactant, a is 0 and m is equal to 2.

32. The composition of Claim 31 wherein, in the cationic surfactant, R4 is methylene and t is equal to 1.

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33. The composition of Claim 32 wherein, in the cationic surfactant, y is from 1 to 10.

34 The composition of Claim 33 wherein, in the cationic surfactant, R1 is CH3.

35. The composition of Claim 34 wherein, in the cationic surfactant, X is selected from the group consisting of chloride, bromide, iodide, methyl sulfate and sulfate.

36. The composition of Claim 35 wherein, in the nonionic surfactant, R is an alkyl chain of from about 10 to about 18 carbon atoms.

37. The composition of Claim 36 wherein, in the cationic surfactant, y is equal to 7.

38. The composition of Claim 37 wherein, in the cationic surfactant, R3 is C12 alkyl.

39. The composition of Claim 27 wherein the ratio of nonionic surfactant to cationic surfactant is from about 1:1 to 5:1, and the reduced cationic monomer concentration of the nonionic/cationic surfactant mixture is from about 0.005 to about 0.2.

40. The composition of Claim 35 wherein the ratio of nonionic surfactant to cationic surfactant is from about 1:1 to 5:1, and the reduced cationic monomer concentration of the nonionic/cationic surfactant mixture is from about 0.005 to about 0.2.

41. The composition of Claim 39 wherein the ratio of nonionic surfactant to cationic surfactant is from about 5:3 to 5:1.

42. The composition of Claim 41 which is substantially free or phosphate, polyphospnate, silicate, and poly-carboxylate builder anions, carboxymethylcellulose, and anionic surfactants.

43. The composition of Claim 39 which is substantially free of oily hydrocarbon materials.

44. The composition of Claim 27 wherein the ratio of non-ionic surfactant to cationic surfactant is from 5.1:1 to about 100:1, the nonionic/cationic surfactant mixture has a cloud point of from about 0 to about 95°C, and the reduced cationic monomer concentration of the nonionic/cationic surfactant mixture is from about 0.002 to about 0.2.

45. The composition or Claim 35 wherein the ratio of nonionic surfactant to cationic surfactant is from 5.1:1 to about 100:1, the nonionic/cationic surfactant mixture has a cloud point of from about 0 to about 95°C, and the reduced cationic monomer concentration of the nonionic/cationic surfactant mixture is from about 0.002 to about 0.2.

46.
The composition of Claim 44 which additionally contains from about 1 to about 60% of a detergency builder salt.

47. The composition of Claim 44 wherein said composition forms separated phases when added to water having a tempera-ture of about 45°C, at a concentration or from about 0.01 to about 0.3%.

48. The composition of Claim 44 wherein the ratio of nonionic surfactant to cationic surfactant is from 5.1:1 to about 50:1.

49. The composition of Claim 26 which has a pH of greater than about 7 in the aqueous laundry solution.