CA1213286A - Ethoxylated amine compounds having clay soil removal/anti-redeposition properties useful in detergent compositions - Google Patents

Abstract

ETHOXYLATED AMINE COMPOUNDS HAVING CLAY SOIL
REMOVAL/ANTI-REDEPOSITION PROPERTIES USEFUL IN
DETERGENT COMPOSITIONS
ABSTRACT
Water-soluble ethoxylated amine compounds having clay soil removal/anti-redeposition properties. The compounds are selected from ethoxylated diamine compounds, ethoxylated polyamines and mixtures thereof. These ethoxylated amine compounds are useful in detergent compositions.

Description

~32~

ETHOXYLATED AMINE COMPOUNDS HAVING CLAY SOIL
REMOVAL/ANTI-~EDEPOSITION PROPERTIES USEFUL
IN DETERGENT COMPOSITIONS
'I Down N. Rubingh Eugene PO ~osselink TECHNICAL FIELD
The present application relaxes to ethoxylated amine , compounds having clay-soil removal/anti-redeposition properties when used in detergent compositions.
AYE particularly important property of a detergent composition is its ability to remove particulate type soils from a variety of i fabrics during laundering. Perhaps the most important particulate soils are the clay-type soils. Clay soil particles generally ( comprise negatively charged layers of aluminosilicates and post-¦15 lively charged cations (e.g. calcium) which are positioned between and hold together the negatively charged layers.
A variety of models can be proposed for compounds which would shave clay soil removal properties, One model requires that thy compound have two distinct characteristics. The first is the ,~`20 ability of the compound to adsorb onto the negatively charged slayers of the clay particle. The second is the ability of the compound, once adsorbed, to push apart (swell) the negatively charged layers so that the clay particle loses its cohesive force Andy can be removed in the wash water.
one class of clay-soil removal compounds which appears to work according to this model are the polyethoxy zwitterionic surfactants disclosed in US. Patent 4,301,044 to Gentler et at., issue Nabber 17, 1981. Representative of such compounds are those having the formula:

R1 No -(CH2)x~-O-(CH2CH20)ySO3 SHEA
wherein R1 is a C14-C20 alkyd group; x is 1 or an integer of from 3 to 5; and y is from 6 to 12. See also US. Patent 3,929,678 to ` Laughlin et at. 3 issued December 30, 1975 (detergent composition containing polyethoxy zwitterionic surfactant plus other detergent `: ;

I
, .. ..
. Jo surfac~ants); US. Patent 39925,262 to Laughlin et at., issued December 9, 1975 detergent composition containing polyethoxy zwitterionic surfactants with detergent builders); US. Patent 4,1575277 to Gosselink et at., issued June 26, 1979 (C4 polyoxy-alkaline 2witterionic surfactants useful in detergent compost-lions); US. Patent 4,165,334 to Gosselink et at., issued AU9LISt '21, 1979 (sulfonium-type polyethoxy zwitterionic surfactants).
These polye~hoxy zwitterionic surfactants are generally computable with other detergent surfactants such as the non ionic, ;10 zwitterionic and ampholytic types. However, as indicated in the Gentler et at. patent, most anionic surfactants interfere with the particulate soil removal performance of these compounds; anionic soils such as fatty acids likewise interfere. Because anionic detergent sur~actants form the most important class of such materials for use in deterrent compositions, the lack of compute-ability between these polyethoxy zwitterionic surfactants and anionic surfactants poses a significant handicap where particulate clue) soil removal is desired.
In addition to clay soil removal, one of the other properties mentioned in the Laughlin et at. patents with regard to these polyethoxy zwitteribnic surfactants is the ability to keep the removed soil in suspension during the laundering cycle. Soil which is removed from the fabric and suspended in the wash water Icon redeposit onto the surface of the fabric. This redeposited .25 soil causes a dulling or "graying" effect which is especially noticeable on white fabrics. Because soil is normally hydropho-big, this graying effect is a particularly important problem for those fabrics made in total or in part from hydrophobic fibers, e.g. polyester.
To minimize this problem, anti-redeposition or whiteness maintenance agents can be included in the detergent composition.
Besides the previously mentioned polyethoxy zwitterionic surface tents, there are a variety of other compounds which can be used as anti-re~eposition agents. One class of agents are the water-soluble copolymers of acrylic or methacrylic acid with acrylic or methacrylic acid-ethylene oxide condensates disclosed in US.

`
Jo ;
.

Lo Patent 3,719,647 to Hardy et at., issued March I 1973. Another class of anti-redeposition agents are the cellulose and car boxy-methyl cellulose derivatives disclosed in US. Patent 3,597,416 to Doyle, issued August 3, 1971 (ionic combination of dodecyltri-methyl phosphonium chloride and sodium carboxymethylcellulose),and US. Patent 3,523,088 to Dean et at., issued August 4, 1970 (anti-redeposition agent consisting of alkali metal carboxymethyl-cellulose and hydroxypropy1ce11ulose). A mixture of compounds has also been used to provide no only anti-redeposition, but also clay soil removal properties. See US. Patent 4,228,044 to Camber, issued October 14, 1980, which discloses detergent combo-sessions having anti-redeposition and clay soil removal properties which can comprise a non ionic alkyd polyethoxy surfactantg a polyethoxy alkyd qua ternary cat ionic surfactant and a fatty aside j 15 surfactant, These anti-redeposition agents do have a number of signify-cant handicaps. While effective to keep soil suspended, these 1, compounds may lack additional clay soil removal properties.
Moreover, as disclosed in the Doyle and Jean et at. patents, mixtures of compounds can be required to achieve the anti-redeposition benefit. To the extent that there are combined anti-redeposition/clay soil removal benefits as disclosed in the ; Camber patent mixtures ox compounds are also required.
It is therefore an object of the present invention to provide compounds useful in detergent compositions which provide part-curate soil, in particular clay soil, removal benefits.
It is a further object of the present invention to provide compounds useful in detergent compositions which provide clay soil removal benefits and are anionic detergent surfactant compatible.
I It is yet another object of the present invention to provide compounds useful in detergent compositions having anti-redeposi-lion properties.
It is yet a further object of the present invention to provide compounds useful in detergent compositions which combine both clay soil removal and anti-redeposition properties.

I

, These and further objects of the resent invention are hereinafter disclosed.
BACKGROUND ART
U. S. Patent 3,301,783 to Dickson, et at., issued January 31, ' 5 1967, discloses oxyalkylated, assaulted, alkylated, carbonylated and olefinated derivatives of polyalkyleneimines9 in particular polyethyleneimines (Pies). For the oxyalkylated derivatives, the alkaline oxide (e.g. ethylene oxide) is reacted with the polyp alkyleneimine in a mole ratio of from 1.1 to 1000 1, and prefer-ably in a ratio of from 1:1 to 200:1. Among the ethoxylated Pies disclosed are Examples 1 07 and 1-8 formed by condensing 105 and 200 moles, respectively, of ethylene oxide with a 900 MOW. PHI.
The degree of ethoxylation calculates out to about 4.5 and about 8 ethics groups per reactive site, respectively. See also Examples 27-05 and 27-06 which disclose ethoxylated polypropyleneimines (MOW. 500) which have about 4 and about 8 ethics units per react live site, respectively. Amongst the numerous disclosed uses of these polyalkyleneim;ne derivatives is a teaching that they are useful as detergents, softening agents and antistatic agents.
t 20 Preferred uses disclosed by thus patent are as chelating agents, f' lubricating oil additives, emulsifying agents, and cutting oils.
US. Patent 2,7929371 to Dick fin, issued May 14, 1957, teaches a process for breaking petroleum emulsions with ox-! alkylated tetraethylene pentaamines (TEA). Ethoxylated Teas 25 specifically disclosed include those having about 5 (Example baa), about 7 (Example baa), about 8.5 (Example pa) and about 15.5 (Example Be) ethics units par rocket site. Similarly, US.
patent 2,792,370 to Dickson issued May I 1957, teaches a process I, for breaking petroleum emulsions with oxyalkylated triethylene 30 tetramines (Toyotas including those having about 5.5 (Example baa), about 7.5 (Example baa), about 9 (Example pa) and about 16.5 (Example By-) ethics units per reactive site. See also U. S.
patent 2,792,372 to Dickson issued May 14, 1957, (oxyalkylated it higher Peas used to break petroleum emulsions); U. S. patent

2,7g2,369 to Dickson, issued May 14, 1957 (oxyalkylated diethylene trimness used to break petroleum emulsions.

, ~2~3~28~i U. S. Patent 4,171~278 in Andre et Allah issued October 16, 1979, discloses cold water detergent compositions containing a detergent surfactant [e.g. anionic) and a hydroxyalkyl amine in a weight ratio of 100:1 to 1:1. The amine can have the formula:
, 5 R i IT - fry O(CH2-CHO)mH R4 Chicano ' : R4 , ON

rein R1 is C1-C16 alkyd; R2 is H or C1-~C16 alkyd; R R ha 1 6-20 carbon atoms; R4 is H or methyl; my n, and ox are each O to 3 and A is bridging group such as I_ Jo OH

Y
f YcH2cHO)pH
I
wherein R3 is H or methyl; x is 2 to 6; y is 1 to 3; and p is O to

3; the sum of m to p being 1 to 5.5, and preferably 1 to 2. See also German Patent Document 2,165,900 to Henkel, published July 5, 1973, which discloses a washing agent for graying prevention formed by the reaction product of a PHI with an alkylglycidylether I and ethylene oxide (2-hydroxyethyl moiety at each reactive site when ethoxylated)-I: European Patent Application 42,187 to Kosher, published !
December 23, 19819 discloses detergent compositions having en-hanged soil release and cleaning properties These compositions contain from about 2% to about 60% by weight of a detergent surfactant ye. 9. anionic and from 0.1% to 1.2% by weight of a ` polyamide. This polyamide has the formula:
Rex - ~R2 R- N _ Sheehan _ No _ ~Rl)z Jo m wherein R is a C10 to C22 alkyd or alkenyl group; R1 is 3~8~

ethyleneoxide/propylene oxide; R2 can be (Roy x, y, and z are ,, numbers such that their sum is from 2 to about 25, n is from 1 to about 6; and m is from 1 to about 9. Preferred palominos are those where I is ethylene oxide, R2 is ethylene oxide, n is 2 or 3, m is 1 to 31 and x, y, z, are each 1 to 4 with their sum being from 3 to 18. Examples 6 and 7 disclose ethoxylated Noah-- drogenated tallow propylene - dominoes, where the sum of x, y, and z are 7 and 12~ respectively.
U. S. Patent 3,838~057 to Barnes et at., issued September 24, 1974, discloses toilet bars containing ethoxylated qua ternary ammonium compounds, including ethoxylated, quaternized Pies taught ', to be useful in the detergent, textile, and polymer industries, as anti-static and softening agents. These ethoxylated quaternized Pies have the formula:

Ho- N -SHEA - CH2-)nHnX
I

EON
wherein R1 is a compatible qua ternary nitrogen substituent; n is at least 2; x is from 3 to 40; and X is a compatible anion.
Preferred compounds are those where R1 is a C8 - C22 alkyd group or the group:
R'C~O(EO)y-CH2CHOHCH2-whine R' is a C8 - C22 alkyd group and y is from 3 to 40. See also U. S. Patent 4,179,382 to Rudkin et at., issued December 18, 1979; U. S. Patent 4,152,272 to Young, issued May 1, 1979; and European Patent Application 2,085 to Rudkin et at., published May 30, 1979, which disclose ethoxylated quaterni~ed polyamides having C10 to C~4 alkyd or alkenyl groups attached to one of the nitrogen j atoms useful as fabric softeners.
There are several patents which disclose detergent compost-lions, shampoo compositions and the like containing slightly ethoxylated Pies (ethylene oxide:PEI weight ratio of 4:1 or less) to enhance the deposition and retention ox particulate substances such as antimicrobial. See, for example U. S. Patent 3,489,686 r DO

'I' ; - 7 -to Porn, issued January 13, 1970; U. S. Patent 3,580,853 to Porn, issued May 25, 1971; British Patent Specification , 1,111,708 to Procter Gamble published May 1, 1968, lJ.S. Patent `, 3,549,546 to Moore, issued December 22, 1970; and US. Patent3,549,542 to Holder by, issued December 22, 1970.
DISCLOSURE OF THE INVENTION
: The present invention relates to water-soluble ethoxylated, amine compounds having clay soil removal/ anti-redeposition properties useful on detergent compositions. These compounds are selected from the group consisting of:
(1) ethoxylated dominoes having the formula:
R2 N - R1 N R2 I N - R1 - N - (R I
L L L
X X X
or it (X-L-)2- N - R1 - N - (R2)2 (2) ethoxylated polyamides having the formula:

R3 - [(A1)q-(R4)t-N-L Up and; (3) mixtures thereof O O O O O O O O
wherein Al is -NC-, -NO-, -NON-, -ON-, -CON-, -CO-, -COO-, I
R R R R R R
O O

25 -CNC-, or I
I R
R is H or C1-C4 alkyd or hydroxyalkyl; R1 is C2-C12 alkaline, hydroxyalkylene, alkenylene, Arlene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to bout 20 oxyalkylene units provided that no O-N bonds are formed; each R2 Jo C1-C4 alkyd or hydroxyalkyl, the moiety -L-X, or two R together form the moiety Jo -(Shorties-, wherein A us -O- or SHEA-, r is 1 or 2, s is 1 or 2, and r s is 3 or 4; X is a nonlonlc group, an anionic group or mlxturP thereof; R3 is a substituted C3-C12 alkyd, hydroxyalkyl, alkPnyl, aureole, or alkaryl group having p ' substitution sites R4 is C1 - C12 alkaline, hydroxyalkylene, Jo I, .. .

-I Z Lo alkoxylene~ Arlene or alkarylene, or a C2 - C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units; L is a hydroph;lic chain which contains the polyoxyalkylene moiety -[(R50)m~CH2CH2o)n]-, wherein R5 is C3-C4 alkaline or hydroxyalkylene and m and n are numbers such that the moiety (Shoeshine comprises at least about 50% by weight of said polyoxyalkylene moiety; for sand dominoes, m us from O to about 3, and n us at least about 6 when R1 us C2-C3 alkaline, hydroxyalkylene, or alkenylene, and at least about 3 when R is other than C2-~3 alkaline, hydroxyalkylene or alkenylene; for said polyamides, m is from O to about 10, and n is at least about 3, p us from 3 to 8; q us 1 or I t us 1 or I provided that t is 1 when q is 1..
The ethoxylated amine compounds of the present invention provide clay soil removal benefits while being anionic detergent surfactant compatible. At most wash oh's, it is believed that the nitrogen atoms of these compounds are partially protonated. The resulting positively charged centers (and remaining polar nitrogen atoms) are believed to aid in the adsorption of the compound onto the negatively charged layers of the clay particle. It is also believed that the hydrophilic ethics units of the compound swell the clay particle so what it loses its cohesive character and is swept away in the wash water.
The anti-redeposition benefits provided by these ethoxylated amine are also believed to by due to the formation of positively charged centers together with the remaining polar nitrogens, in Ills adsorption onto soil suspended in the wash water. As more and more of these compounds adsorb onto the suspended soil, it becomes encased within a hydrophilic layer provided by the attached ethics units. As such, the hydrophilicly encased soil is prevented from redepositing on fabrics, in particular hydrophobic fabrics such as polyester, during the laundering cycle.
Ethox~ated Amine Compounds the water-soluble ethoxylzted amine compounds useful in the '~35 present invention area selected from ethoxylated dominoes and ~LZ~3~

.- g o ethoxylated po7yamines, and mixtures thereof as previously de-fined.
In the preceding formulas, Al can be bran hod S ego. -CH2-CH-, -SHEA -), cyclic (e.g. ) or most preferably linear ego. -CH2CH2-9 -CH2-CH2-CH2-, -SHEA OH-) alkaline, hydroxyalkylene~ alkenylene, alkarylene or oxyalkylene. R is preferably C2-C6 alkaline for the ethoxylated I dominoes. For the ethoxylated dominoes, the minimum degree ofethoxylation required for suitable clay soil removal/ant;-redepo-session properties decreases on going from C~-C3 alkaline [ethyl-one, propylene) to hexamethylene. Each R is preferably the moiety -L-X.
In the preceding formulas, hydrophilic chain L usually j consists entirely of the polyoxyalkylene moiety I O)m(CH2CH20)n~- The moieties -trim- and -(Shoeshine- ox the polyoxyalkylene moiety can be mixed together or preferably form blocks of ~~R50)m~ and -(Shoeshine- moieties. R5 is prefer-i ably C3H6 (propylene). For the ethoxylated pylons, m is preferably from 0 to about 5. For all ethoxylated amine compounds of the present invention, m is most preferably n, i.e. the polyoxyalkylene moiety consists entirely of the moiety 2$ -(Shoeshine-. The moiety -(Shoeshine- preferably comprises at least about 85~ by weigh of the polyoxyalkylene moiety and most preferably lox by weight (m is 0).
In the preceding formula, X can be any compatible non ionic group, anionic group or mixture thereof. Suitable non ionic groups include Cluck alkyd or hydroxyalkyl ester or ether groups, preferably acetate and methyl ether, respectivelyi,hydrogen (Ho; or mixtures thereof. The particularly preferred non ionic group is H.
With regard to anionic groups, P03 and S03 are suitable. The particularly preferred anionic group is 503-. It has been found that the percentage of anionic groups relative to non ionic groups can be important to the clay soil removal/anti-redeposition I

- 1 o properties provided by the ethoxylated amine compound. A mixture no from 0 to about 30% anionic groups and from about 70 to 100~
non ionic groups provides preferred properties. A mixture of from about 5 to about 10% anionic groups and from about 90 to about 95 non ionic groups provides the most preferred properties. Usually, ! a mixture from 0 to about 80X anionic groups and from about 20 to 100% non ionic groups provides suitable clay soil removal/anti-re-deposition properties.
Preferred ethoxylated dominoes have the formula:
' 10( ~2cH2o)n-N-cH2~cH2-(cH2)a-N-(cH2cH2o) -x (Shoeshine X (l~H2CH20)n-X
wherein X and n are defined as before, and a is from 0 to 4 (e.g.
ethylene, propylene, hexamethylene). For preferred exulted dominoes, n is at least about 12 with a typical range of from ' 15 about 12 to about 42.
- In the preceding formula for the ethoxylated palominos R3 `' (linear, branched or cyclic) is preferably a substituted C3-C6 alkyd, hydroxyalkyl or aureole group, Jo 20 A is preferably -ON-; n is preferably at least about 12, with a H
typical range of from about 12 to about 42; p is preferably from 3 to 6. When R3 is a substituted aureole or alkaryl group, q is preferably 1 and R4 is preferably C2-C3 alkaline. When R3 is a ¦ US substituted alkyd, hydroxyalkylg or alkenyl group, and when q is l 0, R4 is preferably a C2-C3 oxya7kylene moiety; when q is 1, R4 is preferably C2-C3 alkaline.
These ethoxylated polyamides can be derived from palomino asides such as:

I
`

I
.

3 2~3~

~CN-(C3H6)-NH2 Ho -CN-~C3H6~-NH2 or ~(C3H6) NH2 O
N (C3H6) NH2 These ethoxylated polyamides can also be derived from palomino-propylene oxide derivatives such as:
Jo C3H6 ) c-NH2 SHEA- (0C3H6)C-NH2 C3H6 ) c NH2 wherein each c us a number of from 2 to about 20.
The level at which the ethoxyalted amine compound(s) of the present invention can be present in the detergent compositions can very depending upon the compounds used, the particular detergent formulation (liquid granular) and the benefits desired. These compositions can be used as laundry detergents, laundry additives, and laundry pretreatment. generally, the ethoxylated amine compounds can be included in an amount of from about 0.05 to about 95.% by weight of the composition with the usual range being from about 0.1 to about 10% by weight for laundry detergents. In terms of the benefits achieved, preferred detergent compositions can comprise from abut 0.5 by about I by weight of the compounds of the present invention. Typically, these preferred compositions comprise from about 1 to about I by weight of these compounds.
These campcunds æ e normally present at a level that provides from ; 30 about 15 Pam to abx~lt 200 Pam, preferably from about 25 Pam toabout 125 Pam, of the compound in the wash solution at recommend US. usage levels, and normally from about 30 Pam to about Lowe Pam, preferably from about 50 Pam to abut 500 Pam for European usage levels.

] ~-~ f' Methods for Making Ethox~lated Amine Compounds The ethoxylaked amine compounds of the present invention can be prepared by standard methods for ethoxylating amine. There is preferably an initial step of condensing sufficient ethylene oxide 3 5 to provide 2-hydroxyethyl groups at each reactive site (hydroxy-, ethylation). This initial step can be omitted by starting with a ¦ 2-hydroxyethyl amine. The appropriate amount of ethylene oxide is then condensed with these 2-hydroxyethylamines using an alkali metal (e.g., sodium, potassium) hydrides of hydroxide as the catalyst to provide the respective ethoxylated amine. The total degree of ethoxylation per reactive site (n) can be determined according to the following formula:
, Degree of Ethoxylation = Ella x R) j wherein E is the total number of moles of ethylene oxide condensed (including hydroxyethylation), A is the number of moles of the ¦ starting amine, and R is the number of reactive sites (typically 4 for dominoes and 2 x p for polyamides) for the starting amine.
Representative synthesis of an ethoxylated Damon of the ¦ present invention is as follows:
O Example 1 I Sieve dried (PA) ethylenediamine (MOW. 60, 42 9., 0.7 moles) Jo was placed on a nominally dry flask, and hydroxyethylated with ethylene oxide En at 25 - 116C with rapid stirring. After 3.3 his., 143,3 S- (3.25 moles) of En had been added for a degree of i 25 ethoxylation of 1.16. After cooling the reaction mixture under argon, 9.82 g. (0.07 moles) of freshly prepared 40% potassium hydroxide solution was added. Water was removed by stirring at 110-115C for 0.5 his with an aspirator vacuum and 0.5 hours with a pump vacuum. En was then added under atmospheric pressure with stirring at 100-138C. After 6 his. 2935 9. (66,7 moles) of En had been added to give a calculated total degree of ethoxylation of 23.82. The ethoxylated Damon obtained was a brown waxy solid when tooled.

~32~1~

I, Clay Soil Removal/Anti-Redeposition Properties of i Various Ethoxylated Amine A. Experimental Method , 1. Clay Soil Removal ; clay soil removal comparisons were conducted in a standard 1 , liter Tergotometer employing water of 7 grain hardness (3:1 I; Cay My ) and a temperature of 100F. Soiled swatches were washed in the Tergotometer for 10 minutes and rinsed twice with water (7 grain hardness) at 70F for 2 minutes.
Lowe% polyester/35% cotton blend fabric was used for the swatches. The swatches were 5 inches by 5 inches in size and were ' soiled by dipping in an aqueous slurry of local clay and subset ! quaintly baked to remove the water. The dipping and baking was repeated 5 times.
¦ one wash employed 2000 Pam of a control liquid detergent I! composition containing the following surfactants:
, Surfactant Amount (~) Sodium C14-C15 alkyd ethoxysulfate 10.8 C13 linear alkylbenzene sulfnnic acid 7.2 C12 C13 alcohol polyp ethnxylate (6.5) 6.5 Clue alkyd trim ethyl-ammonium chloride 1.2 A second wash used the same detergent composition but also con-} twining an ethoxylated amine compound at 20 Pam. Neither ¦ composition contained optical brighteners. The product washes approximated a conventional home use laundry situation. After laundering, the swatches were dried in a mini-dryer.
i The swatches were yarded before and after washing on a ¦ Gardner Whiteness meter reading the L, a and b coordinates.
I; Whiteness (W) was calculated as:
j W = 7L2 _ 40Lb The clay soil removal performance ox each detergent composition .

I

was determined by finding the difference in whiteness OW) before and aster washing as:
W = W aster W before The improvement in clay soil removal performance of the compost-lion containing the ethoxylated amine compound was measured as thedifferenc2 in W values (WOW) relative to the control composition.
' 2. Anti-Redeposition Anti-redeposition comparisons were conducted in a 5 pot Automatic Mini washer (AM) employing 7 grain hardness water and temperature of 95F. Test swatches were washed for 10 minutes and rinsed twice with water I grain hardness) at 75F for 2 minutes.
After the AM pots were filled with 6 liters of water each, the detergent composition to ye tested (control or containing 20 Pam ethoxylated amine as in clay soil removal test) was added and agitated for 2 minutes. A background soil mixture (20D Pam artificial body soil 100 Pam vacuum cleaner soil and 200 Pam clay , soil) was then added and agitated for an additional 3 minutes.
I Three 5 inch square test swatches (50% polyester/50% cotton T-shirt material) were then added along with two 80~ cotton/20%
, 20 polyester terry clothes and two 11 inch square swatches of 100%
i polyester knit fabric. The 10 minute wash cycle commenced at this point, Following the rinse cycles the test swatches were dried in a meanderer. Gardner Whiteness meter readings (L, a and b) were then determined for the three test swatches. Anti-redeposition performance (ART) was then calculated according to the following equation:
ART = 7L2 _ 40Lb ... . .

30 The ART values for the three test swatches were then averaged.
The improvement in anti-redeposition performance of the compost-lion containing the ethoxylated amine was measured as the differ-once in ART values (I ARROWHEAD relative to the control composition.

~3~8~i :. - 15 -B. Test Results The results from testing the clay-soil removal and anti~rede-position performance of various ethoxylated amine compounds is shown in the following Table:
'I 5 Amine * Amine Degree of Type M.W.E~hoxylation OW ART
ETA 60 3 1.7 OWE
8 2.9 8.4 12 5.1 9.4 24 6.1 13.1 42 5.5 12.9 PEA 74 3 2.4 3.2 6 2.4 6.2 13 6.1 10.7 24 5.8 11.4 43 5.4 12.4 HMDA 3 13.3 6 1~.4 EDDY = ethylenediamine, PEA = propylenediamine, HMDA
hexamethylene.
For comparison, PEG 6000 (polyethylene glycol having MOW. or 6000) has a WOW value of 4.9 and award value of 8.9.
Deterrent Surfactants The amount of detergent surfactant included in the detergent ~25 compositions of the present invention can vary from about 1 to about 75~ by weight of the composition depending upon the deter-gent surfactant(s) used, the type of composition to be formulated ego. granular, liquid) and the effects desired. Preferably, the detergent surfactant(s) comprises from about 10 to about 50% by 3C weight of the composition. The detergent surfactant con be non ionic, anionic, ampholytic, 2witterionic, cat ionic, or a mixture thereof:
A. Non ionic Surfactants Suitable non ionic surfactants for use in detergent compost-lions of the present invention are generally disclosed in US.
Patent 3,929,678 to Laughlin et at., issued December 30, 1975 at - ~L2~L3~

column 139 line 14 through column 16, line 6. Classes of non-tome ~urfactants included are:
1. The polyethylene oxide condensates of alkyd phenols.
These compounds include the condensation products of alkyd phenols having an alkyd group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, the ethylene oxide being present in an amount equal to 5 to 25 moles of ethylene oxide per mole of alkyd phenol.
The alkyd substi~uent on such compounds can be derived, for example, from polymerized propylene, diisobutylene9 and the like.
Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol;
. dodecylphenol condensed with about 12 moles of ethylene oxide per ¦ mole of phenol; dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol; and disquietly phenol condensed with about 15 moles of ethylene oxide per mole of phenol. Common-Shea available non ionic surfactants of this type elude Igepal~
C0-630, marketed by the GAY Corporation, and Briton X-45, X-114, X-100, and X-102, all marketed by the Room & Hays Company.
I 20 2. The condensation products of aliphatic alcohols with from j about 1 to about 25 moles of ethylene oxide. The alkyd chain of the aliphatic alcohol can either be straight or branched, primary Jo or secondary, and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol; and the condensation product of about 9 moles of ethylene oxide with coconut alcohol (a lo mixture of fatty alcohols with alkyd chains varying in length from 10 to 14 carbon atoms). Examples of commercial y available non ionic surfactants of this type include rgitol 15~S-9, mar kited by Union Carbide Corporation, ~eodol'J45-9, Nudely 23-6.5, Nudely ~5-7, and Nudely 45-4, marketed by Shell Chemical Company, and Gyro EON, marketed by The Procter Gamble Company.
3. The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds ' "

;

has a molecular weight of from about 150D to 1800 and exhibits waxer ~nsolubil1~y. The Addison of polyoxyethylene moieties to this hydrophobic portion tends to increase the water volubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50~ of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds this type include certain of the commercially available Pluronic~Ysurfactants, marketed by Wyandotte Chemical Corporation.

4. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethyl-enediamine. The hydrophobic eye of these products consists of the reaction product of ethylenediamine and excess propylene oxide, the moiety having a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide Jo the extent thaw the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of non ionic surfactant include certain of the common-Shelley available Tetronic compounds, marketed by Wyandotte Comma eel Corporation.

5. Semi-polar non ionic detergent surfactants which include water-soluble amine oxides containing one alkyd moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyd groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides contain in one alkyd moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyd groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyd moiety of from about 10 to 18 carbon atoms and a moiety selected from the group con-sitting of alkyd and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
I Preferred swampier non ionic detergent surfactants are the amine oxide detergent surfactants having the formula 3~36 ,, ,:;
- 18 ^

~,R3~oR4)~NR52 wherein R is an alkyd 9 hydroxyalkyl, or alkyd phenol group or mixtures whereof containing from about 8 to about 22 carbon atoms;
S R4 is an alkaline or hydroxyalkylene group continuing from 2 to 3 carbon atoms or mixtures thereof; x is from O to about 3; and each R5 is an alkyd or hydroxyalkyl group containing from 1 to about 3 Caribbean atoms or a polyethylene oxide group containing from one to about 3 ethylene oxide groups. The R5 groups can be attached to ¦10 each other, e.g., through an oxygen or nitrogen atom to form a ring structure.
Preferred amine oxide detergent surfactants are C10-Cl8 alkyd dim ethyl amine oxide and C8-C12 alkoxy ethyl dihydroxy ethyl amine , oxide.
156. Alkylpolysaccharides disclosed Jo Canadian Patent No. 1,180,873, issued January 15, 1985, having a ¦ hydrophobic group containing from about 6 to about 30 carbon I' atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, ego a polyglycoside, hydrophilic group con-~t20 twining from about I to about 10, preferably from about I to Abbott 3, most preferably from about 1.6 to about 2.7 saccharine units. Any reducing saccharine containing 5 or 6 carbon atoms can be used, e.g. glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydra phobic group is attached at the 2, 3, 4, etc. positions thus giving a glucose or galactose as opposed to a glucoside or gala-topside.) The intersaccharide bonds can be, e.g., between the one position of the additional saccharine units and the 2-, 3-, 4-, Andre 6 positions on the preceding saccharine units.
30Optionally, and less desirably, there can be a polyalkylene-oxide chain joining the hydrophobic moiety and the polysaccharide moiety. The preferred alkyleneoxide is ethylene oxide. Typical hydrophobic groups include a1kyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to Abbott 18, preferably from about lo to about 16, carbon atoms.
I;

.!

e ~L2~L3~

Preferably, the alkyd group is a straight chain saturated alkyd j group. The alkyd group can contain up to 3 hydroxy groups and/or the polyalky1eneoxide chain can contain up to about 10~ preferably less than 5, most preferably 09 alkyleneoxide moieties. Suitable alkyd polysaccharides are octal, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl 9 pentadecyl 9 hexadecyl 9 heptadecyl, and octadecyl, do-, try twitter-, pent-, and hexaglucosides, galacto-sides, lactosides, glucoses, fructosides, fructoses, and/or galactoses. Suitable mixtures include coconut alkyd, do-, in-, twitter-, and pentaglucosides and tallow alkyd twitter-, pent-, and hexaglucosides.
The preferred alkylpolyglycosides have the formula R 0(CnH2nO)t(9lycosyl)x wherein R is selected prom the group consisting of alkali alkyd-phenol, hydroxyalkyl, hydroxyalkylphenyl 9 and mixtures thereof inch the alkyd groups contain from about 10 to about 18, prefer-ably from about 12 to about 14, carbon atoms; n is 2 or 3, prefer-ably 2; t is from 0 to about 10, preferably 0; and x is from I to about 10, preferably from about I to about 3, most preferably from about 1.6 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkyd-polyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their l-position and the preceding glycosyl units 2-, 3-, 4- and/or 6- position, preferably predominately the 2-position.
7. Fatty acid aside detergent surfactants having the for-mute:
o R6-C~NR72 wherein R6 is an alkyd group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R7 is selected from the group consisting of hydrogen, C1-C~ alkyd, Cluck hydroxyalkyl, and -(C2H40)XH where x varies from about 1 to about 3.

L3~6 /

Preferred amfdes are C.8-C20 ammonia asides, monoethanol-I, amldes, d~ethanolamides, and ~sopropanol asides.
B. Anionic Surfactants Anionic surfactants Sybil in detergent compositions of the present invention are generally disclosed in US. Patent 3,929,578 to Laughlin et at., issued December 30, 1975 at column 23, line 58 through column 29, line 23 . Classes of anionic surface tents included are:
I. Ordinary alkali metal soaps such as the sodium, poles-slum, ammonium and alkylolammonium salts of higher fatty acids containing prom about 8 to about I carbon atoms, preferably from ; about 10 to about 20 carbon atoms.
2. Water-so1uble salts, preferably the alkali metal, ammo-I'm and alkytolammonium salts, of organic sulfuric reaction - 15 products having in their molecular structure an alkyd group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyd"
is the alkyd portion of azalea groups.) Examples of this group of anionic surfactants are the sodium and potassium alkyd sulfates, especially those obtained by sulfate in the higher alcohols (C8-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium a1kylbenzene sulfonates in which the alkyd group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in US. Patents 2,220,099 and 2,477,383. Espy-` Shelley valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyd group is from about 11 to 13, abbreviated as CIl-Cl3LAS.
Preferred anionic surfactants of this type are the alkyd polyethoxylate sulfates, particularly those In which the alkyd group contains from about 10 to about 22, preferably from about 12 ; to about 18 carbon atoms, and wherein the polyetho~yla~e chain contains from about 1 to about 15 etho~ylate moieties preferably from about 1 to about 3 ethoxylate moieties. These anionic ! detergent surfactan~s are particularly desirable for formulating heavy-duty liquid laundry detergent compositions.
Other anionic surfactants of this type include sodium alkyd glycerol ether sulfonates3 especially whose ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil I, fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyd phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyd groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyd ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyd group con-twins from about 10 to about 20 carbon atoms.
Also included are water-soluble salts of esters of Alpine sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic I, acids containing from about 2 to 9 carbon atoms in the azalea group , and from about 9 to about 23 carbon atoms in the Al Kane moiety;
alkyd ether sulfates containing from about 10 to 20 carbon atoms in the alkyd group and from about 1 to 30 moles of ethylene oxide;
water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy Al Kane sulfonates containing from about 1 to 3 carbon atoms in the alkyd group and from about 8 to 20 carbon atoms in the Al Kane moiety.
3. Anionic phosphate surfactants.
4. N-alkyl substituted succinamates.
C. Ampholytic Surfactants Ampholytic surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amine, or aliphatic derive-lives of hetero~yclic secondary and tertiary ammonias in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one contains an anionic water syllable-icing group, erg car boxy, sulfonate, sulfate. See US. Patent 3,929,578 to Laughlin et at., issued December 30, 1975 at column :`

I' I`
;

.

~L3%13~6 19, 1 ins 18-35 for examples of ampholytic surfactants.

; D. Zwitterionic Surfactants Zwitterionic surfactants can be broadly described as deft-valves of secondary and tertiary ammonias derivatives of hotter-. cyclic secondary and tertiary amine, or derivatives of qua ternary ammonium, qua ternary phosphonium or tertiary sulfonium compounds.
See US. Patent 39929,678 Jo Laughlin et at., issued December 30, 1975 at column 19, line 38 through column I line 48 for examples of zwitterionic surfactants.

E. Catlonic Surfactants Cat ionic surfactants can also be included in detergent compositions of the present invention. Suitable cat ionic svrfac-tents include the qua ternary ammonium surfactants having the formula:
2 CR2(oR3)y~rR4(0R3)y]2R5N X
wherein R is an alkyd or alkyd Bunnell group having prom about 8 to about 18 carbon atoms in the alkyd chain; each R3 is selected from the group consisting of -CH2CH2-, -CH2CH(C
-CH2CH(CH20H)-, -C~2CH2CH2-, and mixtures thereof; each R is ; selected from the group consisting of Cluck alkyd, Claus hydroxy-alkyd, bouncily, ring structures formed by joining the two R4 groups -CH2CHOHCHOHCOR6CHOHCH20H wherein R6 is any hoaxes or ; 25 hoaxes polymer having a molecular weight less than about 1000, and hydrogen when y is not OX R5 is the same as R4 or is an alkyd 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 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.
Preferred of the above are the alkyd qua ternary ammonium surfactants, especially the mono-long chain alkyd surfactants described in the above formula when R5 is selected from the same groups as R4. The most preferred qua ternary ammonium surfactants are the chloride, bromide and methyl sulfate C8~C16 alkyd in-methyla~monium salts, C8~C16 alkyd di(hydroxyethyl)methylammonium I' J Lo salts, the C8-C16 alkyd hydroxyethyldimethylammonium slats, and Jo C8-C16 alkyloxypropyl trimethylammonium salts. Of the above, decal trimethylammonium methyl sulfate, laurel trimethylammonium chloride, myristyl trimethylam~onium bromide and coconut in-methylammonium chloride and methy1sulfate are particularly pro-furred.
Detergent Builders Detergent compositions of the present invention can optional-, lye comprise inorganic or organic detergent builders to assist in j 10 mineral hardness control. These builders can comprise from 0 to about 80% by weight of the composition. When included, these builders typically comprise up to about 60% by weight of the ' detergent composition. Built liquid formulations preferably comprise from about 10 to about 25% detergent builder while built 15 granular formulations preferably comprise from about 10 to about 50% by weight detergent builder.
Suitable detergent builders include crystalline aluminosili-gate ion exchange materials having the formula.
Nests (Sue XH20 20 wherein z and y are at least about 6, the mole ratio of z to y is 'I from about 1.0 to about 0.5; and x is from about 10 to about 264.
Amorphous hydrated aluminosilicate materials useful herein have the empirical formula MZ(2Al02~YSi~2) 25 wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2; and y is 1, this material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of Cook hardness per gram of an hydrous aluminosili-gate.
The aluminosilicate ion exchange builder materials are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline alu~inosilicate 3 ion exchange materials contain from about 18% to about 22% water 35 jr their crystal matrix. The preferred crystalline aluminosili-gate 10n exchange materiels are further characterized by a `
., ~32~
,, particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron. More preferred ion exchange ' materials have a particle size diameter of from about 0.2 j 5 micron to about microns. The term "particle size diameter"
represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope. The crystalline aluminosilicate ion exchange materials are usually further characterized by their calcium ion exchange capacity, which ¦ is at least about 200 my. equivalent of Cook water hardness/g.
i; of aluminosilicate, calculated on an an hydrous basis, and ¦ which generally is in the range of from about 300 my. erg to about 352 my. erg The aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Cay/
gallon/minute/gram/gallon of aluminosilicate (an hydrous I` basis), and generally lies within the Lange of from about 2 grains/gallon/minute/gram/gallon to about 6 grains/gallon/
minute/gram/gallon, based on calcium ion hardness. Optimum aluminosilicates for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram~
` gallon.
,, I The amorphous aluminosilicate ion exchange materials I usually have a My exchange capacity of at least about 50 my.
en. Cook. ~12 my. My+ go and a My exchange rate ox at least about 1 graintgallon/minute/gram/gallon. Amorphous materials do not exhibit an observable diffraction pattern ; 30 when examined by Cut radiation (1.54 Angstrom Units).
Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A
method for producing aluminosilicate ion exchange materials is disclosed in US. Patent 3,985,669 to Cromwell, et at.
issued October 12, 1976~ Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available `:
`

`
.

I

under the des1gna~ions elite A, elite P (B), and Zealot X.
In an especially preferred embodiment, the crystalline alumina-silicate ion exchange Muriel has the formula Nulls] XH2 S wherein x is from about 20 to about 30, especially about 27.
Other examples of detergency builders include the various water soluble alkali metal amronium or substituted ammonium phosphates 9 polyphospha~es, phosphona~es, polyphosphonates, carbonates, sockets, borate, polyhydroxysul~onates9 pulse-tales, carboxylates, and polycarboxylates. Preferred are the alkali metal, especially sodium; salts ox the above.
Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophospha~e, polymeric metaphate having a degree of polymerization of from about 6 to 21, and orthophosphate. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethanes 1-hydroxy-1,I-dlphosphonic acid and the sodium and potassium salts of ethanol Tracy-phonic acid. Other phosphorus builder compounds are disclosed in US. Patents 35159,SB1; 3,213,030; 3,422,021; 3,422~137; 3,400,176 and 3t400,148.
Examples of non phosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydratc, and silicate having a mole ratio of Sue to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
Useful water-soluble, non phosphorus organic builders include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxy1ates9 polycarboxylates and polyhydroxy-sulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium lithium; ammonium and substituted ammon~um salts of ethylenediamine tetraacetic acid, nitrilotri-acetic acid, oxydisuccin~c acid, mellitic acid, Bunsen polycar-boxlike acids, and citric acid.
; 35 Highly preferred polycar~oxylate builders are disclosed in US. Patent No 3,308,067 to Doyle issued March 7, 1967. Such .

. `'`. ;, .

- I -materials include the water-soluble salts of home- and copolymers of aliphatic carboxylic acids such as malefic acid, itaconic acid, mesa conic acid fumaric acid, coo-nitric acid citraconic acid and methylenemalonic acid , 5 Other builders include the carboxylated carbohydrates disclosed in US. Patent 3,723,322 to Doyle issued March 28 t OWE
! Other useful builders are sodium and potassium car-boxymethyloxymalonate, car~oxymethyloxysuccinate, is-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxy-late phloroglucinol trisulfonate~ water-soluble polyacry-lazes (having molecular weights of from about 2l000 to ¦ about 200,000 for example), and the copolymers of malefic ¦ android with vinyl methyl ether or ethylene.
Other suitable polycarboxylates are the polyacetal ; carboxylates disclosed in US. Patent 4,144,226, to Jo Crutch field et at. issued March 13, 1979, and US. Patent 4,246,495, to Crutch field et at., issued March 27, 1979.
These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glue oxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemical-lye stable end groups to stabilize the polyacetal car boxy-late against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a f s urfactant.
. Other useful detergency builder materials are the ¦ "seeded builder" compositions disclosed in Belgian Patent Jo No. 798,856, issued October 29, 19730 Specific examples of such seeded builder mixtures are: 3:1 wt. mixtures of sodium carbonate and calcium carbonate having 5 micron i particle diameter; 2.7:1 wt. mixtures of sodium Suzuki-carbonate and calcium carbonate having a particle die-meter of 005 microns; 20:1 wt. mixtures of sodium sues-quicarbonate and calcium hydroxide having a particle diameter of Wool micron; and a 3:3:1 wt. mixture of I: sodium carbonate, sodium acuminate and calcium oxide having a particle diameter of 5 microns.

I

~2~3 I
Other Optional Deterrent Ingredients Other optional ingredients which can be included in detergent compositions of the present invention, in their conventional art-established levels for use (i.e., from O to about 20%), include solvents, bleaching agents, bleach activators, Celsius-pending agents, corrosion inhibitors, dyes, fillers, optical brighteners, germicides, pi adjusting agents (monoethanolam;ne, sodium carbonate, sodium hydroxide, etch enzymes, enzyme-stabil-icing agents, perfumes, fabric softening components, static control agents, and the like.
Detergent Formulations Granular formulations embodying the detergent compositions of the present invention can be formed by conventional techniques, i.e., by slurring the individual components in water and then atomizing and spray-drying the resultant mixture, or by pan or drum granulation of the ingredients. Granular formulations preferably comprise from about 10 to about 30% detergent surface lent, usually anionic.
Liquid fnrmula~ions embodying the detergent compositions can be built or unbolt. If unbolt, these compositions conventional-lye contain approximately 15 to 50% total surfactant, from O to 10%
of an organic base such as a moo-, do-, or tri-alkanol amine, a neutralization system such as an alkali metal hydroxide and a lower primary alcohol such as ethanol or isopropanola and approxi-mutely 20 to 80X water. Such compositions are normally home-generous single phase liquids of low viscosity (approximately 100 to 150 centipoise at 75F).
Built liquid deterrent compositions can be in the form of single phase liquids provided that the builder is solubilized in the mixture at its level of use. Such liquids conventionally contain 10 to 25~ total surfactant, 10 to 25~ builder which can be organic or inorganic, 3 to 10% of a hydrotrope system and 40 to 77~ water Liquids of this type also have a low viscosity (100 to 150 centipoise at 75F). Built liquid detergents incorporating components that form heterogeneous mixtures (or levels of builder that cannot be completely dissolved) can also comprise detergent r i compositions of the present invention. Such liquids conventional-my employ viscosity modifiers to produce systems having plastic shear characteristics Jo maintain stable dispersions and to prevent phase separation or solid settlement.
Near Neutral Wash OH Detergent Formulations While the detergent compositions of the present invention are operative within a wide range of wash pus (erg. from about 5 to about 12), they are particularly suitable when formulated to provide a near neutral wash pry i.e. an initial pi of from about ! 10 6.0 to about 8.5 at a concentration of from about 0.1 to about 2%
by weight in water at 20C. Near neutral wash pi formulations are better or enzyme stability and fur preventing stains from set-tong. on such formulations, the wash pi is preferably from about 7.0 to about 8.5, and more preferably from about 7.5 to about 8Ø
Preferred near neutral wash pi detergent formulations are disclosed in Canadian Application Serial No. 428,642 to JAM
Wits and PUCE Goffinet, filed May 20, 1983. These proofread formulations c~nEYrise:
(a) from about 2 to about 60% (preferably from about 10 to about 25%) by weight of an anionic synthetic surfactant as pro-piously defined;
(b) from about 0.25 to about 12% preferably from about 1 to about 4X) by weight of a cosurfactant selected from the group consisting of:
(i) qua ternary ammonium surfactants having the formula:
~R2(op~3)y][R4(oR3)y]2R5N~-wherein R , each R3, R4, R5, X and y are as previously defined;

; 30 it doctrinaire ammonium surfactants having the formula:
wrier wrier) ]2N+R3N+R5[R4(oR3)y~2 (X I
wherein R , R , R , y and X are as defined above; portico-laxly preferred are toe CB-C16 alkyd pentamethylethylene-Damon chloride, bromide and methyl sulfate salts;
it amine surfactants having the formula:

....
.1 - 2g -, tR2(0R3)~[R4(0R3~Y3R5N
, wherein R , R R , R5 and y are as defined above; portico-I, laxly preferred are the C12-C16 alkyd dim ethyl ammonias (iv) Damon surfactants having the formula:
o'er) owe) ~NR3NR5~R4(oR3)y~
wherein I I R4, R5 and y are as defined above; portico-' laxly preferred are the C~2-C16 alkyd dim ethyl dominoes;(v) amine oxide surfactants having the formula:
~R2 (or ) ] ~R4 o'er yearn lo wherein R , R , R , R5 and y are as defined above; portico-i laxly preferred are the C12 C16 alkyldimethyl amine oxides, i and (vi) Damon oxide surfactants having the formula:
[R OR yore OR yore NO OR (o'er]

> wherein R2, R3, R4, R5 and y are as defined above; preferred are the C12-C16 alkyd trimethylethylene Damon oxides) and (c) from about 5% to about 40% by weight (preferably 7 to about 30X by weight, and most preferably from about 10 to 20% by weight) of a fatty acid containing from about lo to about I
carbon atoms (preferably a ClO-Cl4 saturated fatty acid or mixture , thereof); the mole ratio of the anionic surfactant to the Caesar-fact ant being at least 1 and preferably from about 2:1 to about 20:1.
US Such compositions also preferably contain from about 3 to I; about 15g by weight of an ethoxylated alcohol or ethoxylated alkyd phenol non ionic surfactants) as previously defined. Highly preferred compositions of this type also preferably contain from about 2 to about lo by weight of citric acid and minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffering agents phase regulants, hydrotropes, enzymes, enzyme stabilizing agents, palisades suds regulants, pacifiers; anti-~,~ oxidants bactericide, dyes, perfumes and brighteners such as those described in US. Patent 4,285,841 to Burr et at., issued 35 August 25, 1981.
I`
. Jo I' .
'` ` :

`` .~2~3~36 - I -~ecific Embodiments of Detergent Causations Awkwardness to the Present Invention Embodiment I
The following embodiments illustrate; but are not limiting of detergent compositions of the present invention:
A granular detergent composition is formulated as follows:
Component Wt. %
Compound of Example 1 1.0 Sodium C14-C15 alkylethoxySulfate 10.7 10 C13 linear alkyd Bunsen sulfonic acid OWE
C12-C14 alkylpolyethoxylate I 5 Sodium Tulane sulfonate 1.0 Sodium tripolyphosphate 32.9 : Sodium carbonate 20.3 15 Sodium silicate 5.B
Minors and water Balance Jo 100 The components are added together with continuous mixing and then spray dried to form the composition.
: Embodiment II
mu A liquid detergent composition is formulated as follows:
Component Wt.
Compound of Example 1 1.0 Sodium C14-C15 alkyd polyethoxy (2.5) sulfite C 2 alkyd dim ethyl amine oxide 3.3 ye I Sodium Tulane sulfonate 5.0 Monoethanolamine 2.3 Sodium nitrilotriacetate 18.2 Minors and water Balance to 100 The components are added together with continuous mixing to form the composition.

: 35 SLY

Embodiments III and IV
Liquid detergent compositions are formulated as follows:
Component Wt. %
III IVY
Compound of Example 1 1.5 1.5 C14-C15 alkylethoxysu1furic acid 10.8 C14-C15 alkylpolyethoxy (2.25) sulfuric acid lQ~8 ? C13 linear alkylbenzene sulfonic acid 7.2 7.2 C12 alkyd trimethylammonium chloride 1.2 1.2 C12-C13 alcohol polyethoxylate (6.5) 6.5 6.5 Coconut fatty acid 15.0 15.0 Citric acid MindWrite 6.9 4.0 Diethylenetriami~e pentaace~ic acid 0.9 0.9 Protozoa enzyme 0.8 0.8 '. 15 Aimless enzyme 0.3 0.3 . Monoethanolamine 13.6 2.0 Tr;ethanolamine 3.0 4.0 Jo Sodium hydroxide - 2.0 i Potassium hydroxide - 2.8 1,2-Propanediol 5.0 5.0 Ethanol 3.0 7.0 Sodium format 1 0 1.0 , Sodium Tulane sulfonate S 0 `¦ Minors and water Balance to 100 Embodiment IV is prepared by adding the components together with continuous mixing, in the following order to produce a clear 1 liquid: a paste premix of the alkylbenzene sulfonic acid, 0.9 -I parts of the sodium hydroxide, propylene glycol, and 2.3 parts of the ethanol; a paste premix of the alkylpolyethoxysulfuric acid, 1.1 parts of the sodium hydroxide and 3.1 parts of the ethanol;
alcohol polyethoxylate; premix of monoethanolamine, triethanol-amine and brighteners, 1.5 parts potassium hydroxide; balance of the ethanol; citric acid; format 1.4 parts potassium hydroxide;
fatty acid, pentaacetic acid, alkyd trimethylan~onium chloride;
adjust pi to about 8.4 with potassiunl hydroxide, water or citric .~:

`"''' ,.

~2~L3~

Jo acid enzymes; compound of Example 1 (50% aqueous solutions and perfume. Embodiment III can be prepared in a similar manner.
Embodiment V
A liquid detergent composition is formulated as follows:
Component Wit X
Compound of Example 1 Sodium C12 alkylpolyethoxy (3) sulfate 12.6 - C12-C13 alcohol polyethoxylate t6.5) 23.4 Monoethanolamine 2.0 10 Ethanol 9.0 Citric acid MindWrite 0.8 Minors and water Balance to 100 The components are added together with continuous mixing to form the composition.
WHAT IS CLAIMED IS:

, I

' I .

r

Claims (6)

Claims:

1. A water-soluble ethoxylated polyamine compound having clay soil removal/anti-redeposition properties and having the formula:
where in A1 is R is H or C1-C4 alkyl or hydroxyalkyl; each R2 is C1-C4 alkyl or hydroxyalkyl, or the moiety -L-X; X is a nonionic group, an anionic group or mixture thereof; R3 is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl, or alkaryl group having p substitution sites; R4 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units; L is a hydrophilic chain which contains the polyoxyalkylene moiety -[(R5O)m(CH2CH2O)n]-, wherein R5 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety (CH2CH2O)n-, comprises at least about 50% by weight of said polyoxyalkylene moiety; m is from 0 to 10; n is at least about 3; p is from 3 to 8; q is 1 or 0, t is 1 or 0, provided that t is 1 when q is 1.

2. A compound according to claim 1 wherein R3 is a substituted C3-C6 alkyl, hydroxyalkyl or aryl group; A1 is ; p is from 3 to 6.

3. A compound according to claim 2 wherein each R2 is the moiety -L-X.

4. A compound according to claim 3 wherein m and n are numbers such that the moiety -(CH2CH2O)- comprises at least about 85% by weight of said polyoxyalkylene moiety.

5. A compound according to claim 4 wherein X is H.

6. A compound according to claim 4 wherein m is 0 and n is at least about 12.