CA1129299A - Laundry detergent compositions having enhanced particulate soil removal and antiredeposition performance - Google Patents

Abstract

Abstract Laundry detergent compositions containing specific mixtures of selected nonionic surfactants, selected cationic surfactants and fatty amide surfactants are disclosed. These compositions are unusually effective in removing soils, especially particulate soils, from fabrics, and preventing their redeposition onto the fabrics during the laundering process.

Description

1~2~

Technical Field This invention relates to laundry detergent com~ositionS
containing no or low levels of phosphate materials,which exhibit highly improved particulate soil removal capabilities. These detergent compositions provide surprisingly effective clay soil 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 un-expectedly good removal of greasy/oily and body soils are defined in U. S. Patent 4,259,217 of A. P. Murphy, issued March 31, 1981.
_ckground Art Nonionic surfactants are generally used in laundry de-tergent 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 surfact-ants have been included in detergent compositions for the pur-pose of yielding a germicidal or santization 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 ditallowalkyl-dimethylammonium chloride, are included in detergent compositions for the purpose of yielding a fabric-softening benefit, as dis-closed in U. S. Patent 3,607,763, Salmen et al, issued September 21, 1971; and U. S. Patent 3,64~,203, Lamberti et al, issued February 22, 1972. Such components are also used to control staticO 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, 1975. However, none of these patents indicate that by the careful selection and com-bination of certain nonionic and cationic surfactants, to achieve Z95~

specific nonionic:c~tionic su~f~ctant r~tios and reduced cationic monomer concentrations, outstanding removal of particulate soils may be obtained.
The compositions of the present invention have outstan-ding 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 dramaticall~ better, than fully-built conventional 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 pro-viding, in a single detergent product, particulate soil removal, fabric softening, static control and dye transfer inhibition ben-efits 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 surfactants 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 particulate soil removal, which may be used in a variety of physical 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 invention to provide specific detergent compositions which yield e~cellent Particulate soil removal and which are biodegradable.

- 2 -

3~

It i5 a still further specific object of this invention to de~ine specific novel cationic surfactants which are biode-gradable and which yield excellent particulate and greasy and oily 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 pro-vide amide-containing cationic/nonionic surfactant-containing com-positions which yield both excellent particulate soil removal and 0 anti-redeposition properties.
It is yet another object of this invention to provide a process for laundering fabrics which yields especially good par-ticulate soil removal, using cationic and nonionic surfactant-containing detergent compositions.
Disclosure of the Invention The present invention relates to laundry detergent com-positions, containing from 0 to about 20% phosphate materials, which are especially beneficial for the removal of particulate soils from fabrics and in preventing their redeposition back onto the fabric surfaces, which comprise 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;
(b) a cationic surfactant having the formula RmRXYLZ
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 interrupted by up to four structures selected from the group consisting of l~Z~9~

o O R2 R2 ~
C-O-, -O-C-, -C-N-, -N-C-, -C-N-, -N-C-, -O-, -O-C-O-, -O-C-N-, -N-C-O-, and mixtures thereof, each R containing from about 8 to 2~ carbon atoms, and which may additionally contain up to about 12 ethylene oxide groups, m is a number from 1 to 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 R in a molecule being benzyl, x is a number from 0 to 11, the remainder of any carbon atom positions being filled by hydrogens, Y is selected from the group consisting of (1) --~ -- , \ ~ I
N - C-(~) -C +
~ N - C -(3) -P -

(4) -S -

(5) -N~- , wherein p is from 1 to 12, (C2H4 ) p (C2H4) P

(6) -N+~ , wherein each p is from 1 to 12, ~C2H4 ) p

(7) ~C ~ ~N~
C /

C ~ / , and ~ C\ ~C

(9) mixtures thereof;
L is 1 or 2~ the Y groups being separated by a moiety selected from the group consisting of Rl and R2 analogs having from 1 to about 22 carbon atoms and two free carbon single bonds, when L is 2; Z is an anion in a number to give electrical neutrality, and said cationic sur-factant being at least water-dispersable in admixture with said nonionic surfactant; and (c) a fatty amide surfactant;
said composition having a pH of at least about 6.5 in the aqueous laundry solution, the ratio of said nonionic to said cationic surfactant being in the range of from about 1:1 to about 100:1, and the ratio of the combined nonionic and cationic surfactants to said amide surfactant being in the range of from about 5:1 to about 50:1.
The compositions of the present invention are formula-ted so as to have a pH of at least about 6.5 in the laundry solu-tion 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. ~t pH's lower than about 6.5, the overall cleaning per-formance of the compositions tend to decrease. Particularly pre-ferred compo5itions have a pH of greater than about 8 in the : laundry solution, in order to improve the removal of body soil.
~ . 5 -~2~

The compositions may be formulated so as to be free of oily hydrocarbon materials, such as many dry cleaning solvents, mineral oil, paraffin oil and kerosene, because these materials (which are themselves oily in nature) load the washing liquor with excessive oily material, thereby diminishing the cleaning effec-tiveness of the compositions of the present invention.
The compositions may also be formulated such that thecationic component is free of hydrazinium groups due to their relatively high toxicity level which makes them unsuitable for use in the compositions of this invention.
The compositions of the present invention comprise, by weight, from about 5 to 100%, particularly from about 10 to about 95~, and most preferably from about 20 to about 90% of a mixture of the particularly defined nonionic and cationic surfactants in the ratio 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 and conditioning results.
Further, preferred compositions do not contain more than about 10 of the cationic component, due to cost and commercial availabil-ity considerations.
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, carhon atoms and n is an avera~e of from about 2 to about 12, preferably from about 2 to about 7, and especially from about 4 to about 7. The non-ionic surfactants .included within the present invention includebranched alcohol ethoxylates. The nonionics have an H~B (hydro-philic-lipophilic balance) of from about 5 to about 17, preferably . .~

1~ Z~'~99 from about 6 to about 14 ! and especiall~ from about 10 to about 13.5. These nonionic surfactants are preferably com~ined with less solu~le cationic materials (such as those having 2 or 3 long alkyl chains~. ~here 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, rnc., 1~66, pp. 507-613.
Particularly preferred nonionic surfactants for use in the compositions of the present invention include the condensa-tion product of C10 alcohol with 3 moles of ethylene oxide, thecondensation product of coconut 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 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 condensation 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 2a of C14 15 alcohol with 3 moles of ethylene oxide, the condensa-ion 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 u~ilize oxoalcohols containing about 20% 2-methyl branched isomers, com-mercially available under the trademark "Neodol", from Shell Chemical Company.
The compositions of the present invention may also con-tain mixtures- of nonionic surfactants falling within the above 3Q nonionic surfactant definition, or mixtures of nonionic surfac-tants, some of which do not fall within the above nonionic sur-factant definition, as long as at least one of the nonionic sur-~L2~3z~

factants contained in the mixtu.re falls within the above defin-ition of the nonionic surfactants, and the ratio of that nonionic surfactant to the cationic surfactant falls wit~in the required nonionic/cationic ratio. Where the nonionic surfactant mixture contains a nonion;c surfactant (:or surfactants) which falls out-side of the above nonionic definition, the ratio of the surfact-ant (or surfactants~ wtthin 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 sur-1~ factant mixtures include a mixture of the condensation product of Cl4 15 alcohol with 3 moles of ethylene oxide. "~eodol 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 condensation product of Cl0 alcohol with 3 moles of ethylene oxide together with the condensation product of of secondary Cl5 alcohol with 9 moles of ethylene oxide "(Tergitol 15-S-9)"3, in a ratio of lower ethoxylate nonionic to higher ethoxy-late nonionic of from about 1:1 to about 4:1; and a mixture of "Neodol 45-3" and "Tergitol 15-S-9", in a ratio of lower ethoxy-late nonionic to higher ethoxylate nonionic of from about l:l to about 3~
Preferred nonionic surfactant mixtures contain alkyl glyceryl ether compounds in addition to the required nonionic surfactant. Particularly preferred are glyceryl ethers having the formulae R-OCH2-CIH-CH2OH and R-O(CH2~H2O~rlcH2cHcH2oH
OH OH
wherein R is an alkyl or alkenyl group of from about 8 to about 1. Trademark 2. "
3. "

112~299 18, preferably about 8 to 12 caxbon atoms 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 nonionic surfactant component of the present invention, in a ratio of nonionic surfactant to glyceryl ether of from about 1:1 to about 4:1, particularly about 7:3. Glyceryl ethers of the type useful in the present invention are disclosed in Canadian Patent No. 1,081,574, K. L. Jones, issued July 15, 1980; and U. S. Patent 4,098,713, K. L. Jones, issued ~uly 4, 1'~78.
Other biodegrada~le nonionic surfactants well known in the detergency arts may be used, in combination with one or more of the nonionic surfactants falling within the definition of non-ionic surfactants required in the present invention, to form use-ful nonionic surfactant mixtures. Examples of such surfactants are listed in U. S. Patent 3,717,630, Booth, issued February 20, 1~73, and U. S. Patent 3,332,880, Kessler et al, issued July 25, 1967. Nonlimiting examples of suita~le nonionic surfactants which may be used in conjunction with the required nonionic sur-factants include the condensation products of aliphatic alcohols with from about 13 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include th~ condensation product of myristyl alcohol condensed with about 13 moles of ethylene oxide per mole of alcohol; and the condensa-tion 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 "surfactant" and"cosurfactant" containing at least one nonionic surfactant falling ~ithin the definition of nonionic surfactants useful in the present invention, as described in Canadian Patent No. 1,059,865 of Collins, issued August 7,1979.

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Cationic Component The cationic surfactants used in the compositions of the present invention have the formula RmRxYLZ
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 interrupted by up to four structures selected from the following group:
O O O R R O
a ~r, ~ o-, -o-c-, -c-~ N-C-, O H H O O O H H O
~1 7 ~ tl -C-N-, -N-C-, -O-, -O-C-O-, -O-C-N-, -N-C-O-, and mixtures thereof, and which contains from about 8 to 22 carbon atoms. The Rl groups may additionally contain up to 12 ethoxy groups. m is a number from 1 to 3. No more than one R ~roup 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 R is an alkyl or hydroxy-alkyl group containing from 1 to 4 carbon atoms or a benzyl group with no more than one R 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) --~+_ \ ,/ I
/N - C-(2) -C
N - C-(3) -P -(4) -S+--- 10 ~-2~9 (5) 1 ~ , whercin p is from 1 to 12, (C2H~O)pH

(C~4O)pH
(6) -N _ , whcrein each p is from 1 to 12, (C2H4O)~H

.~,C \ ~, t7) C +N

/c~ /

(8) N +N , and C C \
; N

(9) mixtures thereof;
`` L is 1 or 2, with the ~ groups being separated by a moiety selec-ted from R1 and R analogs (preferably alkylene or alkenylene) having from 1 to about 2~ carbon atoms and two free carbon single bonds when L is 2. Z is a water-soluble anion, such as a halide, sulfate, methylsulfate, hydxoxide, or nitrate anion, particularly preferred being chloride, bromide, iodide, sulfate or methyl sulfate anions, in a number to give electrical neutrality of the cationic component. 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 surfac-tants, as well as the anions discussed hereinafter, remain dis-persed 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.

1~2:3Z~

When used in comblnation with nonionic surfactants, within the specific ratios and the preferred reduced cationic monomer concentrations, defined hereinafter, these cationic com-ponents provide excellent soil removal characteristics, confer static control and fabr~c softening benefits to the laundered fabrics, and inhibit the transfer of certain dyes among the laundered fabrics in ~he wash solution. Preferred cationic sur-factants are those which have critical micelle concentrations less than about 500 ppm.
In preferred cationic materials, L is equal to 1 and Y

is \ / !
C---~- or -C ~ I
~ N _ ~ _ or mixtures thereof. However, L may be 2 and~ in that case, the cationic component contains 2 ca~tionic charge centers. Other cationic materials which are useful in the compositions of the present invention include phosphonium and sulfonium materials.
;; 20 Where m is equal to 1, it is preferred that x is equal to 3 and R is a methyl groupO Preferred compositions of this mono-long chain type include those in which Rl is a C10 to Cl~
alkyl group. Particularly preferred compositions of this class include C12 alkyl trimethylammonium halide, C14 alkyl trimethyl-ammonium halide, coconutalkyl trimethylammonium halide, tallow-alkyl trimethylammonium halide, and C16 alkyl trimethylammonium 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 R chains can be longer than 16 carbon atoms. Thus, ditallow-dimethylammonium chloride and distearyldimethylammonium chloride, ~2~Z99 which are used conventionally as. fahric softeners and static control agents in detergent compositions, are not included within the definition of the cationic components used in t~e present invention. Preferred di-long chain cationics of this type in-clude those in ~hich x is equal to 2 and R 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 alkyldimethylammonium halide, di-C12 alkyl-dimethylammonium halide materials, and dicoconutalkyl dimethyl-lQ ammonium halide.
Where m is equal to 3, only one of the Rl chains can begreater than 12 carbon atoms in length. In this instance, it is pre~erred 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 trioctylalkylmethylammonium halide, and tridecylalkylmethyl-ammonium halide.
~ nother 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:

Z R-tN-(C2H4O)pH H(OC H ) -N~-(C H O) H Z~
R R
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 R is a C10 to C20 alkyl group.
The compositions of the present invention are formulated so as to be substantially free of ethoxylated cationic surfactants whic~ contain an average of about 13 or more, and especially more than about lQ~ moles of ethylene oxide per mole of surfactant.
; - 13 -~' 1~ Z~ 9 These compounds tend to be xelatively nonbiodegradable, do not enhance the cleaning or fabr.ic conditioning benefits provided by the compositions and may, in some circumstances, decrease the overall laundering performance provided by them.
The following formulations have been found to be es-pecially suita~le for removing particulate soils, and provid~ng fabric softening, static control and dye transfer inhibition ben-efits, in a conventional home laundering operation.
(a) Tallowalkyltrimethylammonium halide or methyl-sulfate, such as chloride, together with a nonionic surfactant selected fxom the condensation product of C12-C13 alcohol with 2 to 4 moles of ethylene oxide and the condensation product of C14-C15 alcohol with 3 to 6 moles of the 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 nonionic:cationic ratio of from 5:1 to about 5:3.
(b) Tallowalkyltrimethylammonium halide or methylsul-fate, such as chloride, together with a nonionic surfactant sel-ected 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 conden-sation 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 from 5:1 to about 4:1. Com-positions which exhibit both excellent particulate and greasy/oily soild removal may be formulated by combining this cationic ma-terial 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 a nonionic:
cationic ratios of from 5:1 to about 1:1.
. - 14 -~12~

(c) Coconutalkyltrimethylammonium halide or methyl-sulfate, such as chloride, together with a nonionic surfac-tant selected from the condensation product of C12-C13 alc o with 2 to 4 moles of ethylene oxide and the condensation product of C14-C15 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 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-tant selected 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 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 particu-late and greasy/oily 50il removal may be formulated by combin-ing this cationic material with the condensation product of C12-C 3 aicohol 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 R -N -CH2 - ~ Z ' wherein R , R and Z
R are as defined above, l~LZ929~

together with a nonionic surfactant selected from the con-densation products of C12 -C15 alcohols with 2 to 4 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 nonionic:cationic ratio of from about 3:1 to about 1:1.
(f) A cat onic surfactant of the formula R -N -CH2- ~ Z , wherein R , R and Z are ¦2 as defined above, together with a nonionic surfactant selected from the con-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::L 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, 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. Composi-tions which give both excellent particulate and greasy/oily ,,, 112~$'3 soil removal can be obtained by combining this cationic surfactant with the condensation product of C12-C13 alcohol with 6 to 10 moles of ethylene oxide in nonionic:cationic ratios of from 5:1 to about 4:1.

(h) Tri-C12 alkylmethylammonium 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 moles 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 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 methylsulfate, such as chloride, together with a nonionic surfactant selected from the condensation product of C12-C13 alcohol with 5 to 10 moles of ethylene oxide, and the condensation 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 ethyl-ene oxide, 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 condensa-tion product of C14_15 alcohol with 7 moles of ethylene oxide, the condensation product of C14 lS alcohol with 9 moles of ethylene oxide, or mixtures thereof, in a nonionic:cationic ratio of from about 3:1 to about 1:1.
A particularly preferred type of cationic component, ~i ~29~99 which is described in U.S. Patent No. 4,260,529 of James C.

Letton, granted April 7, 1981, has the formula Rl R2 _ (Zl)a-(R )n~Z ~(CH2)m~N -R X
R
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 R - N-(CH2)S-; wherein s is frGm 0 to 5;

Rl 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 R ~ H H 1~
-C-O-, -O-C-, -O-, -O-C-O-, -C-N-, -N-C-, -O-C-N-, -N-C-O-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 nit-: rate, preferably chloride, bromide, iodide, sulfate, or methyl sulfate.
In addition to the advantages of the other cationicsurfactants disclosed herein, this particular cationic component is environmentally desirable, since it is bio-degradable, 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 compositions of -- s; ~

Z~9 the present invention, they are used in surfactant mixtures which have 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, most preferably about 10:4.
In preferred compositions, the ratios are selected such that the compositions have reduced cationic monomer concentra-tions as specified herein. These preferred cationic surfact-ants may also be used in the detergent systems defined in U.S. Patent No. 4,259,217 of A.P. Murphy, issued March 31, 1981, in nonionic to cationic ratios of 5.1:1 to about 100:1, preferably 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 70C, most preferably from about 20 to about 70C, and in preferred compositions, the surfactant mixture 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.
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.
Particularly preferred cationic surfactants of this type are the choline ester derivatives having the following formula: CH

'i I

., . --19--..

., ll~g~

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 o~ cationic surfactant include stearoyl choline ester quaternary ammonium halides (R2 = C17 alkyl), palmitoyl choline ester quaternary ammonium halides (R2 = C15 alkyl), myristoyl choline ester quaternary ammonium halides (R2 = C13 alkyl), lauroyl choline ester ammonium halides (R2 = Cll alkyl), and tallowvl choline ester quaternary ammonium halides (R = C15-C17 alkyl).
Additional preferred cationic components of the choline ester variety are given by the structural formulas below, where-in p may be from 0 to 20.

Z 11 11 1 +
R -O-C-(CH2)pC-O-CH2-N -CH3 X

X~ CH +N-CH -CH2-O-C-(C~2)p-C O CH2 2 1 3 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 product is then quaternized with a methyl halide, forming the desired cationic material. The choline-derived cationic materials may also be prepared by the direct esterification 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 quaterni~e t_i-methylamine, forming the desired cationic component.

Another type of novel, particularly preferred cationicmaterial, described in U.S. Patent No. 4,228,042 of J.C.Letton issued October 14, 1980, has the formula R2 Rl R -O[(CH)nO]y~(Zl)a~~R )t-Z -(CH2)m-N -R X

Rl In the formula, each Rl is a Cl to C4 alkyl or hydroxy-alkyl group, preferably a methyl group. Each R2 is either hydrogen or C1 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 preferably a C12 alkyl group. R4 is a Cl to C10 alkylene or alkenylene 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 OE 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 O O H H O
Il 11 11 11 1 1 11 11 1 1 il -C-O-, -C-, -O-, -O-C-O-, -C-N-, -N-C-, ~O-C-N-, -N-C-O- ;
zl is selected from the group consisting of:

O O O H H O H O
l! 11 ll I 1 11 1 11 -C-O-, -C-, -C-N-, -N-C-, -N-C-O-and wherein at least one of said 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 selected 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 nonionic/

, 112~

cationic surfactant mixtures in a ratio of nonionic component to cationic component of from about 1:1 to a~out 100:1. When these surfactants are used in the compositions 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 concentration within the range given herein. They may be also used in the nonionic/cationic surfactant mixtures disclosed in U.S. Patent ~,259,217 of Murphy, issued March 31, 1981, wherein the ratio of nonionic component to cationic component would be 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 form-ulating 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 70C, most preferably from about 20 to about 70C, and the surfactant mixture pre-ferably has a reduced cationic monomer concentration of from - 20 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 oily 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 . ~

2g9 cationic surfactant is used, it is preferred that the deter-gent compositions have a pH of not greater than about 11, pre-ferably 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.

~' C~3 -R -~(CII CH~O)~ `T''2)t-C-(~-c~l2-c~l2-~l -Ci13'`
C~3 O CH
R -o(C~12CH2O)~ C-C}12-N -C113 X

R3_o(CHCH2O)y-C~CH2 I C 3 X

3 l IC~13 R -O(CHCH O) -(CH2) -C-O-CH2-CH2-N -CH3 X
c~3 o O CH3 R O( 2CH2O).t, ( 2)t 2 2 , 3 C~3 o El H O Cll ll I I 1~ 1 3 R -O(CH2CH2O)y~C~c=c~c-o-cll2cH2-L~ -C~T3 Y~
c~3 ~!~

~12~99 O CH
R -o(CH2CH2cH2cH2O)y-c-cH2-~ -CH3 X

R3-o(CH2 CH2CH2CH2O)y~(CH2)t C O-CH2C~12 1 3 The preferred derivatives, described above, may be pre-pared by the reaction of a long chain alkyl polyalkoxy (pre-ferably polyethoxy) carboxylate, having an alkyl chain of desired length, with oxalyl chloride, to form the correspond-ing acid chloride. The acid chloride is then reacted with dimethylaminoethanol 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 com-pounds is by the direct esterification of the appropriate long chain ethoxylated carboxylic acid together with 2-haloethanol or dimethyl aminoethanol, in the presence of heat and an acid catalyst. The reaction product formed is then quaternized with methylhalide 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 mono-mer 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 com-ponents 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 additional components to the mixture. This intimate premixing of the nonionic and cationic components enhances per-formance of the compositions.
An approximation of the CR of a surfactant mixture is obtained by dividing the concentration of the cationic surfac-tant monomer in the laundry solution by the critical micelleconcentration (CMC) of the surfactant. As used in the applica-tion, CMC's are determined at 105F in water containing 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 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 Congress of Surface Activity, III, 449 Academic _.
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 (II) in Clint):

*

(clm) 2[ 2 _ 1] + cml(C-c2 + cl) - ~ Ccl = 0 . . .

112~?9 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" denotes cationic surfactant) cl = critical micelle concentration (CMC) of nonionic surfactant (moles/l.) C2 = critical micelle concentration of cationic surfactant (moles/l.) x = total mole fraction of nonionic surfactant in the solution = Cl/(Cl + C2) ~ = a constant based upon the heat of mixing =-2.8 clm = nonionic monomer concentration c2m = cationic monomer concentration e = base of Mapierian logarithm system = 2.71828 x = mole fraction of the nonionic surfactant in the micelle at concentration C

fl = nonionic activity coefficient in the mixed 20 micelle = e~ (1-x)2 f2 = cationic activity coefficient in the mixed micelle = e~x ~ = f2C2 - flCl 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 solved for the nonionic monomer concentration by taking its positive root (equation (12) in Clint).
cm = {_(C-(c2-cl))+[~C-(c2-cl) )2 ~ 4~C(c2-cl)]l/2}
-- .... . _ .
*

j 2( * -1) Cl By modifying this equation based on the assumptions of a regular, rather than an ideall solution, the CR range for optimum performance was derived from the following equation:

-(C-~) + ~(C-~) + 4~C~ (1) x = 2h For a given cleaning test for a nonionic/cationic systeml x was found by inserting the values known from the * *
test (i.e., cll c2l ~ , C and ~ ) into equation (1) and solving iteratively for xl such that the error in x is less , than O.001. This procedure was repeated for a large number of such testsl over varying usage conditions. The x values obtained were then used to solve for the cationic monomer concentrations using the following equation:
c2m = (1-X)f2C2 (2) The CR value was then calculated using equation (3).

R 2/ 2 (3) The CR values obtained cover a large number of com~ina-tions and ratios of various nonionic and cationic surfactants ' at various conce~trations and temperaturesl which have been ' evaluated for their ability to clean greasy/oily soils. The ,,: .

.. ..
:

~9~g~

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 over-all 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 equztion (l-x)e3 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 Ml - - = [x (x-l)~ ]
using 100 ppm and 10,000 ppm as the boundary values for W, fox each end of the CR range;
(c) the nonionic/cationic ratio (NCR) range for optimum performance is then within the range obtained by substituting the boundary values for Y into the formula NCR -~,_y Put another way, steps ~b) and (c) may be combined into a single equation which may be solved directly for the NCR.

~' NCR = X = (lOOC/W)~ + M2-T--1) _Y (10-Oa/~)~ +
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 con-centration, CR is essentially independent of concentration.
This means that or conventional laundry usage concentrations (e.g., 100 ppm to 10,000 ppm, and especially from about 250 ppm to about 3,000 ppm), the CR of most commercial cationic, nonionic surfactant mixtures (wherein the cationic component 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 concentra-tion, so that using a concentration of about 1,000 ppm in the above calculation will be satisfactory approximation for the entire range. As used herein, if a concentration range is not specified, the 1,000 ppm CR is meant.

By way of example, the optimum ratio for grease/oil removal or Composition A (palmitoylalkyl trimethylammonium chloride plus the condensation product of C12 alcohol with 5 moles of ethylene oxide) of Example I, described in U.S.
Patent No. 4,259,217 of A.P. Murphy, issued March 31, 1981, 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 5ppm c2- 2.1875 x 10 5ppm ~= -2.8 .;,

11~3~t 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):
(l-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-0 922) _ 032202(1-Y) 1OOO (0.922) (0.922-1) (~.73 x 10-5) Y = 0.938 Substituting this value for Y into equation (c), the nonionic/cationic ratio is determined.
NCR =1 o:9388 = 15.1 It will be noted that this ratio corresponds to the 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 detergency, 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 70C, more prefer-ably between about 20 and about 7QC, 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 out-standing removal of greasy/oily soils. If a composition does not have a cloud point within the temperature range specified, it will not yield outstanding greasy/oily soil cleaning within that temperature range. 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 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 about 25C, most preferably about 20C, above that cloud point temperature.
As used herein, the term "cloud point" means the temper-ature 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 Model VM-12397 Photogoniodiffusometer, manufactured by.Societe .~, 9~

Francoise d'instruments de controle et d'analyses, France (the instrument being hereinafter referred to as (SOFICA).
The SOFICA s~mple 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. Appro~imately 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 ~he sample cell lid, so that the cell interior is not exposed to atmospheric dust. The sample is kept in a variable temp~
erature bath, and both the bath and the sample are subject to constant stirring. The bath temperature is heated using the SOFICA's heater and cooled by the addition of ice (heat-ing rate 1C/minute); the temperature of the sample is deter-mined by the temperature of the bath. The light scattering intensity of the sample is then determined at various temp-eratures, 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 from about 2 to about 16%, and most preferably from about 3 to about 10%, of a fatty amide surfactant. Any nonionic surfactant conventionally used in detergent compositions;
may be used in these compositions; however, preferred compo-sitions contain the nonionic surfactants defined above, in order to maximize the cleaning benefit obtained. These amide surfactants may be used ~n nonionic/cationic surfactant mixtures having nonionic:cationic ratios of from about 1:1 3Q to about 100:2. When they are used in the compositions of th~ 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 nonionic/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 well as improved soil anti-redeposi-tion characteristics.
Amides useful in these preferred compositions include, but not limited to, carboxylic acid amides, sulfonic acid amides, phosphonic acid amides, and boronic acid amides.
Preferred amides include those having the formulae:

O R2 R -S- ~
\ R2 O/ O R

wherein Rl is a C8-C20 alkyl, alkenyl, alkyl phenyl or alkyl benzyl group, preferably C10 C18 alkyl, and most preferably Cll alkyl; and each R2 is hydrogen, or Cl-C8 alkyl or hydroxyalkyl, preferably hydrogen. Specific examples of 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 hydrogeni present in the wash solution at about 50 parts per million); and a mixture of stearoyl choline bromide (100 ppm)~ the condensation product of coconut alcohol with 5 moles of ethylene oxide 9~'g~

(357 ppm), and lauramide (Rl = Cll and R2 is hydrogen; at45 ppml. These amides may also be used in the surfactant mixtures described in U.S. Patent No. 4,259,217 of A.P. Murphy, issued March 31, 1981,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 par-ticularly from about 6:1 to about 20:1. In forming such com-positions, 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 10 to about 70C, especially from about 20 to about 70C, and the surfactant mixture preferably has a ratio which corres-ponds 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 compositions the amount of anion-producing materials, and hence anions which will make the particular cationic surfactant used in the com-positions 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 10 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. Su~h a complexing of the anionic material with the cationic surfactant decreases the overall cleaning and fabric 1~2~32~9 conditioning performance of the composition.
Suitable anionic materials may be selected based on their strength of complexation with the cationic material included in the composition (as indicated by their dissoci-ation constant). Thus, ~hen 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%, hy weight, of the cationic surfactant;
~here 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 invention 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 phosphatç 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 1:~292~9 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 beneficial effect on clean-ing performance.
The compositions of the present invention may contain up 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 ~
t sio~
R' wherein x is from about 20 to about 2,000, and R and R' are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl. The polydimethylsiloxanes (R and R' are ~L~2~2~

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-, phenyl-methyl-polysiloxanes and the like. Additional useful silicone suds controlling agents can be represented by a mi~ture of an alkylated siloxane, as referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica. A preferred silicone suds controlling agent is represented by a hydrophobic silianated (most preferably trimethylsilanated) silica having a particle size in the range from about 10 millimicrons to 20 millimicrons and a specific surface of above about 50 m2/gm. intimately admixed with dimethyl silicone fluid having a molecular weight in the 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-emulsify-ing silicone suds suppressors, described in Canadian Patent No. 1,085,697 of Gault et al, issued September 16, 1980. 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 range from 35C-115C and a saponification value of less than *Trademark . . .

~2$~

100 represent additional examples of a preferred suds regulat-ing component for use in the 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 microcrystalline waxes have a metling point from about 65C to 100C, a molecular weight in the range from 400-1,000; and a penetration value of at least 6, measured at 77F by ASTM-D1321. Suitable examples of the above waxes include: microcrystalline and oxidized microcrystalline petro-latum waxes; Fischer-Tropsch and oxidized Fisher-Tropsch waxes;
ozokerite; ceresin; montan wax; beeswax; candelilla; and car-nauba wax.
Alkyl phosphate esters represent an additional preferred suds suppressant for use herein. These preferred phosphate esters are predominantly monostearyl phosphate which, in add-ition thereto, can contain di- and tristearyl phosphates and monooleyl phosphates, which can contain di- and trioleyl phos-phates.
The alkyl phosphate esters frequently contain some tri-alkyl phosphate. Accordingly, a preferred phosphate ester can 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 conven-tional 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.

:-.

1~2~3Z99 However, because of the numerous and diverse performance ad-vantages 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 manufac-tured 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, Jones, issued October 3, 1978; and U.S. Patent No. 4,113, 630, Hagner et al, issued September 12, 1978.
These articles consist of a water-insoluble substrate which releasably incorporates an effective amount, preferably from about 3 to 120 grams, particularly from about 20 to 80 grams; of the detergent compositions of the present invention.
A particularly preferred substrate article incorporates 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 addition-al 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.

~2;~

When this process is used to make 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, O CH
ll 1 3 17H3s C O-CH2CH2-N -CH3 Br . CH3 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 coconut 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 stear-oyl 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, ~L~23299 at a nonionic:cationic ratio of about 10:4, a thick pasteproduct is formed. If t~e same components are mixed together at about 25C, the mixture remains a liquid, which is much less desirable for use in making substrate articles. Sub-stantially similar results are obtained when the nonionic surfactant is the condensation product of coconut alcohol with 5 moles of ethylene oxide. Where this process is used in making the compositions described in U~S. Patent No. 4,259, 217 of A.P. Murphy, issued March 31, 1981, nonionic:cationic ratios of from 5.1:1 to about loa 1, preferably from 5.1:1 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 preferred 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% 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 surfactant ~3 ~9Z~9 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 adsorp~ion 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 t~le present invention are used in a laundry solution, a threshold concentration of at least about 50, preferably about 100, most preferably about 150, parts per million on the cationic component must be present in the laundry solution in order to give the particulate 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 threshold concentra-tion in the laundry solution. In washing processes which utilize higher concentrations of detergent composition, such as European washing processes, it is possible to use higher nonionic surfactant to cationic surfactant ratios, while still attaining the necessary cationic threshold concentration.
Under these European washing conditions it is possible to obtain excellent particulate soil removal, in addition to r outstanding greasy and oily soil and body soil removal, using the nonionic surfactant to cationic suxfactant ratios of from 5.1:1 to about 100:1 defined in U.S. Patent No. 4,259, 217 of A.P. Murphy, issued March 31, 1981.
All percentages, parts, and ratios used herein are by weight unless otherwise specified.
~ The following nonlimiting examples illustrate the com-i positions and the method o- the present invention.
, -42-., llZ~3~

_XAMPLE I
Identical cotton, polyester/cotton, and polyester swatches were stained with a clay-in-water suspension and three stained swatches of each fabric type were washed in a one gallon washing machine, which simulates the action of a commercial washing machine, using two different detergent compositions. One 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 of swatches was laundered in a detergent com-position of the present invention, having the following formul-ation:
Component % by Weight Dicoconutalkyl dimethyl- 19 ammonium bromide Condensation product of C 4 5 48 alcohol with 7 moles ofl ethylene oxide (Neodol 45-7) 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 of about 500 ppm, and had a 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 100 F (38 C). 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 re-- *Trademar~

~2,f~g flectance readings of the individual swatches. A higher re-flectance 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 Vnits. These data demonstrate the outstand-ing clay soil removal performance of the unbuilt compositions of the present invention, which equaled the performance pro-vided by the conventional built, brightener-containing deter-gent composition.
Substantially similar cleaning results are obtained where 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 chloride, di-C12 alkyl dimethylammonium chloride, tri-C8 alkyl methylammonium hromide, tri-C10 alkyl methylammonium c~oride, or the cationic s~factants listed below:

HOH4C2-N -C2H4OH Cl ~ -~4-1~2 .~
C12H25 C \ ¦ Cl N -CH
/ \

C18H37-N -CH2- ~ Cl i O CH
li 1 3 C16H33-C-O-cH2cH2 N CH3 Br I

O o CH3 1~ 11 1 C H --C-cH2cH2-c--cH2cH2 1 3 Br lOH21 O(CH2CH2O)lo~C~CH2~N -CH3 Cl Substantially similar cleaning results are also ohtained where the cationic surfactant used above is replaced by a mixture of dicoconutalkyl dimethyl-ammonium bromide (A) together with C12 alkyl trimethyl-ammonium chloride (B) in a ratio of A:B of about 4:1, 3:1, 2:1, 1:1, 1:2, or 1:4, a mixture of ~, l~Z~3~99 O CE~
ll 1 3 C17H35-C-O-cH2cH2 N C 3 Br (C) together with di-Cl~ alkyl dimethylammonium chloride (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 C H -O-(CH2C~2O)7 CH2-C O CH2 2 3 Cl (E) 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 ethylene oxide, the condensa-tion product of coconut alcohol with 7 moles of ethylene oxide (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 unethoxy-lated 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 : -46-l~lZ~ 9 higher ethoxylate nonionic of about 2:1, or the mixture of the condensation product of coconut alcohol wit~ 5 moles of ethylene oxide together with an alkyl glyceryl ether having the structural formula:

C12H25-0CH2ClH C~2 OH
in a ratio of alcohol ethoxylate to glyceryl ether of about 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 addi-tion of monoethanolamine, to have a pH in the laundry solution of about 7, 8, 8.5, 9 or 10.

EXAMPLE II
Identical cotton, polyester/cotton, 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 compo-sition, optimized for grease and oil removal, having for form-ulation given below, at its recommended usage level.

~2~ 9 Component % by Weight "Neodol 45-7" 15.0 Mg Linear alkyl benzene31.3 sulfonate Triethanolamine 3.5 Ethanol 6.5 Coconut alkyl fatty acid1.0 Water 41.8 Brightener and minorsBalance 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 % by Weight

12 25 ( 2cH2o)7-cH2-c-o-cH2~H2-N+-cH Cl-Condensation product of C12_13 71.4 alcohol with 3 moles of ethylene oxide, stripped to remove lower ethoxylate and unethoxylated fractions ("~eodol 23-3T)"
The detergent composition of the present invention has 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 9~

readings, obtained 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 fa~ric ty~es) Bacon Dirty Grease Morcor Oil Liquid laundry composition 58.2 45.5 lQ Nonionic/cationic mixture 58.8 57.5 These data demonstrate the effective grease and oil removal obtained using the preferred cationic components in the detergent compositions of the present invention. The detergent composition of the pre~ent invention, as formulated above, also yields excellent particulate soil removal per-formance, and gives fabric softening, static control and dye transfer inhibition benefits to fabrics laundered therewith.
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 ethy-lene oxide, the condensation product of C12 alcohol with 5 moles of ethylene oxide ~HLB=ll), the condensation product of coconut alcohol with 5 moles of ethylene oxide, the con-densation product of coconut alcohol with 7 moles of ethylene oxide, the condensation product of C12_13 alcohol with 6-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.

~L~2~Z99 Similar results are also obtained where the cationic surfactant, used above, is replaced by one of the following surfactants:
+
C14H2~-O(CH2CH2O)7-CH2-C-O-CH2CH2-N -CH3 Br I

O CH
ll 1 3 C12H25-O(CH2CH2O)g-CH2-C-O-CH2-O-CH2CH2-N -CH3 Br o CH
ll 1 3 lOH21 O(CH2CH2O)lo~C~CH2~N -CH3 Cl O H H O CH
~ 3 C13H27-O(CH2CH2O)8-C-C=C-C O CH2CH2 1 3 Cl O CH

(C~I2CH2C~2CH2O)7-C-CH2-N -CH3 Br 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:
O CH
ll 1 3 C H -C-O CH2CH2-N -CH Cl -5~-~L2~9 in a ratio of nonionic surfactant to cationic surfactant 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 deter-gent composition of the present invention was formula~ed by combining the same nonionic and cationic surfactants in the same ratio as above. The composition also contained mono-ethanolamine as an alkalinity source, in an amount such that the monoethanolamine was present at about 30 ppm in the wash-ing solution when the entire composition was used at a concentra tion of about 530 ppm. The pH of the second detergent com-position 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 containing 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 dat~ demonstrate that improved soil removal per-formance i3 obtained by the use of cationic/nonionic detergent compositions having a higher alkalinity such as that obtained , :

1~2~299 by the inclusion of monoethanolamine.
Substantially similar results are obtained when other sources of alkalinity, such as sodium hydroxide, sodium carbon-ate, triethanolamine, and sodium silicate, are used, in com-parable amounts, in place of or in com~ination with the mono-ethanolamine.
Similar results are also obtained where the nonionic component used above is replaced by the condensation product of C10 alcohol with 3 moles of ethylene oxide, the condensa-tion product of coconut alcohol with ~ moles of ethylene oxide, the condensation product of cocon~lt 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 conden-sation product of C12_13 alcohol with 3 moles of ethylene oxide stripped so as to remove the lower ethoxylate and unethoxylated fràctions.
Excellent cleaning results are also obtained where the detergent compositions used contain nonionic to cationic sur-factant 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 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 ~:1, or a mixture of the condensation product of coconut alcohol with 5 moles of ethylene oxide together with an al~ylglyceryl ether having the formula:

~ . .

~2~9 C12H25-OCH,~CH--CH20H

OH

in a ratio of alcohol ethoxylate to glyceryl ether of about 7:3.
Substantially 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 cationic components having the formulae given below:

~ N CH2 14 29 C \ ¦ Br N+ - CH2 C16H33-C-O-cH2cH2 N CH3 Cl ; C12H25 ~ C~CH2CH2~C ~ CH2CH2-N~ -CH3 Cl .~

CH O O CH
1 3 ~ 3 Br CH3- N-cH2cH2-o-c-(cH2)l2-c-o-cH2cH2-N+-cH3 Br Il i +
ClOH21 O(CH2CH2O)lo~C~CH2~N -CH3 Cl EXAMPLE IV

A detergent composition of the present invention was formulated by combining the condensation product of coconut alcohol with 5 moles of ethylene oxide together with the cationic surfactant having the formula:
- O CH
Cl7H35-C-O-c~2cH2 N CH3 Cl such that the ratio of nonionic surfactant to cationic sur-factant was about 10:4. The detergent composition 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 additionally 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 5Q ppm when the composition was used at a concentration of S00 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 1~L2~3Z~S~

one gallon washing machine which simulates the action of a commercial washing machine, using each of the above two deter-gent 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 swatches. The washing process was carried out for 10 minutes in water of about 100~ (38C), containing 6.5 grains per gallon of mixed calcium 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 excel-lent. In addition, the first composition, containing only the nonionic and cationic components, yielded terry cloths hav-ing 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 antiredepo-sition 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 con-centration of amide in the washing solution is about 80 ppm, 75 ppm, 65 ppmr 55 ppm, 40 ppm, or 30 ppm. Similar results - are also obtained where the amide component used above is replaced by amides having the formula:
o R2 R2 R -C-N or R -S-N
\ R2 O~ O \ 2 ,, 1~2~Z~9 wherein Rl is C8 alkyl, Cl0 alkyl, C12 Y ~ 13 Cl5 alkyl or C17 alkyl, and R2 is hydrogen, methyl, ethyl, propyl, or hydroxymethyl.
Excellent results are also obtained where the nonionic surfactant used above is replaced by the condensation product of C10 alcohol with 3 moles of ethylene oxide, the condensation product of coconut alcohol with 6 moles of ethylene oxide, the condensation product of coconut alcohol with 7 moles of ethy-lene oxide, the condensation product of C12 13 alcohol with 6.5 moles of ethylene oxide, the condensatiQn product of C14 15 alcohol with 7 moles of ethylene oxide, or the conden~sa-t on product of Cl2_l3 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 replaced b~ a mixture of the 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, 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 alkyl 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 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 ~.

2~9 COmponent of the above compositions is replaced by C12 alkyl trimethylammonium chloride, C14 alkyl trimethylammonium chloride di-Clo alkyl dim~thylammonium bromide, di-C12 alkyl dimethyl-ammonium ~romide, tri-C8 alkyl methylammonium chloride, or tri-C10 alkyl methylammonium ~romide.

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 8Q50 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 components.

Component W
O CH
ll 1 3 C17H35 C -CH2cH2-N -CH3 Cl 24.6 I

Condensation product of 61.6 - coconut alcohol with S
moles of ethylene oxide C12_16 alkyl fatty acid 8.6 ammonia amide 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 50 as to enclose the composition. This article has a pH in the laundry solution of a~out 9.5, and provides a convenient method for introducing the aompositions of the present . ~ .

1~2.9;~

invention into the laundering solution, as well as providing excellent cleaning performance.
A substrate article may also ~e made by coating one side of an ll" x 11" sheet of melt-blown polypropylene, having a thickness of about 29 mils, a ~asis weight of about 58.5 grams per sq. yd., and an air permea~ility 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 composition 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 form~llated by mixing to-sether the following components in the stated proportions.

Component Weight %
O CH

Cl2H25-o(cH2cH2o)7-cH2-c-o-cH2cH2-N+-cH3 Cl 14.3 Condensation product of coconut 35.7 alcohol with 5 moles of ethylene oxide Monoethanolamine 45.0 Lauramide 4.0 Minors (suds suppressor,perfume 1.0 ~rightener, etc.) CR=0.026 112g~

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/oil~ soils, as well as exhibiting good antiredeposition properties.

EXAMæLE VII
A solid particulate detergent composition of the present invention, having the formulation given below, is made by mixing together the following components.

Component Weight %

Dicoconut alkyl dimethylamonium 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 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 compo-sition, defined above, bicarbonate anions do not constitute "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.

Il I
C12H 5-0 (CH C~I O) --CH --C--O--CH CH --N~--CH Cl I

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 lO0 ml. of methylene chloride at room tem-perature.
o Cl2H25-O(cH2cH2o)7cH2 Na 1~.8 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 producer were then dissoved in lO0 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 drop-wise from the dropping funnel into the reaction mixture, at a rate such that the reaction heated to a boil. The reaction was stirred at reflux during the addition step, and was allow-ed to stir overnight at ambient temperature. The methyl chlor-ide solution was then washed with an aqueous base solution, following by two water washesO 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 *Trademark ~Z~99 sodium alkyl ethoxy ecetate compound described above.
37 Grams of this amine ester compound were then placed in a round ~ottom 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 sur-factant having the formula given above.
This cationic surfactant, when used in the detergent com-positions 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 soften-ing, 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.

ll 1 3 17H3s C 0-CH2CH2_N -CH3 Cl 200 Grams o~ stearic acid, 138 grams of N,N-dimethylamino-ethanol, 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, following by three water washes. The solution was then dried over sodium sulfate and '~' ~lZ~

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 ammoniu~ ester began to precipitate out of solution. The re-action 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 lQ stearoyl choline ester cationic surfactant.
This biodegradable cationic surfactant, when used in the detergent compositions defined herein, yields excellent par-ticulate soil removal performance, as well as fabric softening, static control and dye transfer inhibition benefits to fabrics laundered with those compositions.

Claims (40)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A detergent composition, which contains from 0 to about 20% phosphate materials, 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;
(b) a cationic surfactant having the formula wherein each R1 is an organic group containing a straight or branched alkyl or alkenyl group optionally substituted with up to three phenyl or hydroxy groups and optionally interrupted by up to four structures selected from the group consisting of ,,,,, ,, -O-,,,, and mixtures thereof, each R1 containing from about 8 to 22 carbon atoms, and which may additionally contain up to about 12 ethylene oxide groups, m is a number from 1 to 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, x is a number from 0 to 11, the remainder of any carbon atom positions being filled by hydxogens, Y is selected from the group consisting of:

(1) , (2) , (3) , (4) , (5) , wherein p is from 1 to 12, (6) , wherein p is from 1 to 12, (7) , (8) , and (9) mixtures thereof;
L is 1 or 2, the Y groups being separated by a moiety selected from the group consisting of R1 and R2 analogs having from 1 to about 22 carbon atoms and two free carbon single bonds, when L is 2; Z is an anion in a number to give electrical neutrality, and said cationic surfactant being at least water-dispersible in admixture with said nonionic surfactant; and (c) a fatty amide surfactant;
said composition having a pH of at least about 6.5 in the aqueous laundry solution, the ratio of said nonionic to said cationic surfactant being in the range of from about 1:1 to about 100:1, and the ratio of the combined nonionic and cationic surfactants to said amide surfactant being in the range of from about 5:1 to about 50:1.

2. The composition according to Claim 1 wherein the fatty amide surfactant component is selected from the group consist-ing of , , and mixtures thereof, wherein, in the amide component, R1 is a C8-C20 alkyl, alkenyl, alkyl phenyl or alkylbenzyl group; and each R2 is C1-C8 alkyl or hydroxyalkyl, or hydrogen.

3. The composition according to Claim 2 wherein the ratio of the combined cationic and nonionic surfactants to the amide surfactant is from about 8:1 to about 25:1.

4. The composition according to Claim 3 wherein the amide surfactant is

5. The composition according to Claim 4 wherein, in the amide component, R1 is C10-C18 alkyl.

6. The composition according to Claim 5 wherein, in the amide component, R1 is C11 alkyl.

7. The composition according to Claim 2 wherein the ratio of said nonionic surfactant to said cationic surfactant is from about 1:1 to 5:1, and the reduced cationic monomer con-centration of the nonionic/cationic surfactant mixture is from about 0.005 to about 0.2.

8. The composition according to Claim 7 wherein, in the cationic surfactant, no more than one R1 in a molecule can have 16 or more carbon atoms when m is 2, or more than 12 carbon atoms when m is 3.

9. The composition according to Claim 8 wherein the ratio of said nonionic surfactant to said cationic surfactant is from about 5:3 to 5:1.

10. The composition according to Claim 9 which is sub-stantially free of phosphate, polyphosphate, silicate, and polycarboxylate builder anions, carboxymethylcellulose, and anionic surfactants.

11. The composition according to Claim 10 wherein the ratio of said nonionic surfactant to said cationic surfactant is from about 10:5 to about 10:3.

12. The composition according to Claim 9 wherein, in the nonionic surfactant, R is an alkyl chain of from about 10 to about 18 carbon atoms.

13. The composition according to Claim 12 wherein in the nonionic surfactant, n is an average of from about 2 to about 9.

14. The composition according to Claim 9 wherein the cationic surfactant has the formula wherein R2 is C10-C30 straight or branched chain alkyl or alkenyl or alkylbenzyl; and X is an anion selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate.

15. The composition according to Claim 14 wherein R2 is C17 alkyl and X is selected from the group consisting of chloride, bromide, iodide, methyl sulfate and sulfate.

16. The composition according to Claim 9 wherein the cationic surfactant has the formula wherein R3 is C4-C30 straight or branched chain alkyl, alkenyl or alkylbenzyl; y is from 1 to 20; and X is an anion selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate.

17. The composition according to Claim 16 wherein R3 is C12 alkyl, y is 7 and X is selected from the group consisting of chloride, bromide, iodide, methyl sulfate and sulfate.

18. The composition according to Claim 2 which is sub-stantially free of oily hydrocarbon materials.

19. The composition according to Claim 2 which has a pH of greater than about 7 in the aqueous laundry solution.

20. The composition according to Claim 2 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 substan-tially all lower ethoxylate and nonethoxylated fractions, 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 condensation product of C14-15 alcohol with 3 moles of ethylene oxide, the conden-sation 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 there-of.

21. The composition according to Claim 2 wherein the ratio of said nonionic surfactant to said cationic surfactant is from 5.1:1 to about 100:1, the cloud point of the nonionic/
cationic surfactant mixture is 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.

22. The composition according to Claim 21 which addition-ally contains from about 1 to about 60% of a detergency builder salt.

23. The composition according to Claim 21 which forms separated phases when placed in water at a temperature of about 45°C, at a concentration of from about 0.01 to about 0.3%.

24. The composition according to Claim 21 wherein the ratio of said nonionic surfactant to said cationic surfactant is from 5.1:1 to about 50:1.

25. The composition according to Claim 24 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 nonethoxylated fractions, the con-densation product of C12-13 alcohol with 6.5 moles of ethy-lene oxide, the condensation product of C12-13 alcohol with 9 moles of ethylene oxide, 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, 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.

26. The composition according to Claim 24 wherein the cationic surfactant has the formula wherein R2 is C8-C30 straight or branched chain alkyl, alkenyl, alkyl phenyl, or alkylbenzyl; and X is selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate.

27. The composition according to Claim 26 wherein R2 is C17 alkyl and X is selected from the group consisting of chloride, bromide, iodide, methyl sulfate and sulfate.

28. The composition according to Claim 24 wherein the cationic surfactant has the formula wherein R3 is C4-C30 straight or branched chain alkyl, alkenyl, alkyl phenyl, or alkylbenzyl; y is from 1 to 20, and X is an anion selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate.

29. The composition according to Claim 28 wherein R3 is C12 alkyl, y is 7 and X is selected from the group consisting of chloride, bromide, iodide, methyl sulfate and sulfate.

30. The composition according to Claim 7 wherein the amide surfactant is

31. The composition according to Claim 30 wherein, in the amide component, R1 is C10-C18 alkyl.

32. The composition according to Claim 31 wherein, in the amide component, R1 is C11 alkyl.

33. The composition according to Claim 21 wherein the amide surfactant is

34. The composition according to Claim 33 wherein R1 is C10-C18 alkyl.

35. The composition according to Claim 34 wherein R1 is C11 alkyl.

36. The composition according to Claim 33 wherein the non-ionic 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 ethoxylated and nonethoxylated fractions, the con-densation product of C12-13 alcohol with 6.5 moles of ethy-lene 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.

37. The composition according to Claim 33 wherein the cationic surfactant has the formula wherein R2 is C8-C30 straight or branched chain alkyl, alkenyl, alkyl phenyl, or alkylbenzyl; and X is selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate.

38. The composition according to Claim 37 wherein R2 is C17 alkyl and X is selected from the group consisting of chloride, bromide, iodide, methyl sulfate and sulfate.

39. The composition according to Claim 33 wherein the cationic surfactant has the formula wherein R3 is C4-C30 straight or branched chain alkyl, alkenyl, alkyl phenyl, or alkylbenzyl; y is from 1 to 20, and X is anion selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate.

40. The composition according to Claim 39 wherein R3 is C12 alkyl, y is 7 and X is selected from the group consisting of chloride, bromide, iodide, methyl sulfate and sulfate.