CA1204980A - Detergent composition - Google Patents

Abstract

ABSTRACT

This invention relates to detergent compositions for use in washing textiles containing an essential three component surfactant system consisting of specific alkyl sulfate, specific sulfonate and cationic detergent surfactants. Such three component surfactant system provides excellent detergency, especially on organic soils such as lipid, greasy and oily soils. Also, such compositions provide unusually low levels of soil redeposition.

Description

:~0'~91~

DETERGENT COMPOSI~ION
Charles F. Bleil Lawrence A. Gilbert John B. Welch III
Benny S. Yam TECH~ICAL ~IELD

This invention relates to detergent compositions cont~; n i ng specific alkyl sulfate, specific sul~onate and cationic detergent surfactants for use in washing textiles. The compositions ran be in any form, such as granules, liquids, tablets or pastes. In prQferred embodiments the detergent compositions within the inven-tion contain a detergency builder and/or a nonionic sur~actant and/or a fatty acid soap and~or enzy~e~.
BACXGROUND ARl`
Cationis surfactants have been incorporated in 20 detergent compositions for purposes other than cleaning;
for example, for a germicidal or sanitization bene~it, a fabric softening ~enefit or a static contrDl b~nefit.
More recently it has been disclosed that cat~ onic sur-factants in combination with anionic and/or nonionic 25 surfactan~s are effective for cleaning purposes . U. SO
Patent 4,235,759, Ohbu e~ al (November 25, 1980), discloses liquid detergent compositions that are super-ior in detergency conta; ni ng an alkyl polyoxyalkylene ether sulfate anionic surfactant and a mono- long chain 30 alkyl quaternary ammonium cationic surfactant wherein the molar ratio of anionic surfactant:cationic surfac-tant is from 8 :1 to 1:1.
U.SO Patent 4,321,165, Smith et al ~March 23, 1982), discloses solid detergent compositions containing 35 from 2~ to 60% of a surfactant system consisting of a wa~er soluble anionic surfactant, an alkoxylated alcohol .. . . ..

0 ~ 9 ~ ~

nonionic surfactant and a water-soluble quaternary ammonium cationic surfactant wherein the ratio o ani-onic surfactant:ca~ionic surfactant is from 5:1 to 1:3 and the ratio of nonionic surfactant:cationic suractant is from 100:1 to 2:3. Tt iS disclosed that such compo-sitions have improved greasy soil removal capabilities.
European Patent Application 0j026,529, Spadini et al (published August 4, 1981), discloses detergent compositions containing from 3~ to 40% of an anionic surfactant, from 0.5~ to 15% of a mono- long chain alkyl quaternary ammonium compound or an aliphatic amine and from 1.5~ to 45~ of an impalpable smectite-type clay wherein the molar ratio of the nitrogenous compound:
anionic surfactant is less than 1. It is stated that such compositions clean well and also act as te~tile softeners.
U.S. Patent 4,333,862, Smith et al (June 8, 19823, discloses liquid detergent compositions conta;n;ng from about 10% to about 82~ of an anionic surfactant, from about lO~ to about 82% of an alkoxylated alcohol noni-onic surfactant and from about 4% to about 35~ of a water-soluble quaternary salt cationic surfactant. It is disclosed that such combinations exhibit improved cleaning performance on greasy and oily soils.
It is an object of the present invention to provide detergent compositions for washing textiles that provide excellent 50il removal, especially organic soil removal, with an unusually low level of soil redeposition onto the surface of the textiles.
30~ Another object of the present invention is to provide detergent compositions that provide such bene-fits over a wide range of washing temperatures~
SUMMARY OF T~IE l~v~ ION
The present invention comprises a detergent compo-sition containing, by weighto a (a) from about 2% to about 50~ of a water-soluble alkyl sulfate detergent surfactant having the formula:
RO(C2H~O)XSO3M
wherein R is an alkyl chain having from about 8 to about 18 carbon atoms, saturated or unsaturated, wherein the longest linear alkyl porkion of the chain extending from the head group is lS carbon atoms or less on th~ aver-age; M is the cation, preferably an alkali metal, ammonium or substituted ammonium cation and x is from 0 to about 4;
(b) rom about 1/4% to about 12~ of a ca~ionic surfactant selected from the group consisting 15~ of:-: ~i) compounds having the general formula:
~: [R2 ~oR3 ) ml[R4 (oR3 ) y] zR5Q X
: wherein Q is N, P or S; z is 1 if ~ is: S
and 2 if Q is N or P; R2 is selected from the group consisting of alky~ and alkyl benzyl groups having from about 6 to about 16 carbon atoms excluding the benzyl group; each R3 is selected from the group consisting of -CH~CH2-, -C~2C~CH3)-, -CH2CH~C~2OH)-, CE2CH
C~2, and mixtures thereof; each R is selected from the group consisting o~ H
when y is not 0, Cl_4 alkyl, Cl_4 : . hydroxyalkyl, benzyl groups, ring struc-tuxes formed by joining the t~o R4 groups, and -C~2CHOHCHOHCHOR6CHOHCH2OR
: wherein each R6 is H or any hexose wherein at least one R6 is ~; R5 is selected from the group consisting of : 35 [R2(oR3)m], [R4(oR3)V] and ring struc-tures formed by joining any of the :~ ~a ~

carbon atoms of R2 and R5 wherein the total number of carbon atoms of R2 plus R is not more than about 18, a benzane ring being treated as equivalent to about 2 carbon atomsJ and wherein if R4 is less than about 4 carbon atoms then R contains from about 8 to aboùt 16 carbo~ atoms excludins the benzyl group;
each y is from 0 to about 3, m is from 0 to about 3) and X is any compatible anion, particularly one selected from the group consisting of halide, hydrox-ide, methylsulfate and acetate anion~
and mixture~ thereo~; and (ii) compounds having the general formula:
~R (OR )y~n Q X
(CH2)a H - C - ~(R O~mR ]2 wherein Q, R , R , y, m and X are as ~ defined above; n is 2 if Q is S and 3 if Q is N or P; each R is ~elected from the group consisting of an alkyl or alkyl benzyl group containing at least ahout 1 carbon atom excluding the benzyl ~5 group and said R groups can be joined - to form 5 or 6 membered ring structures, and wherein the sum of the carbon atoms : of [(R O)mR ]2 is from about 9 carbon atoms to about 16 carbon atoms when m is 0 and from about 10 ca~bon atoms to about 18 carbon atoms when m is ~rom 1 to about 3, with each R preferably contA;n;ng at least 2 carbon atoms, a benzene ring being treated as equivalent to about 2 carbon atoms; and a is from 0 to about 3;

~ ~d0 ~9 ~

(iii) aliphatic amines having the general formula:
[R (OR )m][R (OR )y]R N
wherein R , R , R , R , m and y are as defined above and the pKa is at least about 1/2 unit abo~e the initial pH of the wash li~uor;
(iv) compounds having the general formula [R tOR )m] N -~R toR3) y]4 ~_ 2 wherein R2, R3 t R4, R5, m, y and X are as defined above;
(v) compounds having the general formula:

2 3 [R (OR )m] -N-5 y 2 R
: ~ R -N-wherein R , R3~ R , R , m and y are as : defined above and the pKa i5 at least : 20 about 1/2 unit above the initial pH of the wash liquor and mixtures thereof;
(cl from about 1/2% to a~out 50~ of a sulfonate : det~rgent surfactant selected from the group ; ~ 25 ~ consisting o~ the water soluble salts of Cg lS
alkyl benzene sulfonates, C8 ~4 paraffin lfonates~ C8-18 alkyl glycery7 ether sulfon-ates, esters of ~-sulfonated fatty acids ContA; n; ng from about 6 to about 20 carbon ~ 30 atoms in the fatty acid group ana from about 1 ; to about 10 carbon atoms in the ester group and Cl 6 alkyl ox aryl sulfonates containing an ether, ester or amide linkage to a C7 lS
alkyl chain;

td) from 0% to about 50% of a nonionic detergent surfactant; and (e) from about 0% to about 70~ of a detergency builder;
wherein the molar ratio of (b~:(c) is less than about 1.5.
DETAILED DESCRIPTION OF THE lNv~LlON
This invention comprises detergent compositions conta; n; ng an essential three component detergent sur-factant system consisting of specific alkyl suLfate tspeci~ic sul~onate and cationic detergent surfac~ants.
This specific three component surfactant system is~ an extremely effective detergent. It is particularly e~fecti~e on organic soils, for example, lipidt greasy and oily soils. AIso, the use of such sys~em results in an unusu~lly low level of soil redeposition. Soil redepo~ition results when soi~ that is removed ~rom the texti}es into the wash liquor during the wash process is redepo~ited onto the textiles.
The detergen~ compositions within ~he invention provide the desired superior performance over a broad range of wash water conditions. The wash water tempera-ture can range from about 5C. to about 95~C. It is preferred that the initial pH of the wash liquor; i~e., the detergent com~osition and wash water mixture, be greater than about 8 and most preferably ~rom about 9 to abou~ Il.
The detergent compositions within the invention can be in any form-, such as granules, liquids, ta~lets or pastes, but the granulax compositions are preferred.
The granules- can range in density from about .15 gramst cubic centimeter to about .8 grams~cubic centimeter.
Without being bound by theory, it is believed that the detergent compositions within the invention provide the desired superior performance on organic soils because the alkyl sulfate detergent surfac~ant and the 134~

sulfonate detergent surfactant each ~orm an electxo-neutral complex with the cationic surfactant. The mechanism of organic soil removal is believed to be based upon the surfactant adsorbing to the soil surface to reduce the soil/water interfaclal tension to such an extent that the mechanical action of the washing process removes soil from the textile surface. Since the com-plexes formed are electrically neutral and, therefore, do not repel each other, they can pack densely when they adsorb onto the soil surface. This results in a much lower soil/water interfacial tension and thereby extremely effective soil r~moval. It should be noted that in order to obtain the desired superior performance of the present invention both the alkyl sulfate deter-gent surfactant and the sulfonate detergent surfactantmust be present. However, experimental evid~nce indi-cates that it is essential that the molar ratio of cationic surfactant to sulfonate detergent surfactant be less than about l.5. Otherwise, the desired superior per~ormance is not obtained.
Additionally, it is preferred that there be a molar excess o the sum of the alkyl sulfate detergent surf~c-tant and the sulfonate detergent surfactant with respect to the cationic surfactant to ensure proteinaceous and particulate soil removal and the suspension in the wash liquor of the soil removed from the textiles. Such soil suspension prevents soil redeposition.
The following is a detailed description of the essential and the optional components of the detergent compositions within the invention. All perc~ntages, parts and ratios are by weight unless otherwise indi-cated.
THE ~ATIONIC SURFACTANT
The cationic suxfactant is an essential component of the compositions within the invention. Without the cationic surfactant, the electro-neutral complex cannot ~ ~4~

be formed with the alkyl sulfate detergent surfactant and/or the sulfonate detergent surfactant and, there-fore,. the desired superior performance is not obtained.
Though, theoretically, essentially any cationic surfac-tant can be utillzed to provide such benefit, ni~rogen-ous surfactants that are cationic or capable of existing in cationic form are the most prac~icable. Also, the cationic surfactants within the invention can be satur-ated or unsaturated.
The cationic suxfactants within the invention are selected from the group consisting of:
~i3 compounds having the general formula:
lR (OR ~m~[R tOR )y]2R Q X
wherein Q is N, P or S; æ is 1 if Q is S
and 2 if Q is N or P; R2 is selected from the group consisting of alkyl and alkyl benzyl groups having from about 6 to about 16 carbon atoms excluding the benzyl group; each R3 is selected from the group consisting of -CH2C~2-, -CH2-CH(cH3)_, -cH2cHlc~2oH) r -CH2CH~H~' and mixtures thereof; each R is selected from the group consisting of H
when y is not 0, C1_4 alkyl~ C1_4 hydroxyalkyl, benzyl groups, ring struc-tures formed by joining the two R
groups, and -CH2CHOHCHOHC~OR6CHO~CR20R6 wherein each R6 is H or any hexose wherein at least one R is H; R is selected from the group consisting of [R (OR3)m], [R (oR3)y] and ring struc-tures formed by joining any o the carbon atoms of R and R whexein the total number of carbon atoms of R plus R5 is not more than about 18, a benzene ring being treated as equivalent to about 2 carbon atoms~ and wherein if R
is less than about 4 carbon atoms then R contains from about 8 to about 16 carbon atoms excluding the benzyl group;
S each y is ~rom O to about 3, m is :from O
to about 3~ and X is any compatible anion, particularly one selected from th~ group consisting of halide, hydrox-ide, methylsulfate and acetate anions an~ mix~ures thereof; and (ii~ compounds having the general formula:
~R (OR )y]~ Q ~
(C~2)a H - C - [(R O~mR ~2 wherein Q, R3, R4, y, m and X are as defined above; n is 2 ff Q is S an~ 3 if.

Q is N or P; each R' is selected from the group consisting of an alkyl or ~...
alkyl benæyl group cont~in;ng at Ieast about l carbon a~om exclwding the benzyl group and said R7 groups can be joined to form 5 or 6 membered ring structures, and wherein the sum of the carbon atoms of [(R O~mR ]2 is from about 9 carbon a~oms to about l6 carbon atoms when m is 0 and from about l0 carbon a~oms ~o about 18 carbon atoms when m is ~rom l to about 3, with each R preferably c~ntaining at least^ 2: carbon atoms, a benzene ring being treated as equivalent to about 2 carbon atoms; and a is from 0 to about 3;
(iii) aliphatic amines having the general formula:
[R (OR )m][R (OR )y]R N
h i R2 R3 R4 R5 m nd y are s ~-~o'~

defined above and the pKa is at least about 1/2 unit above the initial p~ of the wash liquor;
(iv) compounds having the general formula:
ER (OR )m] -N+~
[R ~OR ~y]4 K Xz wherein R2 r R3, R4, R5, m, y and X are as defined above;
t~) compounds having the general formula:
~R (OR )m] -N~
~R5~OR )y]2 R
R -N-wherein R2, R3, R4, R5, m and y are as defined above and the ~Ka is at least about 1/2 unit above the initial pH of : the wash liquor;
and mixtures thereof.
Preferred cationic surfactants are~
~i) compounds having the general formula:
~R (OR )m]~R (OR )y]~R Q X
~herein Q i5 N,- P- or ~::z is. 1 if Q is S
and 2 if Q is N or P; R is an alkyl or alkyl benzyl group having from about 8 to about 16 carbon atoms in the alkyl chain; each R3 is selected from the group consisting of -CH2CH2-, -CH2CH-(CH3~-, -CH2CH~CH2OH)-, -CH2CH2CH2, and mixtures thereof; each R is selected from the group consisting of H when y is not 0, C~ ~ alkyl, C1 4 hydroxyalkyl, benzyl groups, ring structures formed by joining the two R groups, and -CH2CHOH-C~O~CHOR6CHOHCH20H wherein R6 is H or any hexose; R5 is the same as R or is an alkyl chain wherein the total number o'~

of carbon atoms of R2 plus R5 is not more than about 18; each y is from 0 to about 3, m is from 0 to about 3 and X is any compatible anion, particularly one selected from the group consisting of halide, hydroxide, methylsulfate and acetate anions; and (ii3 alipha~ic amines having the general . formula:
[R21oR33 3~R4(oR3) 3R5N
wherein R2, R3, R4, R , m and y are as defined above and the pKa is at least about 1/2 unit above the initial p~ o~
the wash liquor, (iii) ~ompounds having the general foxmula~
[R (OR )m][R (OR )y]2N R3N R [(R3O)yR4]2X 2 wherein R2 R3 R4 R5 m y and X are - as de~ined above;
(iv) compounds having the general ~ormula-[R (OR )m][R (OR )y3NR NR [~R O)yR 3 wherein R2 R3 R4 R5 m and y are as defined above and the pKa is at least about 1/2 unit above the initial pH of the wash liquor;
and mixtures thexeof.
Because of their practicability, nitrogenou~ sur-factants, which are described in (i) when Q is N, (ii)~
(iii) and (iv) are the preferred cationic surfactants.
In this discussion ~i), (ii3, (iii), and (iv) refer to the compounds in the Summary of the Invention. Espec-ially preferred are the alkyl quaternary ammonium sur-~actants which are described in (i), and, in particular, the mono- long chain alkyl and alkoxy quaternary ammon-ium surfactants, which are descrihed in ~il when R is selected from the same groups as R . The most preferred I

cationic surfactants are the chloride, bromide and methylsulfate salts of C8 12 alkyltrimethyl . ~nium surfactants, C8 12 alkylhydroxyethyldimethyl ammonium ~urfactants~ C8_12 alkylmethyldihydroxyethyl ammonium surfactants, C10 14 alkoxytrimethyl ammonium surfac-tants, C10_14 alkoxydihydroxyethylmethyl A ~nium sur-factants and C10 14 alkoxyhydxoxyethyldime~hyl ~ -n;um æurfactants.
As an option, the salts of the cationic surfactants can be.prepared by precomplexing the cationic sur~actant directly with an anionic detergent surfactant within the invention rather than having such complex be formed in the wash liquor.
~nder cold water washing conditions, i.e., below about 45C, the preferred cationic surfactants are:
(i~ compounds having the general formula:
[R2(oR3) ~ ~R4(oR3) ] Q~X-wherein Q is N, P or S; z is 1 if Q is ~
and 2 if Q is N or P; each R2 is selected from the group consisting of an alkyl or alkyl ben~yl group cont~inin~
from about 4 to about 10 carbon atoms excluding the benzyl group; each R3 is selected from the group consisting of -C~2CH2-, -CX2CH(CH3)-, ~CH2CH(CH2OH)-, -CH2C~2CH2, and mixtures thereof; and wherein the sum of the carbon atoms of [R (OR )m]2 is from about 10 carbon atoms to about 16 carbon atoms when m is 0 and from about 10 carbon atoms to about 18 carbon atoms when m is from 1 to about 3, a b~nzene ring heing treated as equivalent to about 2 carbon atoms; each R is selected from the group consisting of H when y is not 0, Cl 3 alkyl, Cl 4 ~!
,~ .~

hydroxyalkyl, benzyl groups, ring struc-tures formed by joining the two R4 groups, and -C~2CHOHC~OHCHOR6CHO~CH20R6 wherein R6 is H or any hexose wherein at least one R6 is H; each y is from 0 to about 3, each m is ~rom 0 to about 3 wherein m is 1 wh~n R3 is -CH2C~2-; and X is any compatible anion, particularly one selected from the group consisting of halide, hydroxide~ ~ethylsulfate and acetate anions and mixtures thereof~
(ii) compounds having the general formula~
t~4(oR3)yin Q+X-(CH2)a H - C - ~(R3O)mR ]2 wherein Q, R3, R4, y, m and X zre as defined above; n is 2 i~ Q is S and 3 if Q is N or P; each RS is selected from the group consisting of an alkyl or alkyl benzyl group containing at least about 1 carbon atom excluding tha benzyl group and said R5 groups can be jolned ~o form 5 or 6 membered riny structure~, and wherein the sum of the caxbon atoms of t(R O)mR ]2 is from about 9 ¢arhon atoms to about 16 carbon atoms when m is O and from about 10 carbon atoms to about 18 carbon atoms when m is from 1 to about 3, a benzene ring being ~reated as equivalent to about ~ carbon atoms;
and a is from 0 to about 3;
~iii) aliphatic amines having the general formula:
tR ~OR )m]2[R (OR )y]N

~ ~f~

wherein R2, ~3, R4, m and y are as dQfined above and the pKa is at least about 1/2 unit above the initial pH of the wash liquor;
(iv) compounds having the general f~rmula:
[R (OR )m]2 -N -~ R ( oR3 ~ y ] 4 -N
wherein R2, R3, R4, m, y and X are as defined above; and ~v) compounds having the gene-al formula:
[R (OR )m]2 -N-lR (OR )y]~ _~
wherein R r R ~ .R , m and y are as defined above and the pKa is at least about 1~2 uni~ above the initial pH o~
the wash liquor;
and mixtures thereof.
Such cationic surfactants are preferred under cold water washing conditions because when they are utili2ed in combination with the alkyl sulfate detergent surfac-tant and the sulfonate detergent surfactant the Plectro-neutral complex formed does not crystallize or bPcome highly viscous~ It has been observed that the electro-neutral complex formed under cold water washing condi-~ tions with a cationic surfactant such as C12 trimethyl : . Amm~nium chloride results in such complex being crystal-line or highly viscous and, thereby, is render~d less

3~ ef~ective.
Once again, because o~ their practicability, nitrogenous surfactants, which are described in (i) and ~ii) when Q is N, (iii), iiv) and (v) are the preferred cationic surfac~ants for use under cold water washing conditions. Especially preferred are the alkyl quater-nary ammonium surfactan~s which are described in (i) and (ii). The mo5t preferred cationic surfactants are the chloride, bromide and methylsulfate salts of the alkyl quaternary ammonium surfactants which are described in (i) when each R is an alkyl group containing from 4 to about 10 carbon atoms wherein the sum of the carbon atoms of [R (oR3)m]2 is from about 10 carbon atoms and to abou~ 14 carbon atoms and preferably from about 10 to about 12 carbon atoms; each m and y are 1 or 0, prefer-ably 0; and each R is selected from the group consist-ing of mathyl and hydroxyethyl. Also, most preferredare the chloride, bromide and methyls~lfate salts of the alkyl quaternary a~monium sur~actants which are described in (ii) when each R5 is selected from the group consisting of an alkyl group containing at least one carbon atom and ring structures formed ~y joining each ~5 con~;ning five or six carbon atoms wherein the sum o~ the carbon atoms o~ [(R o~mR532 is from about 10 to about 16 carbon atoms and preferably from about 10 to about 14 carbon atoms; each m and y are 1 or 0, prefer-ably 0; and each R is selected from the group consist-ing of methyl and hydroxyethyl.
It is essential that cationic surfactants derived from aliphatic amines have a pKa at least about 1/2 unit above the initial pH of the wash liquor. Other~ise, ~he ~5 desired superior performanca is not achieved. It is believed that such a pKa and pH limita~io~ ensures that a substantial portion of such amines are protonated and, thus, exist in cationic form and, there~ore, are able to complex with the alkyl sulfate detergent surfactant and sulfonate detergen~ surfactant.
The level of cationic surfactant within the inven-tion is related to the level of sulfonate deter~ent surfactant. The molar ratio of cationic surfactant:
sulfonate detergent surfactant is at most about 1.5 and preferably less than about 1. It is desirable to have some molar excess sulfonate detergent surfactant present ,~ ~

because it is effective at stripping fabric softenexs that have been deposited on the textile surface in previous wash cycles. The sum of the equimolar lavels of cationic surfactant and sulfonate detergent surfac-tant is preferably at least about 2%, more preferablyabove about 5% and most preferably above about 10% of the total level of anionic detergent surfactant present.
Such ex~e~s of anionic detergent surfactant is preferred to ensure proteinaceous and particulate soil removal and the suspension in the wash liquor o~ the 50il removed from the textiles.
The level of cationic surfactant within the inven-tion is from about 1/4% to about 12%, preferabl~ from about 1/2% to about 3~ and most preferably from about 1/2% to about 6%.
T~E ALKYL SUL~ATE DErF~r7~NT SURF~CTA~T
The alkyl sulfate detergent surfactant is an essen-tial component of the detergent compositions within the invention. Detergent compositions without the alkyl sulfate detergent surfactant do not provide the desired superior performance. Such compositions provide poor particulate soil removal and increased soil redeposi-tion. It i5 believed that the alkyl sulfate detergent surfactant, in addition to forming the electro-neutral complex with the cationic surfactant, is particularly efficacious for such purposes. Furthermore, only speci-fic alkyl sulfate detergent surfactants provide the desired superior performance. Performance i9 quite poor with an alkyl sulfate detergent surfactant in which the ~0 alkyl chain contains more than abou~ 15 carbon ato~ in a linear portion of the chain extending fxom the head group and/or more than about four ethoxy groups.
The alkyl sulfate detergent surfactants o~ the present inven~ion are of the general for~ula:
3S R(C2H4)xS3M

Q~

wherein R is an alkyl chain having from about 8 to about 18 carbon atoms, saturated or unsaturated, wherein the longest linear portion of the alkyl chain extending from the head group is 15 carbon atoms or less on the aver-age, M is a ca~ion which makes the compound water-soluble, especially an alkali metal, ammonium or substi-tuted ammonium cation and x is from 0 to about 4. The preferred substituted ammonium cations are the mono- and diethanol ammonium cations.
Preferably, the alkyl sulfate detergent surfactants are not ethoxylated. The preferred alkyl sulfate deter-gent surfactants are the sodium and potassium salts of C12 15 primary and C12_1~ secondary alkyl sulfates. The most preferred alkyl sulfate detergent surfactants are the sodium and potassium salts of C12_15 methyl branched alkyl sulfates.
Under cold water wash conditions, i.e., below about 45C, the preferred alkyl sulfate detergent sur~actants are the secondary-and shorter alkyl chain alkyl sulfate detergent surfactants within the invention.
The level of alkyl sulfate detergent surfactant within the present invention is from about 2% to about 50%, preferably from about 3% to about 30~ and most preferably from about 5~ to about ~0%.
THE SULFONATE DETERGENT SURFACTANT
A sulfonate detergent surfactant is an essential component of the compositions within the invention.
Compositions without the sulfonate detergent surfactants within the invention do not give the desired superior performance.
A very wide range of sulfonate detergent sur~ac-tants can be used in the compositions of the invention, However, it is believed that the alkyl chain portion o~
such surfactants should be saturated. For example, -olefin sulfonates, which have an unsaturated carbon bond, do not provide the desired superior performance.

~ .....
,~

L~ 9~1C.) - 18 ~
Suitable sulfonate detergent surfactants are Cg 15 alkyl benzene sulfonates, C8 24 parafSin sulfonates, C8 18 alkyl glyceryl ether sulfonates, esters of ~ -sulfonated fatty acids con~; n; ng from about 6 to abou-t 20 carbon atoms in the fatty acid group and from about 1 to about 10 carbon atoms in the ester group and Cl 6 alkyl or aryl sulfonates containing an ether, ester or amide linkage to a C7 15 alkyl chain.
The preferred sulfonate detergent surfactants are the secondary alkyl benzene sulfon~tes having from about 9 to about 15, preferably from about 11 to about 13 carbon atoms in the alkyl chain.
Suitable paraffin sulfonates contain from about 8 to about 24 caxbon atoms and preferably from about 12 to about 18 carbon atoms. The alkyl glyceryl ether sulfon-ates are those ethers of C8 18 alcohols, e.g., those derived from tallow and coconut oil. Suitable esters of ~-sulfonated fatty acids contain from about 6 to about ~0 carbon atoms in the fatty acid group and from about 1 to about 10 carbon atoms in the ester group.
Suitable alkyl sulfonates with an ether, ester or amide linkage have the general formula:
R7 - A - R8 _ SO3 wherein R is an alkyl chain having about 7 to about lS
carbon atoms, R is an alkyl chain having from about 1 to about 6 carbon atoms ~r a benzyl group and A is selected from the group consisting of:
O O H
-C-O-, -C-N- and -O-~nder cold wash water conditions, i.e., below abou~
45C, the shorter alkyl chain sulfonate detergent sur-factants are preferred.
The level of sulfonate detergent surfactant within the invention is such that the molar ratio o~ cationic 3S surfactant:sulfonate detergent surfactant is less than about 1.5 and preferably less than about 1. The sum of ~:

the equimolar levels of cationic surfactant and sulfon-ate detergent surfactant is preferably at least above 2~, more preferably above about 5~ and most preferably above about 10% of the total anionic suxfactant pre~ent.
5 The level of sulfonate detergent surfactant of the detergent compositions within the present invention is from about .5% to about 50%, preferably from about 2g to about 30~ and most preferably from about 3% to about 20~.
THE DETERGENCY BUILDER
In a highly preferxed embodiment the detergent compositions within the invention contain a detergency ~uilder. The level of detergency builder in the deter-gent compositions is from about 0~ to about 70%, prefer-ably from about 10% to about 60% and~most prefera~lyfrom about 2~% to about so%~ by weight of the composition of the detergency builder.
The preferred detergency builders are the water-soluble sequestrants such as tripolyphosphates, hexa-metaphosphates and higher polymerization species, citrates, nitrilotriacetates and water-soluble poly-acetals as disclosed in U~S. Patents 4,144,266 and

4,246,495, and mixtures thereof. The most preferred detergency builders are tripolyphosphates, nitrilotriacetates and water-soluble polyacetals and mixtures thereof.
Water-soluble inorganic or organic electrolytes are suitable builders. The electrolytes have an equivalent weight of less than 210, especially less than 100 and include the common alkaline polyvalent calcium ion sequestering agents. The builder can also be water-insol~bl~ calcium ion exchange materials, however, nonlimiting e~amples of suitable water-soluble, inor-ganic detergent builders include: alkali metal carbon-ates, borates, phosphates, bicarbonates, silicates, sulfates and chl~rides. Specific examples of such salts include sodium and potassium tetraborates, perborates, , ~, ,! ~

bicarbonates, carbonates, percarbon~tes, orthophos-phates, pyrophosphates and sulfates.
Examples of suitable organic alkaline detergency builders include: (1) water-soluble aminocarboxylates S and aminopolyacetates, for example, sodium and potassium glycinates, ethylenediaminetetraacetates and N-(2-hy-droxyethyl)nitrilodiacetates and diethylenetriamine-pentaacetates; (23 water soluble salts of phytic acid, f~r example, sodium and potassium phytate~; (3) water-soluble polyphosphonates, including sodium, potassium,and lithium salts of ethane-1-hydroxy-l, 1-diphosphonic acid; sodium, potassium, and lithium salts of ethylene diphosphonic acid; and the like; (43 water-soluble polycarboxylates such as the salts of lactic acid, succinic acid, malonic acid, maleic acid, citric acid, car~oxymethyloxysuccinic acid, 2-oxa-1,1,3-pr~pane tricarboxylic acid, 1,1,2,2-ethane tetracarboxylic acid, cyclopentane~cis, cis, cis - tetracarboxylic acid, mellitic acid and y~L~ ~llitic acid; (5) water-soluble organic amines and amine salts such as monoethanolamine, diethanolamine and triethanolamine and salts thereof;
(6~ water soluble polyacetals as disclosed in U.S.
Patents 4,144,266 and 4,246,495;
and (7) water soluble salts of fatty acids;
for example, C12_18 fa~ty acids-Another type o detergency builder material usefulin the present compositions comprises a water-soluble material capable of forming a water-i~soluble reaction product with water hardness cations preferably in combination with a crystallization seed which is capable of providing growth sites for said reaction product~
Such "seeded builder" compositions are fully disclosed in British Patent Specification No. 1,424,406.
A furthe.r class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those described in .
, 3.~

Belgian Patent 814,874, issued November 12, 1974.
This patent discloses and claims detergent compositions cont~in;ng ~odium alumino-silicates havin~ the formula:
S Naz(Alo2)z(sio2)yxH2o wherein z and y are integers equal to at least 6, the molar ratio of z to y is in the range of rom 1.0:1 to a~out 0.5:1, and X is an integer from about 15 to about 264, said aluminosilicates having a calcium ion ~xch~ng~
capacity of at least 200 milligrams eq~ivalent/gram and a calcium ion exchange rate of at least about 2 grains/
gallon/minute/gram. A preferred material is:
Nal2 (sio2Al2~ 1227H2 ' THE NONIONIC SU~FAC~ANT
As an op~ion, the compocitions o~ the inventi~n can contain a nonionic surfactant. Such surfactants ~or use herein comprise those typical nonionic surfac~ants well known in the detergency arts. The preferred nonionic surfactants are fatty acid amide surfactants 7 amine oxide surfactants and ethoxylated alcohols.
Suitable fatty acid amide surfactants are A ~n i a ~ amides, monoethanol amides, diethanol amides and ethoxy-lated amides. The preferred amides have the formula O H
U lY
R - C - N - ~tcH2cH2o)zcH2cH2oH]xt wherein. R is a C8 20 alkyl group, x + y = 2 and z is from 0 to about 5. Particularly preferred amides are those where the alkyl group contains from about 10 to about 16 carbon atoms, such as coconut alkyl monoethanol or diethanol amide. Such compounds are comm~rcially available under the trade marks"Super-Amide" L-9 and GR, from Onyx C~emical Company, Jersey City, NJ;"Super-Amide F~3" from Ryco, Inc., Conshohocken, PA and "Gafamide CDD-518, available from GAF Corp., New York, NY.

, ., The amine oxide surfactants of the present inven-tion co~prise compounds and mixtures of compounds ha~ing the formula R
R (OC2H4) n ~ t O

wherein Rl is an alkyl, hydroxyalkyl, alkoxyhydroxy-propyl radical, alkoxyhydroxyethyl, alkyl amido or alkyl carboxylate in which the alkyl and alkoxy~ respectively, contain from about 8 to about 18 carbon atoms, R and R
are methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, ~-hydroxypropyl, 3 hydroxypropyl, or together are a heterocyclic, e.gO, morpholino structure in which the nitrogan is part of the heterocyclic ring and n is from 0 to about 10.
Specific examples of amine oxide surfactants include: dimethyldodecylamine oxide, dimethyltetra-decylamine oxide, ethylmethyltetradecylamine oxide, cetyldimethyla~ine oxide, dimethylstearylamine oxide, :20 cetylethylpropylamine oxide, diethyldodecylamine oxide, diethyltetradecylamine oxide, dipropyldodecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, his(2-: hydroxyethyl)-3-dqdecoxy-2-hydroxypropylamine oxide, I~-hydroxypropyl)methyltetradecylamine oxide, dimethyl oleylamine o~ide, dimethyl-(2-hydroxydodecyl)ami~e oxide, C8 20 alkyl(alpha-dimethylamine oxide) carboxy-late, and the corresponding decyl, hexadecyl and octa-decyl homologs of the above compounds. A particularly preferred material is dimethYl C12_16 alkyl amine oxi e The ethoxylated alcohols for us~ herein have the formula RlOC2H4O)XO R
wherein R is an alkyl, hydroxy alkyl, alkylene, hydroxy alkylene acyl, or hydroxy acyl group containing from about 8 to about 22 carbon atoms or an alkylbenzene group wherein the alkyl group contains from about 6 to ~o~

about 15 carbon atoms or mixtures thereof; X is a number from about 2 to about 30; and R1 is selected from the group consisting of H, alkyl groups containing from 2 to about 4 carbon atoms, acyl groups con~;n;ng from 2 to about 4 carbon atoms and mixtures thereof. The HLB Of these nonionic surfactants is preferably fro~ about 5 to about ~0, most preferably from about 8 to about 14.
Other suitable nonionic surfactants are: (1) the condensation products of ethylene oxide with a hydro-phobic base formed by the con~nsation of propyleneoxide and propylene glycol, and (2) the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethy~enedia-mine. These surfactants are marketed by BASF Wyandotte under the trade marks"Pluronic"andnTetronic"re~pectively The level of nonionic surfactant that can be pres-ent is from about 0~ to about.50%, preferably from about .5~ to about 10% and mo~t pre~erably from about 1% to about 5~.
MISCELLANEOUS I~GREDIENTS
In addition to the ~bove named ingredients, the compositions of this invention can contain all of the usual components of detergent compositions including the ingredients set forth in U.S. Patent 3,936,537, Baskerville et al.
Such components include color speckles, ble~ching agents, bleach activators, suds boosters, suds suppres-sors, antitarnish and/or anticorrosi,on agents, soil-suspending agen~s, soil-release agents~ dyes, fillers, optical brighteners, germicides, p~ adjusting ag~nts, ~ ~ k~ 1 i n; ty sources, hydro~ropes, antioxidants, enzymes, enzyme stabilizing agents, perfumes, etc.
In addition to being able to function as a deter-gency builder, water soluble salts of fatty acids can be added as part of the surfactant system. Surprisingly, i\

~.20'~

they are most effective under cold water wash condi-tions. Suitable water soluble salts of fatty acids have from about 8 to about 18 carbon atoms. The preferred water soluble salts of fatty acids are the sodium, potassium and magnesium salts of C12_14 fatty acids-They can be present at levels up to about 10~.
Enzymes are believed to be particularly effective in the detergent compositions of this invention. The enzyme-cont~i n; ng detergent composition~ are particu-larly effective on enzyme sensitive st~ins ~uch as ~rassand blood while maint~in;~g greasy and oily soil deter-gency. Suitable enzymes are those, for example, dis-clo-~ed in U.S. Patent 4,176,079, Guerry et al (Move~ber 27, 1979), The enzymes are included at a level of from about .02% to about 3~, preferably from about .1% to about 1%.
Nonlimiting examples of bleaching agents are sodium per~orate (as the monohydrate or tetrahydxate), sodium percarbonate and other perhydrates, at levels from about

5% to 35% by weight of the composition, and activators therefor, such as tetraacetylethylenediamine, tetra-acetylglycouril and others known in the art~ and stabil-izers therefor, such as magnesium silicate, and ethyl-enediaminetetraacetate. Peroxy carboxylic acids, for example, such as those disclosed in U.S. Patent 4,091,544, Hutchins (May 30, 1975), are especially useful.
Preferred optional ingredients include suds m~di-fiers particularly those of suds suppxéssing types, exemplified by silicones, and silica-silicone mixtures.
U.S. Patents 3~933,672, issued January 20, 1976 to ~artolotta et al, and 4,136,045, issued January 23, 1979 to Gault et al, dis-olose silicone suds controlling agents. The silicone35 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 form-ula: . _ R
-SiO-~.1 wherein x is from about 20 to about 2/000 and R and are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl. The polydimethylsiloxanes IR
a~d R are methyl) having a molecular weight wi~hin the ra~ge of from about 200 to about 2,000,000, and higher, are all useful as suds controlling agen~s. ~dditional suitable silicone materials wherein the side chain groups R and Rl are alkyl, aryl, or mixed alkyl or aryl hydrocarbyl groups exhibit u~e~ul suds controlling properties. Examples of the like ingredients include diethyl-, dipropyl-, dibutyl-, methyl-, ethyl-, phenyl-methylpoly-siloxanes and the like. Additional useful silicone suds controlling agents can be represented by a ~0 mixture of an alkylated siloxane, as referred to herein~
before, and solid silica. Such mixtures are prepared by afixing the silicone to the surface of the solid silica. A preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethylsilanated) silica having a par-ticle size in the range from about 10 millimicrons to 20 millimicrons and a specific surface area above about 50 m /gm. intl~ately 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 ~ilanated silica of from about 19 1 to about 1:2. The silicone suds suppressing agent is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent-impermeable carrier.
Particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in U.S.

t - ~

~o'~

Patent 4,073,118, Gault et al, issued February 21, 1978, An example of suc~ a compound is D~-544*, commercially available from ~ow Corning, which is a siloxane/glycol copolymer.
Suds modifiers as described above are used at levels of up to approximately 2%, preferably ~rom about 0.1 to about 1>~ by w~ig~t of the surfactant.
Microcrystalline waxes having a melting point in the range from 35C-115C and a saponification value of less than 100 represent additional axamples of preferred ~uds control components for use in the subject composi-tions, and are described in detail in U.S. Patent 4,056,481, Tate, issued Novembar 1, 1977.
The microcrystalline waxes are substantially water-in~o~uble, but are water-disper ible in ~he presence of organic surfactants. Preferred microcrystalline waxes have a melting point from about 65C to 10~C, a molecular weig~t in the range from 400-1~000; and a penetration value of at least 6, meas-ured at 77F by ASTM-D1321. Suitable examples of the above waxes include: microcryst~ll; ne and oxidized microcrystalline petroleum waxes; Fischer-~ropsch and oxidized Fischer-Tropsch waxes; ozokeritP; ceresin;
montan wax; beeswax; candelilla; and carnauba wax.
~5 Alkyl phosphate esters represent an additional preferred suds control agent for use herein. These preferred phosphate esters are predo~;n~ntly monostearyl phosphate which, in addition thereto, can contain di-and tristearyl phosphates and monooleyl phosphate, which can contain di- and trioleyl phosphate.
The alkyl phosphate ester~ frequently contain 90~e trialkyl 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.

*Trade Mark .. . . . .. . .. ... . . . . ... . .. .. ....

,~ ' 4~

Small amounts of zwitterionic and/or ~mpholytic surfactants can be present, but because of the outstand-ing performance characteristics of the composi~ions within the present invention, surfactants additional to 5 the essential components will not generally be neces-sary.
. The following examples are given to illustrate the parameters of and compositions within the invention.
All of the compositions are stated in percent by weight.
EXAMPLE I
Wash water solutions were prepared that represented the following compositions:
A B C
C8 alkyltrimethy1ammonium chloride 0 0 3.0 C12 alkyltrimethylammonium chloride 3.3 0 0 Sodium C13 linear alkylbenzene sulfonate ~Cl3 LAS) 4 9 5.l 4.
Sodium C14 15 methyl branched alkyl sulfate (C45AS) l~.6 13.5 12.6 Cg_ll alkvl polyethoxylate2 ST*
( 9l AE2.5T) 3.3 3.4 3 3 Sodium carbonate 24.6 25.4 24.7 Sodium tripolyphosphate 28.l 29.l 28.2 Sodium nitrilotriacetate 8.6 8.9 8.6 Sodium sulfate 12.3 l?.7 12.3 Sodium siLicate t1.6 r) 2.0 2.0 2.0 Op~ical brightener .29 .30 .29 *Stripped of lower ethoxylated fractions and fatty alcohol.
Three sets of four 3"x3" swatches consisting of standard textiles stained with standard soils were prepared.
A laundry load consisting of one set of the swatches along with six clean terrv cloth towels and one terry cloth towel soiled with a mixture of particulate soil and oily soil was placed in a mini-wash system.
The load was then washed with a quantity of Composition A that corresponds to detergent concentrations utilized in conventional automatic wash processes. The mini-wash system with such a load simulates a conventional auto-matic washing process. The wash water had a temperature of 95~F and contained 5 grains/gallon water hardness.
This wash process was repeated two moxe times, once with the second set of swatches and Composition B and once with the third set o~ swatches and Composition C.
- Each of the four swatch types was then comparison graded against its identical counterpart that had been washed with a different detergent composition to deter-mine relative soil removal. A grading scale of -4 to 4 was used, with -4 indicating much less 50il removal, 0 indicating no dif~erence and 4 indicating much more soil removal.
The entire above procedure, consisting of preparing three sets of four swatches and three wash cycles, was repeated four more times. Therefore, each swatch type of each detergent composition was graded a total of four times. Such four grades were then averaged. Finally, the avarage of such averages for each deteryent composi-tion was calculated. This average is known as the Cleaning Index.
The results were as follows:
A B C
Cleaning Index 0 .56 +.38 Least Significant Difference (.05) .4l .41 .41 COmpOSitiQnS A and C provided significantly more soil removal than Composition B, which did not contain the essential cationic surfactant.
EXAMPLE II
Wash water solutions were prepared that represented the following compositions:

~2~.

~o~

A B C D E
Sodium C16 alk~l-4-sulfate O O O 0 5.1 0 Sodium ~-olefin sulfonate O O 0 5.5 0 0 a-sulfonated coconut fatty acid hexyl ester O 0 6.4 0 0 O
Sodium C16 alkyl paraffin sulfonate 0 5.4 0 0 0 0 C13 ~AS 5.4 0 O O ~ 5.4 C"5 AS 11.7 1107 11.611.7 11.711.7 C12 alkyltrimethyl ammonium chloride 3.1 3.1 3.0 3.1 3.1 3~1 Cgl AE2.5T 3.1 3.1 3.0 3.1 3.1 3.1 Sodium carbonate22.4 22.5 22.322.4 23.022.4 Sodium tripoly-phosphate 36.3 36.4 36.136.3 36.636.3 Sodium nitrilo-triacetate 5.7 5.7 5.6 5.7 5.7 5.7 Sodium sulfate 9.9 9.9 9.8 9.9 9.9 9.9 Soaium silicate tl.6r~ 1~.8 1.8 1.8 1.8 1.8 1.8 Optical ~rightenex .27 .27 .27 o27 .27 .27 Soil removal capabilities of Compositions A-D were then compared by determining the Cleaning Index by the same procedure as described in Example I. Such compari-son was also maae with Compositions E and F. The results were as follows:
A B C D E F
Cleaning Index O .3 -.4 -.9 -.48 0 Least Significant Difference (.05) .46 .46 .46 .46 .31 ,31 v ~J'~

~.2~

Compositions A, B and C provided significantly more soil removal than Composition D which did not contain a sulfonate detergent surfactant within the invention.
Composition F provided significantly more soll removal than Composition E. Thus, it appears that sodium C16 alkyl-4-sulfate cannot "substitute" for a sulfonate detergent surfactant within the invention.
EXAMPLE III
Wash water solutions were prepared that represented the following compositions:
A B C
C13 LAS 5.3 10.6 17.6 C45 AS 12.3 7 0 C12 alkyltrimethylammonium chloride 3.1 ~ 1 3.1 Cgl AE2 5T 3.1 3.1 3.1 Sodium carbohate 22.4 22.4 22.4 Sodium tripolyphosphate 36.3 36.3 36.3 Sodium nitrilotriacetate 5.7 5.7 5.7 Sodium sulfate 9.9 9.9 9.9 Sodium silicate (1.6 r) 1.8 1.8 1.8 Optical brightener .27 .27 .27 Six 3"x3" clean swatches of various textile tvpes were made. The six swatches and six clean terry cloth towels were placed in a mini-wash system. The load was then washed in wash water containing lipid soil and organic and inorganic particulate soil with a quantity of Composition A that corresponds to detergent concen~
trations utilized in conventional automatic wash pro-cesses. The textiles were then dried. The sameswatches and terry cloth towels we~e washed in such process five more cycles.
After the sixth cycle the six swatches were meas-ured to obtain the difference in Hunter Whiteness Units Filtered (~HWUF). This measurement corresponds to the amount of soil deposited onto the swatches, with the ; ~-4~

lower number signifying greater soil redeposition. The average ~HWUF grades for the six swatches, ~-HWUF avg., was calculated.
The entire ahove procedure was repeated two more times, once with Compositions B and once with Composi-tion C. The results were as follows:
A B C
~-HWUF avg-. -10.5 -14.0 -26.5 Least Significant Difference (.05) 2.5 2.5 2.5 There was significantly less soil redeposition on the swatches with Compositions A and B than with Compo-sition C. This result indicates that the alkyl sulfate detergent surfactant, which was not present in Composi-tion C, is es~ential to prevent soil redeposition.
Also, Composition B. had somewhat more soil redeposition than Composition A. This is due to the decreased level of alkyl sulfate detergent surfactant of Composition B.
EXAMPLE IV
Wash water solutions were prepared that represented the following compositions:
A B C
Sodium ~-olefin sulfonate 0 0 12.1 Sodium C16 alkyl paraffin sulfonate 0 12~1 0 C13 LAS 5.1 5.6 5.6 C~5 AS 12.1 0 0 ~12 alkyltrimethylammonium chloride 3.1 3.1 3.1 Cgl AE2.5T 3.1 3.1 3.1 Sodium carbonate 22.5 22.5 22 . 5 Sodium tripolyphosphate 36.5 3 6 . 5 3 6 . 5 Sodium nitrilotriacetate 5.7 5.7 5.7 Sodium sulfate 9.9 9.9 9.9 Sodium silicate (1. 6 r) 1. 8 1. 8 1. 8 Optical brightener ~27 . 27 . 27 Soil removal capabilities of each of the composi-tions were then compared by determining the Cleaning Index by the same procedure as described in Example I.
The results were as follows:
A B C
Cleaning Index 0 -1.06 -~56 Least Significant Difference (.05) .31.31 .31 Composition A provided significantly more soi.
removal than Compositions B and C. It i5 believea tha~
this is because Compositions ~ and C did not conta,n an alk~l -sulfate detergent surfactant. ~herefore, the alkyl sul ate detergent surfactant i5 also essential for soil removalO
~X~MPLE V
Wash water solutions were prepared ~hat represenLed the following compositions.
13, C i:
Sod~um t~
: 20 alkyl sulrate 0 11.8 0 0 C4~ linear primary AS 0 0 0 12~8 C13 LAS 5.0 5.0 5.5 5.5 C45 AS 11. 8 0 12e8 0 C12 alkyltrimethylammonium chloride 3.1 3.1 3.3 3.3 CglAE2 5T 3.1 3O1 3.3 3.3 Sodium carbonate 22.5 22.6 24.9 24.9 Sodium tripolyphosphate 36~ 7 36~ 7 28 ~ 4 28 ~ 4 Sodium nitrilotriacetate 5.7 5.7 8 ~ 8 8 ~ 8 30 Sodium sulfate 10.0 10.0 13.8 10~8 Sodium silicate ~1.6 r~ 1~8 1~8 2~0 2nO
Optical brightener .27 .27 ~27 ~27 Soil removal capability of Composition A was com~
pared to that of ~ompos.ition B by determining the Clean~
irlg Index by the same procedure as descri~ed in Example g~

I. Such comparison was also made between Compositions C
and D. The results were as follows:
A B C D
Cleaning Index 0 -.96 0 -1.2 Least Significant Vifference (.05) .55 ,55 .7 .7 Composition A provided significantly more soil removal than Composition B and Composition C provided significantly more soil removal than Composi~ion D.
This result is due to that the length of the longest portion of the alkyl sulfate detergent surfactant of Compositions B and D is too long.
EXAMPLE VI
Wash water solutions were prepared that represented 15 the following compositions:
A B C
C13 LAS O 2.4 5.0 C45 AS 16~7 14.3 11.7 C12 alkyltrimethylammonium chloride 3.0 3.0 3.0 91 AE2.ST 3.0 3.0 3~0 Sodium carbonate 22.9 22.9 22.9 Sodium tripolyphosphate 36.6 36.6 36.6 Sodium nitrilotriacetate 5.7 5.7 5.7 Sodium sulfate 9.9 9.9 9.9 Sodium silicate (1.6 r) 1~8 1.8 1.8 Optical brightener .23 .23 .23 Soil removal capabilities of each of the composi-tions were then compared by determining the Cleaning30 Index by the same procedure ~s described in Example I.
The results were as follows:
A B C
Cleaning Index -.76 ~r 61 0 Least Significant ~ifference (.05) .35 ,35 .35 Molar ratio o~ C12 alkyltrimethyl-ammonium chloride:C13 LAS 0 1.7 .83 - 34 ~
Composition C provided significantly more soil removal than Compositions A and B. It is believed that this is because Compositio.n A and B did not conta.in a suffic-ent level of Cl3 LAS in order to form a suffi-s cient level of cationic surfactant-alkyl sul~onate detergent surfactant complex.
EXAMPLE VII
Wash water solutions were prepared that represented the following compositions:
A B
Cl3 LAS 7.3 7.5 C45 AElS ~-4 5.6 S.5 5.7 C12 alkyltri~ethylammonium chloride 3.~ 3,4 9l 2.5T
Sodium carbonate 24.9 25.7 Sodium tripolyphosphate 28.4 29.4 Sodium nitrilotriacetate 8.7 9.l Sodium sulfate l0.8 ll.2 Sodium silicate 2.0 2.0 Optical brightener .3 .3 Soil removal capabilities of each of the composi-tions were then compared by determining the Cleaning Index by the same procedure as descri~èd in Example I~
The results were as follows:
A B
Cleaning Index 0 -.5 Least Significant Difference ~.05) .50 .S0 Composition A, which contains an optional nonionic surfactant, provided only marginally significantly mor~
soil removal than Composition B.
EXAMPLE VIII
Wash water solutions were prepared that represented the following compositions:

B
C13 LAS 5.4 5.5 10.1 10.2 C12 alkyltrimethylammonium chloride 2.6 0 C12 primary amine (pKa 10.8) 0 1.8 CglAE2 5T 3.1 3.1 Sodium carbonate 23.4 23.5 Sodium tripolyphosphate37.4 37.6 Sodium nitrilotriacetate5.8 5.9 Sodium sulfate 10.1 10.2 Sodium silicate (1.6r) 1.9 1.9 Opticàl brightener .2 .2 Soil removal capabilities of ~ach of the CoMposi-tions were then compared by determining the Cleaning Index by the same procedure as described in Examp~e I.
The initial pH of the wash liquor was 10.1. The results were as follows:
A B
Cleaning Index 0 -.40 Least Significant Difference (.05) .~7 .~7 Composition B, which contains an amine suxfactant, did not remove significantly less soil ~han Composition A, which contains an alkylammonium surfactant.
When dihexyldimethylammonium chloride is s~sti-tuted for the C12 alkyltrimethylammonium chloride, the cool water, e.g., 20C, performance is improved.
EXAMPLE IX
The following is a compcsition within the inventio~
that contains a water soluble salt of a fatty acid:
Sodium laurate 5.7 C,H3 loH21 (cH2)3N[(cH2)2oH]2 2.7 C45 AS 7.2 C13 LAS 3.9 Sodium sulfate 29.0 ~' ~o~g~

. - 36 -Sodium carbonate l6.1 Sodium tripolyphosphate 32.2 Sodium silicate t1.6r) 3.0 Optical brightener .2 EXA~L~LE X
The ~ollowing is a granular detergent composition within the invention that has a density of about .73 grams/cubic centimeter:
Cl2 alkyl trimethyl.- - n i um chloride 3.0 C13 LAS 4.9 C45 ~ ll.3 ~45 AE7 1.6 Sodium carbonate 22.3 Sodium tripolyphosphate 27.5 Sodium nitrilotriacetate 7.8 Sodium sulfa~e 12.9 Sodium ~ilicate (l.6 r) 1.8 Optical brightener .22 Water 6.7 EXAMPLE XI
The following is an enzyme-containing detergent composition within the invention:
En7ymes '~Alcalase~" .8 C13 LAS 5.2 C45 AS 13.5 C12 alkyltrimethylammonium chloride 3.5 9l 2.5T 1.7 Sodium carbonate 13.1 So~ium tripolyphosphate 42.0 Sodium nitrilotriacetate ~.6 Sodium sulfate ll.4 Sodium silicate (l.6 r3 2.l Optical brightener .26 *Trade Mark . ~
. . .~ .

~ ~04gl3~

Th1s composition provides the desired superior performance on conventional soils in addition to being extremely effective on enzyme-sensitive stains.
EXAMPLE XII
The following is a composition within the invention that contains a water soluble salt of a fatty acid:
Sodium laurate 5.7 C12 alkyltrimethylammonium chloride 2.7 C23AE6.5 1.5 C45 7.2 C13 LAS 3.9 Sodium sulfate . 27.5 Sodium carbonate 16.1 Sodium tripolyphosphate 32.2 15 Sodium silicate (1.6r) 3.0 Optical brightener .2 EXAMPLE XIII
A B
C13LAS 7.5 7.5 C45AS 7.5 7.5 C12 alkyltrimethylammonium chloride 2 2 ~la2 CO3 20 15 Sodium nitrilotriacetate 0 15 Sodium hydrated Zeolite A (1-3~) 25 20 Na~SO4 25 20 Sodium silicate (1.6 r) 2.5 2.5 Minors, water, etc. Balance Balance .,,

Claims (50)

- 38 -

1. A detergent composition comprising, by weight:
(a) from about 2% to about 50% of a water-soluble alkyl sulfate detergent surfactant having the formula:
RO(C2H4O)xSO3M+
wherein R is an alkyl chain having from about 8 to about 18 carbon atoms saturated or unsat-urated, wherein the longest linear alkyl portion of the chain extending from the head group is no more than about 15 carbon atoms on the average; M is any compatible cation and x is from 0 to about 4, (b) from about 1/4% to about 12% of a cationic surfactant selected from the group consisting of:
(i) compounds having the general formula:
[R2(OR3)m][R4(OR3)y]zR5Q+X-wherein Q is N, P or S; z is 1 if Q is S
and 2 if Q is N or P; R is selected from the group consisting of alkyl and alkyl benzyl groups having from about 6 to about 16 carbon atoms excluding the benzyl group; each R3 is selected from the group consisting of -CH2CH2-, -CH2-CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2?, and mixtures thereof; each R4 is selected from the group consisting of H
when y is not 0, C1-4 alkyl, C1-4 hydroxyalkyl, benzyl groups, ring struc-tures formed by joining the two R
groups, and -CH2CHOHCHOHCHOR6CHOHCH2OR6 wherein each R6 is H or any hexose wherein at least one R6 is H; R5 is selected from the group ' consisting of [R2(OR3)m], [R4(OR3)y] and ring struc-tures formed by joining any of the carbon atoms of R2 and R5 wherein the total number of carbon atoms of R2 plus R5 is not more than about 18, a benzene ring being treated as equivalent to about 2 carbon atoms, and wherein if R4 is less than about 4 carbon atoms then R2 contains from about 8 to about 16 carbon atoms excluding the benzyl group;
each y is from O to about 3, m is from O
to about 3, and X is any compatible anion; and (ii) compounds having the general formula:

wherein Q, R3, R4, y, m and X are as defined above; n is 2 if Q is S and 3 if Q is N or P; each R7 is selected from the group consisting of an alkyl or alkyl benzyl group containing at least about 1 carbon atom excluding the benzyl group and said R7 groups can be joined to form 5 or 6 membered ring structures, and wherein the sum of the carbon atoms of [(R3O)mR7]2 is from about 9 carbon atoms to about 16 carbon atoms when m is 0 and from about 10 carbon atoms to about 18 carbon atoms when m is from 1 to about 3, a benzene ring being treated as equivalent to about 2 carbon atoms;
and a is from O to about 3;
(iii) aliphatic amines having the general formula:
[R (OR3)m)(R4(OR3)y]R5N
wherein R2, R3, R4, R5, m and y are as defined above and the pKa is at least about 1/2 unit above the initial pH of the wash liquor:
(iv) compounds having the general formula:
wherein R2, R3, R4, R5, m, y and X are as defined above;
(v) compounds having the general formula:
wherein R2, R3, R4, R5, m and y are as defined above and the pKa is at least about 1/2 unit above the initial pH of the wash liquor;
and mixtures thereof;
(c) from about 1/2% to about 50% of a sulfonate detergent surfactant selected from the group consisting of the water soluble salts of C9-15 alkyl benzene sulfonates, C8-24 paraffin sulfonates, C8-24 alkyl glyceryl ether sulfon-ates and esters of .alpha.-sulfonated fatty acids containing from about 6 to about 20 carbon atoms in the fatty acid group and from about 1 to about 10 carbon atoms in the ester group, and C1-6 alkyl or aryl sulfonates containing an ether, ester or amide linkage to a C7-15 alkyl chain;
(d) from 0% to about 50% of a nonionic detergent surfactant; and (e) from about 0% to about 70% of a detergency builder;
wherein the molar ratio of (b):(c) is less than about 1.5.

2. The detergent composition of Claim 1 wherein the cationic surfactant (b) is selected from the group consisting of:
(i) compounds having the general formula:
[R (OR3)m][R4(OR3)y]zR5Q+X-wherein Q is N, P or S; z is 1 if Q is S
and 2 if Q is N or P; R is an alkyl or alkyl benzyl group having from about 8 to about 16 carbon atoms in the alkyl chain; each R3 is selected from he group consisting of -CH2CH2-, -CH2CH-(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2?, and mixtures thereof; each R is selected from the group consisting of H when y is not 0, C1-4 alkyl, C1-4 hydroxyalkyl, benzyl groups, ring structures formed by joining the two R4 groups, and -CH2CHOH-CHOHCOR6CHOHCH2OH wherein R6 is H or any hexose; R is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R5 is not more than about 18; each y is from 0 to about 3, m is from 0 to about 3 and X is any compatible anion; and (ii) aliphatic amines having the formula:
[R (OR3)m][R4(OR3)y]R5N
wherein R2, R3, R4, R5, m and y are the same as defined above and the pKa is at least about 1/2 unit above the initial pH of the wash water;
(iii) compounds having the general formula:
[R2(OR3)m][R4(OR3)y]2N+R3N+R5[(R3O)yR4]2X?2 wherein R2, R3, R4, R5, m, y and X are as defined above;
(iv) compounds having the general formula:
[R2(OR3)m][R4(OR3)y]NR3NR5[(R3O)yR4]

wherein R2, R3, R4, R5, m and y are as defined above and the pKa is at least about 1/2 unit above the initial pH of the wash water;
and mixtures thereof.

3. The composition of claim 1 wherein the alkylsulfate deter-gent surfactant is present in an amount of from about 3% to about 30%, the cationic surfactant is present in an amount of from about 1/2% to about 8%, and the sulfonate detergent sur-factant is present in an amount of from about 2% to about 30%, said percentages being by weight of said composition.

4. The composition of claim 1 wherein the alkylsulfate deter-gent surfactant is present in an amount of from about 5% to about 20%, the cationic surfactant is present in an amount of from about 1/2% to about 6%, and the sulfonate detergent sur-factant is present in an amount of from about 3% to about 20%, said percentages being by weight of said composition.

5. The composition of claim 3 wherein the alkylsulfate deter-gent surfactant is present in an amount of from about 5% to about 20%, the cationic surfactant is present in an amount of from about 1/2% to about 6%, and the sulfonate detergent sur-factant is present in an amount of from about 3% to about 20%, said percentages being by weight of said composition.

6. The composition of Claim 1 wherein the alkylsulfate detergent surfactant is selected from the group consist-ing of alkali metal, ammonium, and substituted ammonium salts of C12-15 primary and C12-18 secondary alkyl sulfates.

7. The composition of Claim 3 wherein the alkylsulfate detergent surfactant is selected from the group consist-ing of alkali metal, ammonium, and substituted ammonium salts of C12-15 primary and C12-18 secondary alkyl sulfates.

8. The composition of Claim 6 wherein the alkylsulfate detergent surfactant is selected from sodium and potas-sium salts of C12-15 linear and methyl branched alkyl-sulfates.

9. The composition of Claim 7 wherein the alkylsulfate detergent surfactant is selected from sodium and potas-sium salts of C12-15 linear and methyl branched alkyl-sulfates.

10. The composition of Claim 1 wherein the cationic surfactant is selected from the group consisting of:
i. [R2(OR3)m][R4(OR3)y]2R5N+X-; and ii. [R2(OR3)m][R4(OR3)y]R5N.

11. The composition of Claim 3 wherein the cationic surfactant is selected from the group consisting of i. [R2(OR3)m][R4(OR3)y]2R5N+X-; and ii. [R2(OR3)m][R4(OR3)y]R5N.

12. The composition of Claim 10 wherein the cationic surfactant has the formula:
[R2(OR3)m][R4(OR3)y]2R5N+X-.

13. The composition of Claim 11 wherein the cationic surfactant has the formula:
[R2(OR3)m][R4(OR3)y]2R5N+X-.

14. The composition of Claim 12 wherein the cationic surfactant has the formula:
[R2(OR3)m][R4(OR3)y]3N+X-.

15. The composition of Claim 13 wherein the cationic surfactant has the formula:
[R2(OR3)m][R4(OR3)y]3N+X-.

16. The composition of Claim 14 wherein the cationic surfactant is selected from the group consisting of chloride, bromide, and methylsulfate salts of C8-12 alkyl-trimethyl ammonium surfactants, C8-12 alkylhydroxyethyl-dimethyl ammonium surfactants, C8-12 alkylmethyldihy-droxyethyl ammonium surfactants, C10-14 alkoxytrimethyl ammonium surfactants, C10-14 alkoxydihydroxyethylmethyl ammonium surfactants and C10-14 alkoxyhydroxyethyldi-methyl ammonium surfactants.

17. The composition of Claim 15 wherein the cationic surfactant is selected from the group consisting of chloride, bromide, and methylsulfate salts of C8-12 alkyl-trimethyl ammonium surfactants, C8-12 alkylhydroxyethyl-dimethyl ammonium surfactants, C8-12 alkylmethyldihy-droxyethyl ammonium surfactants, C10-14 alkoxytrimehyl ammonium surfactants, C10-14 alkoxydihydroxyethylmethyl-ammonium surfactants and C10-14 alkoxyhydroxyethyldi-methyl ammonium surfactants.

18. The composition of Claim 1 wherein the sulfonate detergent surfactant is a secondary alkyl benzene sul-fonate having from about 9 to about 15 carbon atoms in the alkyl chain.

19. The composition of Claim 3 wherein the sulfonate detergent surfactant is a secondary alkyl benzene sul-fonate having from about 9 to about 15 carbon atoms in the alkyl chain.

20. The composition of Claim 18 wherein the sulfonate detergent surfactant is a secondary alkyl benzene sul-fonate having from about 11 to about 13 carbon atoms in the alkyl chain.

21. The composition of Claim 19 wherein the sulfonate detergent surfactant is a secondary alkyl benzene sul-fonate having from about 11 to about 13 carbon atoms in the alkyl chain.

22. The composition of Claim 1 wherein the molar ratio of (b):(c) is less than about 1.

23. The composition of Claim 11 wherein the molar ratio of (b):(c) is less than about 1.

24. The composition of Claim 1 wherein the sum of the equimolar levels of cationic surfactant and sulfonate detergent surfactant is at least about 2% of the total level of anionic surfactant.

25. The composition of Claim 11 wherein the sum of the equimolar levels of cationic surfactant and sulfonate detergent surfactant is at least about 2% of the total level of anionic surfactant.

26. The composition of Claim 24 wherein the sum of the equimolar levels of cationic surfactant and sulfonate detergent surfactant is above about 5% of the total level of anionic surfactant.

27. The composition of Claim 25 wherein the sum of the equimolar levels of cationic surfactant and sulfonate detergent surfactant is above about 5% of the total level of anionic surfactant.

28. The composition of Claim 26 wherein the sum of the equimolar levels of quaternary ammonium surfactant and sulfonate detergent surfactant is above about 10% of the total anionic surfactant.

29. The composition of Claim 27 wherein the sum of the equimolar levels of quaternary ammonium surfactant and sulfonate detergent surfactant is above about 10% of the total anionic surfactant.

30. The composition of Claim 1 wherein the detergency builder is present in an amount of from about 10% to about 60% by weight of said composition.

31. The composition of Claim 3 wherein the detergency builder is present in an amount of from about 10% to about 60% by weight of said composition.

32. The composition of Claim 30 wherein the detergency builder is present in an amount of from about 20% to about 50% by weight of said composition.

33. The composition of Claim 31 wherein the detergency builder is present in an amount of from about 20% to about 50% by weight of said composition.

34. The composition of Claim 30 wherein the detergency builder is selected from the group consisting of tri-polyphosphates, hexametaphosphates and higher polymeri-zation species, citrates, nitrilotriacetates and water-soluble polyacetals and mixtures thereof.

35. The composition of Claim 31 wherein the detergency builder is selected from the group consisting of tri-polyphosphates, hexametaphosphates and higher polymeri-zation species, citrates, nitrilotriacetates and water-soluble polyacetals and mixtures thereof.

36. The composition of Claim 1 wherein the nonionic surfactant is present in an amount of from about .5% to about 10% by weight of said composition.

37. The composition of Claim 3 wherein the nonionic surfactant is present in an amount of from about .5% to about 10% by weight of said composition.

38. The composition of Claim 36 wherein the nonionic surfactant is present in an amount of from about 1% to about 5% by weight of said composition.

39. The composition of Claim 37 wherein the nonionic surfactant is present in an amount of from about 1% to about 5% by weight of said composition.

40. The composition of Claim 36 wherein the nonionic surfactant is selected from the group consisting of fatty acid amide, amine oxide and ethoxylated alcohol detergent surfactants.

41. The composition of Claim 36 wherein the nonionic surfactant is selected from the group consisting of fatty acid amide, amine oxide and ethoxylated alcohol detergent surfactants.

42. The composition of Claim 1 wherein enzymes are present at a level of from about .2% to about 3% by weight of said composition.

43. The composition of Claim 3 wherein enzymes are present at a level of from about .2% to about 3% by weight of said composition.

44. The composition of Claim 1 wherein water soluble salts of fatty acids are present at levels up to 10% by weight of said composition.

45. The composition of Claim 3 wherein water soluble salts of fatty acids are present at levels up to 10% by weight of said composition.

46. The composition of Claim 44 wherein the water soluble salts of fatty acids have from about 8 to about 18 carbon atoms.

47. The composition of Claim 45 wherein the water soluble salts of fatty acids have from about 8 to about 18 carbon atoms.

48. The composition of Claim 46 wherein the water soluble salts of fatty acids are the sodium, potassium and magnesium salts of C12-14 fatty acids.

49. The composition of Claim 47 wherein the water soluble salts of fatty acids are the sodium, potassium and magnesium salts of C12-14 fatty acids.

50. The composition of Claim 1 wherein the cationic surfactant (b) is selected from the group consisting of:
(i) compounds having the general formula:
[R2(OR3)m]2[R4(OR3)y]zQ+X-wherein Z is N, P or S; z is 1 if Q is S
and 2 if Q is N or P; each R2 is selected from the group consisting of an alkyl or alkyl benzyl group consisting from about 4 to about 10 carbon atoms excluding the benzyl group; each R3 is selected from the group consisting of -CH2CH2-, -CH2-CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH?, and mixtures thereof; and wherein the sum of the carbon atoms of [R2(OR3)m]2 is from about 10 carbon atoms to about 16 carbon atoms when m is 0 and from about 10 carbon atoms to about 18 carbon atoms when m is from 1 to about 3, a benzene ring being treated as equivalent to about 2 carbon atoms; each R4 is selected from the group consisting of H
when y is not 0, C1-3 alkyl; C1-4 hydroxyalkyl, benzyl groups, ring struc-tures formed by joining the two R4 groups, and -CH2CHOHCHOHCHOR6CHOHCH2OR6 wherein R6 is H or any hexose wherein at least one R6 is H; each y is from 0 to about 3, each m is from 0 to about 3 wherein m is 1 when R3 is -CH2CH2-; and X is any compatible anion selected from the group consisting of halide, hydrox-ide, methylsulfate and acetate anions and mixtures thereof;
(ii) compounds having the general formula:

wherein Q, R3, R4, y, m and X are as defined above; n is 2 if Q is S and 3 if Q is N or P; each R5 is selected from the group consisting of an alkyl or alkyl benzyl group containing at least about 1 carbon atom excluding the benzyl group and ring structures formed by joining any of the carbon atoms of each R5 and wherein the sum of the carbon atoms of [(R3O)mR5]2 is from about 9 carbon atoms to about 16 carbon atoms when m is 0 and from about 10 carbon atoms to about 18 carbon atoms when m is from 1 to about 3, a benzene ring being treated as equivalent to about 2 carbon atoms; and a is from 0 to about 3;
(iii) aliphatic amines having the general formula:
[R2(OR3)m]2[R4(OR3)y]N
wherein R2, R3, R4, m and y are as defined above and the pKa is at least about 1/2 unit above the initial pH of the wash liquor;
(iv) compounds having the general formula:

wherein R2, R3, R4, m, y and X are as defined above; and (v) compounds having the general formula:

wherein R2, R3, R4, m and y are as defined above and the pKa is at least about 1/2 unit above the initial pH of the wash liquor;
and mixtures thereof.