CA1210009A - Ethoxylated amine polymers having clay soil removal/anti-redeposition properties useful in detergent compositions - Google Patents

Abstract

ETHOXYLATED AMINE POLYMERS HAVING CLAY SOIL
REMOVAL/ANTI-REDEPOSITION PROPERTIES USEFUL IN
DETERGENT COMPOSITIONS

ABSTRACT

Water-soluble ethoxylated amine polymers having clay soil removal/anti-redeposition properties, which comprise a polymer backbone other than a polyalkyleneamine backbone, and at least 2 M
groups and at least one L-X group, wherein M is a tertiary amine group attached to or integral with the backbone; X is a nonionic group, an anionic group or mixture thereof; and L is a hydrophilic chain connecting groups M and X or connecting X to the polymer backbone. L also contains the polyoxyalkylene moiety -[(R'O)m(CH2CH2O)n]-, wherein R' is C3-C4 alkylene or hydroxyalkylene, m and n are numbers such that the moiety -(CH2CH2O)n- comprises at least about 50% by weight of said polyoxyalkylene moiety, and n is at least about 3 except when the polymer backbone is a polyalkyleneimine backbone, and n is at least about 12 when the polymer backbone is a polyalkyleneimine backbone. these ethoxylated amine polymers are useful in detergent compositions.

Description

~2~

- ETHOXYLATED AMINE POLYMERS HAVING CLAY SOIL
REMOVAL/ANTI-REDEPOSITION PROPERTIES USEFUL IN
DETERGENT COMPOSITIONS
Eugene P. Gosselink TECHNICAL FIELD
The present application relates to ethoxylated amine polymers having clay-soil removal/anti-redeposition properties when used in detergent compositions.
A particularly important property of a detergent composition is its ability to remove particulate type soils from a variety of faDrics during laundering. Perhaps the most important particulate soils are the clay-type soils. Clay soil particles generally comprise negatively charged layers of aluminosilicates and posi-tively 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 have clay soil removal properties. One model requires that the compound have two distinct characteristics. The first is the ability of the compound to adsorb onto the negatively charged layers 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 and 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 U.S. Patent 4,301,044 to Wentler et al., issued November 17, 1981. Representative of such compounds are those having the formula:

R1 _ N ~(CH2)xC~O-(CH2CH20)yS03 wherein R1 is a C14-C20 alkyl group, x is 1 or an integer of from 3 to 5, and y is from 6 to 12. See also U.S. Patent 3,929,678 to Laughlin et al., issued December 30, 1975 (detergent composition containing polyethoxy zwitterionic surfactant plus other detergent surfactants); U.S. Patent 3,925,262 to Laughlin et al., issued ~2~Q9 December 9, 1975 (detergent composition containing polyethoxy zwitterionic surfactants with detergent builders); U.S. Patent 4,157,277 to Gosselink et al., issued June 26, 1979 (C4 polyoxy-alkylene zwitterionic surFactants useful in detergent composi-tions); U.S. Patent 4,165,334 to Gosselink et al., ;ssued August 21, 1979 (sulfonium-type polyethoxy zwitterionic surfactants).
These polyethoxy zwitterionic surfactants are generally compatible with other detergent surfactants such as the nonionic, zwitterionic and ampholytic types. However, as suggested in the Wentler et al. 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 surfactants form the most important class of such materials for use in detergent compositions, the lack of compati-bility between these polyethoxy zwitterionic surfactants and anionic surfactants poses a significant handicap where particulate (clay) soil removal is desired.
In addition to clay soil removal, one of the other properties mentioned in the Laughlin et al. patents with regard to these polyethoxy zwitterionic 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 can redeposit onto the surface of the fabric. This redeposited soil causes a dulling or "graying" effect which is especially noticeable on white fabrics. Because soil is normally hydro-phobic, this graying ef~ect is a particularly important problem for those fabrics made in total or in part from hydrophobic fi-bers, 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 surfac-tants, there are a var;ety of other compounds which can be used as anti-redeposition 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 U.S. Patent 39719,647 to Hardy et al., issued March 6, 1973.

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Another class of anti-redeposition agents are the cellulose and carboxymethylcellulose derivatives d;sclosed in U.S. Patent 3,597,416 to Diehl, issued August 3, 1971 (ionic combination of dodecyltrimethyl phosphonium chloride and sodium carboxymethyl-cellulose), and U.S. Patent 3,523,088 to Dean et al., issued August 4, 1970 (combination of alkali metal carboxymethylcellulose and hydroxypropylcellulose). A mixture of compounds has also been used to provide not only anti-redeposition, but also clay soil removal properties. See U.S. Patent 4,228,044 to Cambre, issued October 14, 19~30, which discloses detergent compositions having anti-redeposition and clay soil removal properties which can comprise a nonionic alkyl polyethoxy surfactant, a polyethoxy alkyl quaternary cationic surfactant and a fatty amide surfactant.
These anti-redeposition agents do have a number of signifi-cant handicaps. While effect;ve to keep soil suspended, these compounds may lack additional clay soil removal properties.
Moreover, as disclosed in the Diehl and Dean et al. patents, mixtures of compounds can be required to achieve the anti-redepo-sition benefit~ To the extent that there are combined anti-rede-position/clay soil removal benefits as disclosed in the Cambre patent, mixtures of compounds are also required.
It is therefore an object of the present invention to provide compounds useful in detergent compositions which provide particu-late soil, especially 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.
It is yet another object of the present invention to provide compounds useful in detergent compositions having anti-redeposi-tion 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.
These and further objects of the present invention are hereinafter disclosed.

~2~ 9 These and further objects of the present invention are hereinafter disclosed.
BACKGROUND ART
U. S. Patent 3,301,783 to Dickson, et al., issued January 31, 1967, discloses oxyalkylated, acylated, alkylated, carbonylated and olefinated derivatives of polyalkyleneimines, in particular polyethyleneimines (PEIs). For the oxyalkylated derivatives, the alkylene oxide (e.g. ethylene oxide) is reacted with the poly-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 e~hoxylated PEIs disclosed are Examples 1-07 and 1-8 formed by condensing 105 and 200 moles, respectiYely, of ethylene oxide with a 900 M.W. PEI.
The degree of ethoxylation calculates out to about 4.5 and about 8 ethoxy groups per reactive site, respectively. See also Examples 27-05 and 27-06 which disclose ethoxylated polypropyleneimines (M.W. 500) which have about 4 and about 8 ethoxy units per reac-tive site, respectively. Amongst the numerous disclosed uses o~
these polyalkyleneimine derivatives is a teaching that they are useful as detergents, softening agents, and anti-static agents.
2D Preferred uses disclosed by this patent are as chelating agents, lubricating oil additives, emulsifying agents, and cutting oils.
U.S. Patent 2,792,371 to Dickson, issued May 14, 1957, teaches a process for breaking petroleum emulsions with oxy-alkylated tetraethylene pentaamines (TEPA). Ethoxylated TEPAs specifically disclosed include those having about ~ (Example 3aa), about 7 ~Example 4aa), about 8.5 (Example Sa) and about 15.5 (Example Bc) ethoxy units per reactive site. Similarly, U.S.
patent 2,792,370 to Dickson issued May 14, 1957, teaches a process for breaking petroleum emulsions with oxyalkylated triethylene tetramines (TETAs) including those having about 5.5 (Example 3aa), about 7.5 (Example 4aa~, about 9 (Example 5a) and about 16.5 (Example Bc) ethoxy units per reactive site. See also U. S.
patent 2,792,372 to Dickson, issued May 14, 1957, (oxyalkylated higher PEAs used to break petroleum emulsions); U. S. patent

2,792,369 to Dickson, issued May 14, 1957 (oxyalkylated diethylene triamines used to break petroleum emulsions).

~Z~ 9 - U. S. Patent 4,171,278 to Andree et al., 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:

(cH2-cHo)mH R4 (CH2CHO)nH
~4 A -N \
(CH2CHO)oH
~4 1 1 C16 alkyl; R2 is H or C1-C16 alkyl; R1 + R2 have 6-20 carbon atoms; R4 is H or methyl; m, n, and o, are each O to 3 and A is bridging group such as (CH)x N/

_ y (cH2c\Ho)pH

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 ~uly 5, 1973, which discloses a washing agent for graying prevention formed by the reaction product of a PEI with an alkylglycidylether and ethylene oxide (2-hydroxyethyl moiety at each reactive site when ethoxylated).
U. S. Patent 3,838,057 to Barnes et al., issued September 24, 1974, discloses toilet bars containing ethoxylated quaternary ammonium compounds, including ethoxylated, quaternized PEIs taught to be useful in the detergent, textile, and polymer industries, as anti-static and softening agents. These ethoxylated quaternized PEIs have the formula:

H(-~ - CH~ - CH2-) HnX~

~2~ 9 wherein R1 is a compatible quaternary nitrogen substituent; n is at least 2; x is from 3 to 40; and X is a compat;ble anion.
Preferred compounds are those where R1 is a C8 - C22 alkyl group or the group:
R'COO(EO)y~CH2CHOHCH2-where R' is a C8 - C22 alkyl group and y is from 3 to 40. See also U. S. Patent 4,179,382 to Rudkin et al. 3 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 al., published May 30, 1979, which disclose ethoxylated quaternized polyamines having C10 to C24 alkyl or alkenyl groups attached to one of the nitrogen atoms useful as fabric softeners.
There are several patents which disclose detergent composi-tions, shampoo compositions and the like containing slightly ethoxylated PEIs (ethylene oxide:PEI weight ratio of 4:1 or less) to enhance the deposition and retention of particulate substances such as antimicrobials. See9 for example, U.S. Patent 3,489,686 to Parran, issued January 13, 1970; UOS. Patent 3,580,853 to Parran, issued May 25, 1971; British Patent Specification 1,111,708 to Procter & Gamble published May 1, 19689 U.S. Patent 3,549,546 to Moore, issued December 22, 1970; and U.S. Patent 3,549,542 to Holderby, issued December 22, 1970.
DISCLOSURE OF THE INVENTION
The present invention relates to water-soluble ethoxylated amine polymers having clay soil remo~al/anti-redeposition properties useful in detergent compositions. These polymers comprise a polymer backbone other than a polyalkyleneamine backbone, at least 2 M groups and at least one L-X group, wherein M is a tertiary amine group attached to or integral with the backbone; X is a nonionic group, anionic group or mixture ther~of;
and L is a hydrophilic chain connecting groups M and X or connecting X to the backbone. L also contains the polyoxyalkylene moiety -~(R'O)m(CH2CH20)n]-9 wherein R' is C3-C4 alkylene or hydroxyalkylene, m and n are numbers such that the moiety -(CH2CH20)n- comprises at least about 50% by weight of said polyoxyalkylene moiety, and n is at least about 3, except when the -~lZ~ 9 - polymer backbone is a polyethyleneim;ne backbone, and n ;s at least about 12 when the polymer backbone is a polyethylene;m;ne backbone.
The ethoxylated am;ne polymers of the present ;nvention provide clay soil removal benef;ts wh;le be;ng an;onic detergent surfactant compatible. At most wash pHs, it is believed nitrogen atoms of the polymer are protonated to form positively charged centers which, together with the remaining polar nitrogen atoms, cause adsorption of the polymer onto the negatively charged layers of the clay particle. It is also believed that the hydrophilic ethoxy units attached to the polymer backbone swell the clay part;cle so that it loses ;ts cohesive character and is swept away in the wash water.
The anti-redeposition benefits provided by these ethoxylated amine polymers are also believed to be due to the positively charged centers which, together with the remaining polar nitrogen atoms, cause it to be adsorbed onto soil suspended in the wash water. As more and more of these polymers adsorb onto the sus-pended soil, it becomes encased within a hydrophilic layer pro-vided by the attached ethoxy units. As such, the hydrophilicallyencased soil is prevented from redepositing on fabrics, in particular hydrophob;c fabr;cs such as polyester, dur;ng the laundering cycle.
Ethoxylated Am;ne Polymers The water-soluble ethoxylated am;ne polymers of the present ;nvention comprise a polymer backbone other than a polyalkylene-amine backbone, and at least 2 M groups and at least one L-X
group, wherein M is a tertiary am;ne group attached to or integral with the backbone; X ;s a nonionic group, an an;onic group or mixture thereofj and L is a hydrophilic chain connecting groups M
and X, or connecting X to the polymer backbone.
As used herein, the term "polymer backbone" refers to the polymeric rrroiety to which groups M and L-X are attached to or integral with. Included with;n th;s term are oligomer backbones (2 to 4 uni~s), and true polymer backbones (5 or more un;ts).

~2~ 9 As used herein, the tèrm "attached to" means that the group is pendent from the polymer backbone, examples of which are represented by the following general structures A and B:
T M L
~ ~
X

A B
As used herein, the term "integral with" means that the group forms part of the polymer backbone, examples of wh;ch are repre-sented by the following general structures 0 and D:
M - - M
L
X X
C D
Any polymer backbone ~other than a polyalkyleneamine back-bone) can be used as long as the ethoxylated amine polymer formed is water-soluble and has clay soil removal/anti-redeposition properties. Suitable polymer backbones can be derived from the polyurethanes, the polyesters, the polyethers, the polyamides, the polyimides and ~he like, the polyacrylates, the polyacrylamides, the polyvinylethers, the polyethylenes, the polypropylenes and like polyalkylenes, the polystyrenes and like polyalkarylenes, the polyalkyleneimines, the polyvinylamines, the polyallylamines, the polydiallylamines, the polyvinylpyridines, the polyaminotriazoles, polyvinyl alcohol, the aminopolyureylenes and mixtures thereof.
As used herein, the term "polyalkyleneamine backbone" refers to polymer backbones hav~ng the following general formula:
lH2N~W- _[-R1_N_]X_ -l-Rl-N-]y~ -~-Rl-NH21z wherein Rl is C2 C12 atkylene, hydroxyalkylene~ alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no 0-N or 0-0 bonds are formed; w is I or 0; x + y + z is from 2 to 9~ and y + z is from 2 to 9. Such polymer backbones are particularly represented by the polyethyleneamines (PEAs) where p1 is ethylene, and x + y +
z is from 3 to 7. These PEAs can be obtained by reactions ~.., involving ammonia and ethylene dichloride, followed by fractional distillation. The common PEAs obtained are triethylenetetramine ~TETA) and tetraethylenepentamine (TEPA). Above the pentamines, i.e., the hexamines, heptam;nes, octamines and possibly nonamines, the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See U.S.
Paten~ 2,792,372 to Dickson, issued May 14~ 1957, which describes the preparation of PEAs.
As used herein, the term "polyalkyleneimine backbone" refers to d polymer backbones havlng ~he following general formula:
lH2Nl~ Rl-N-]X~ Rl-N-ly~ -l-Rl-NH2]z wherein R is ~f;nP~ as above; x + y ~ z is at 1east l~, M can be any compatible tertiary amine group. The tertiary amine group can be represented by the following general structures E and F: ~
- N - N

E F
Particularly preferred M groups are those represented by general structure E. The tertiary am~ne group M is also preferably Positioned close to or integral w~th the polymer backbone.
2~ In the precedinq formula, X can be any oompatible nDnionic group, anionic group or mixture thereof. SuQtable nonionic groups include Cl-C4 alkyl or hydroxyalkyl, ester ~r ether group6, preferably the acetate ester or methyl ether, respectively; hydrogen ~); or mixtures thereof. The part k ularly preferred nonionic group is H.
With regard to anionic groups, po3 2 and S03 are suitable. The particualrly preferred anionic group is S03 . It has been found that the retative percentage of anionic groups to nonionic groups can be important to the clay soil removallanti-redeposition properties provided by the ethoxylated amine polymer. A mixture of from 0 to about 30X anionic groups and from about 70 to 100~, nonionic groups provides preferred properties. A mixture of from ,~

about 5 to about 10% anionic groups and from about 90 to about 95%
nonionic groups provides the most preferred properties. Usually, a mixture of from O to about 80X anionic groups and from about 20 to 100% nonionic groups provides suitable clay soil removal/anti-redeposition properties.
The ethoxylated amine polymers of the present inventionnormally have a rat1o of groups M to groups X of 1:1. However, by appropriated copolymerization of tertiary amine, anionic (non-ionic) ~i.e. containing the group L-X), or mlxed tertiary amine/
anionic (nonionic) -s, the ratio o~ groups M to group6 X
can be varied. The ratio of groups M to group6 X can usually range fram about 2:1 to about 1:10. In preferred p~lymer~, the ratio is from ab~ut 1:1 to ab~ut 1:5. The polymers fonmed from such copolymerization are typically r~ndom, i.e. the tertiary amine, ~nio~iC (nonionic), or mixed tertiary amine/anionic (nonionic) . ?~S o~polymeri~e in a nOIlr~reA~ i ng sequenc~.
The units which contain groups M and groups L-X most prefer-ably comprise 100% of the ethoxylated amine polymers of the present invention. However, inclusion of other units (preferably nonionic) in the polymers is also permissible. Examples of other units include the acrylamides and the vinylethers. These other units can comprise from O to about 90~ of the polymer (from about lO to lOOX of the polymer being units containing M and L-X
groups). Typically, these other units comprise fro~ O to about 50X of the polymer (from about 50 to 100% of the polymer being units containing M and L-X groups).
The number of groups M and L-X usually ranges from about 2 to about 200. Typically, the number of groups M and L-X is from about 3 to about 100. Preferably, the number of groups M and L-X
is from about 3 to about 40.
Other than moieties for connecting groups M and X, or for attachment to the polymer backbone, hydrophilic chain L usually consists entirely of the polyoxyalkylene moiety -[(R'O)~-(CH2CH20)n]-. The moieties ~(R'O)m~ and -(CH2CH20~n- of the polyoxyalkylene moiety can be mixed together or preferably form blocks of ~(R'O)m- and -~CH2CH23)n- moieties. R' is preferably ~L2~ g C3 H6 (propylene); m is preferably from 0 to about 51 and most preferably 0, i.e. the polyoxyalkylene moiety consists entirely of the moiety -(CH2CH20)n-. The moiety -(CH2C~I20)n- preferably comprises at least about 85% by weight of the polyoxyalkylene moiety, and most preferably 100% by weight (m is 0). For the moiety -(CH2CH20)-n, n is usually from about 3 to about 100.
Typically n is from about 12 to about 42.
A plurality (2 or more) of moieties -L-X can also be hooked toyether and attached to group M or to the polymer backbone, examples of which are represented by the following general struc-tures G and H:
T L I L
l L X X
X X
G H
Structures G and H can be formed, for example, by reacting glycidol with group M or the polymer backbone, and then ethoxylatin~ the subsequently formed hydroxy groups.
The level at which the ethoxylated amine polymers of the present in~ention can be present in the detergent compositions can vary widely depending upon the polymer used, the type of detergent formulation (liquid, granular), and the benefits desired. These compositions can be used as laundry detergents, laundry additives, or laundry pretreatments. Generally, these polymers can be included in an amount of from about 0.05 to about 95% by weight of the composition, with a usual range of from about O.l to about 10%
by weight for laundry detergents. Preferred detergent composi-tions comprise from about 0.5 to about 5% by weight of the polymerof the present invention. For these preferred compositions, the polymer is typically present at from about 1 to about 3% by weight. The polymer is normally present at a level that provides from about 2 ppm to about 200 ppm, preferably from about 10 ppm to about lO0 ppm, of the polymer in the wash solution at recommended U.S. usage levels, and normally from about 30 ppm to about 1000 ~Z~Q~9 ppm, preferably from about 50. ppm to about 500 ppm for European usage level 5 .
Representative classes of ethoxylated amine polymers of the present invention are as follows:
A. Polyurethane, Polyester, Polyether, Polyamide or Like Polymers One class of suitable ethoxyla~ed amine polymers are derived from polyurethanes, polyesters, polyethers, polyamides and the like. These polyrners comprise units selected from those having formulas I, II and III:
(A1-R1-A1) _R2 N - R3 I (R )k-[(C3H60)m(CH2CH20)n~-X

15 - R~
- (A -R1 - A1) R2 -N R3 -- R~ _ . 20- - (Al Rl Al ~ _R2 ~ R3 _ ( )k-[(~3H50)m(CH2CH2Q)n]-X
III
1l 1l wherein A is -NC-, -CIN-, -CO-, -OC- or -C-;

x is O or 1; R is H or Cl-C4 alkyl or hydroxyalkyl; R1 is C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units, provided that no O-O or O-N bonds are formed with A1; when o x is 1, R2 is -R5- except when A1 is -~-, or is -~OR7)y- or -ORS-provided that no O-O or N-O bonds are formed with A1, and R3 is , ~

~2~

o -R5- except when Al~s -~-, or is -(R70)y- or -R50- provided that no 0-0 or 0-N bonds are formed with Al; ~hen x is 50, R is -(oR73y~, -ORS-, -coR5 - ~ -ocR5 - ~ -~oR5-~ -IN~R -, -IN~lOR -, -~R -, or -o~R5- and R3 is -R5-: R4 is C1-C4 alkyl or hydroxyalkyl;

R5 is C1-C12 alkylene, hydroxyalkylene, cycloalkylene, alkenylene, arylene, or alkarylene; R ls H or R4; R7 is C2-03 alkylene or hydroxyalkylene; X is R, S03 , or a mixture thereof; k is 0 or 1;
m is from 0 to about 5; n is at least about 3; m and n are numbers such that the moiety -~CH2CH20)n- comprises at least about 85% by weight of the moiety -~(C3H60)m(CH2CH20)n]-; y is from 2 to about 20; the number of u , v and w are such that there are at least 2 N
groupS and at least 2 X groups.

In the above formulas, A1 is preferably NC- or -~N-2 ~ ~;
A i5 preferably -0-; x is preferably 1; and R is preferably H.
R1 can be linear (e.y. -CH2-CH2-CH2-1 -CH2-CH-) or branched ~H3 (e.g. -CH2-CH, -C~2 ~ -) alkylene, hydroxyalkylene, alkenylene, H3 ~
cycloalkylene, alkarylene or oxyalkylene; when R is a C2-C3 oxyalkylene moiety, the number of oxyalkylene units is preferably from 2 to about 12; R1 is preferably C2-C~ alkylene or phenylene, and most preferably C2-C6 alkylene (ethylene, propylene, hexamethylene). R is preferably -oR5- or -(oR7); R3 is preferably -R~0- or (oR7)y; R4 is preferably methyl. Like Rl, R can be linear or branched, and is preferably C2-C3 alkylene; R6 is preferably H or Cl-C3 alkyl; R7 is preferably ethylene; X is preferably H or methyl; k is preferably 0; m is preferably 0; r and 5 are each preferably 2; y is preferably from 2 to abou~ 12.
In the above formulas, n is preferably at least about 6 when the number of N and X groups are each 2 or 3; n is most preferably at least about 12, with a typical range of from about 12 to about 42 for all ranges of u + v + w. For homopolymers (v and w are 0), u is preferably from about 3 to about 40, and ls most preferably from about 3 to about 20. For random copolymers (u is at least 1 or preferably 0), v and w are each preferably from about 3 to about 40.
B. Polyacrylate, Polyacrylamide, Polyvinylether or Like Polymers Another class of suitable ethoxylated amine polymers are derived from polyacrylates, polyacryla~ides, polyvinylethers and the like. These polymers comprise units selected from those having formulas IV, V and VI.
~Rl~
ll ~u lS 2 ~ A ) ~R ).
R3-~ (R~k-t(C3H60)m(cH2cH20)]n X
IV

20 , R1 - _ L ¦ _ v _ ¦ -w tAl)j 2~(A )j ~ N -(R )2 (R )k-[(C3H60)m(CH2CH~O)]n-X
V VI

wherein A1 is -O-, -.NC-9 -NCO-, -CNC-, -CN-, -OCN-~ R R ~ R

Il 11 l I 11 -OC-, -0~0-, -CO-, or -ycp-;

R is H or Cl-C4 alkyl or hydroxyalkyl; R1 is substituted C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene, or alkarylene or C2-C3 oxyalkylene; each R2 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; R3 is C1-C4 alkyl or ~:`' t~

~2~Q9 hydroxyalkyl, or the moiety -(R2)k-~(C3H60)m(CH2CH20)n]-X; each R
is Cl-C4 alkyl or hydroxyalkyl, or together form the moiety -(CH2)r-A2-(CH2)s-, wherein A2 ;s -O- or -CH2-;R5 is c2-C3 alkylene or hydroxyalkylene; X is R, S03 , or a mixture thereof; j is 1 or O; k is 1 or 0; m is from O to about S; n is at least about 3; m and n are numbers such that the moiety -(CH2CH20)n- comprises at least about 85X by weight of the moiety -~(C3H60)m(CH2CH20)n~-; r is 1 or 2, s is 1 or 2 and r + s is 3 or 4; the number u, v and w are such that there are at least 2 N groups and at least 2 X
groups.
O O
In the above formulas, Al is preferably -~N-, ~0- or -0-;

A2 is preferably -O-, R is preferably H. R1 can be linear (e.g.

CH2-CH-CH2-, -CH ~ -) or branched (e.g. -CH2-~-, -CH2CH-, ICH3 l?
-CH ~ 9 -CH2 -) substituted alkylene, hydroxyalkylene, ~ ¢~2 alkenylene, alkarylene or oxyalkylene; Rl is preferably C2-C6 alkylene and most preferably C~H3 -CH2CH- or CH2-C-~ Each R2 is preferably C2-C3 alkylene; R3 is preferably methyl; each R is preferably methyl; X is preferably H or methyl; j is prefPrably l; k is preferably O; m is preferably O; r and s are each preferably 2.
In the above formulas, n, u, v and w can be varied according to the n, u, v and w for the polyurethane and like polymers.
C. Polyalkyleneimine or Like Po1ymers Another class of suitable ethoxylated amine polymers are derived from polyalkyleneimines and the like. These polymers have the general formula YII:

/

(R )k-~(C3H60)m(CH2CH20)n]-X
[(R2)-N^]--[Rl-N-]-X -[-Rl-N ]-y -~-Rl~l]z ( 3)k-~(c3H6o)m(cH2cH2o)nJ-x (R3)k-[(c3H6o)m(cH2cH2o)n]-x ~ VII
wherein p1 is C2 - C12 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C2-C3 polyoxyalkylene moiety havin~ from 2 to ab~ut 20 oxalkylene units; R2 is Cl-C4 alkyl or hydroxyalkyl, or the moiety -QR3)k-[(C3H6o)m(CH2CH2o)n]-X;
R is Cl-C12 alkylene, hydroxyalkylene, alkenyl~ne, arylene or alkarylene; X is H, So3, or mixtures thereof; k is 1 or 0; m is frcm 0 to a~out 5; n is at least ab~ut 12; m and n are numbers such that ~he moiety -(CH~CH2O)n-oomprises at least about 85~ by weight of the moiety S )m(CH2CH2O)n] ; x + y + z is at least 10.

In the above formulas, A is preferably 0-, Rl can be varied like pl of the polyurethane and like polymers; R2 is preferably methyl or the moiety -(R3)-k[(C3H6o)m(CH2CH2o)n]-X; each R3 is preferably C2-C3 alky1ene; X is preferably H; k is preferably 0; m is preferably 0.
In the above formulas, n has a typical range of from about 12 to about 42 for all ranges of y ~ z.
Preferred ethoxylated amine polymers of this class are the ethoxylated C2-C3 polyalkyleneimines. Particularly preferred ethoxylated polyalkyleneimines are the ethoxylated ethyleneimines (PEls). These preferred polymers have the general formula:
~N]--[CH2CH21]-x-~CH2CH2N]y~~~CH2CH2N]z ¦ ¦ ~(CH2cH2)n-x]2 ~(CH2CH2)n-x]2 (CH2CH20)n-X
VIII
wherein X, x, y, z and n are defined as before.
The PEIs used in preparing the polymers of the present invention have a molecular weight of at least about 440 prior to ethoxylation, which represents at least about 10 units. Preferred ~,.1 PEIs used in preparing these compounds have a molecular weight of from about 600 to about 1800. The polymer backbone of these PEls can be represented by the general formula:

2 [CH2cH2N]x- -~CH2cH2N]-y -[C~2CH2NH2]
wherein the sum of x, y and z represents a number of sufficient magnitude to yield a polymer having the molecular weights pre-viously specified. Although linear polymer backbones are pos-sible, branch chains can also occur. The relative proportions of primary, secondary and tertiary amine groups present in the polymer can vary, depending on the manner of preparation. The distribution of amine groups is typically as follows:
-CH2CH2-N~2 30X
-CH2CH2-NH- 40~
-CH2C~2-N- 30%
Each hydrogen atom attached to each nitrogen atom of the PEI
represents an active site for subsequent e~hoxylation. These PEIs can be prepared9 for example by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing PEls are disclosed in U.S.
Patent 2,182,306 to Ulrich et al., issued December 5, 1939; U.S.
Patent 3,033,746 to Mayle et al., issued May 8, 1962; U S. Patent 2,208,095 to Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839 to Crowther, issued September 17, 1957; and U.S. Patent 2,553,696 to Wilson, issued May 21, 1951.

As defined in the preceding formu1as, n is at least about 12 for the ethoxylated PEIs. However, it should be noted that the minimum degree of the ethoxylation required for suitable clay soil removal/anti-redeposition performance can increase as the mole-cular weight of the PEI increases, especially much beyond about 1800. Also, the degree of ethoxylation for preferred compounds increases as the molecular weight of the PEI increases. For PEIs having a molecular weight of at least about 600, n is preferably at least about 12, with a typieal range of from about 12 to about .., ,~

42. For PEIs having a molecular weight of at least 1800, n is preferably at least about 24, with a typical range of from about 24 to 42.
D. Diallylamine Polymers Another class of suitable ethoxylated amine polymers are those derived from the diallylamines. These polymers cornprise units selected from th~se having formulas IX and X:
--(CH2)y (CH2) \~CH2~/

~N ~

(R )k-~(C3H60)m(CH2CH20)n]-X
_ IX
(CH2)y (CH2)`---\~CH2)X
N -\Rl wherein R1 is Cl-C4 alkyl or hydroxyalkyl; R2 is C1-C12 alkylene, hydroxyalkylene, alkylene, arylene or alkarylene; X is H, S03 , or mixture thereof; k is 1 or Q; m is from 0 to about 5; n is at least about 3; m and n are numbers such that the moiety -(CH2CH20)n- comprises at least about 85% by weight of the moiety -~(C3H60)m(CH2CH20)n-]; x is 1 or 0; y is 1 when x is 0 and 0 when x is 1; the number of u and v is such that ~here are at least 2 N
groups and at least 2 X groups.
In the above formulas, R1 is preferably methyl; ~2 is preferably C2-C3 alkylene; X is preferably H; k is preferably 0; m is preferably 0.

~2~ 9 In the above formulas, n is preferably at least about 6 when the number of N and X groups are each 2 or 3; n is most preferably at least about 12, with a typical range of from about 12 to about 42 for all ranges of u + v. Preferably v is 0, and u is from about 3 to about 40.
Methods for Making Ethoxylated Amine Polymers A. Polyurethane The polyurethane versions of the present invention can be prepared according to the following general scheme:

~2~

~O~Q~H NaH

~o,(CH2CH20)n-H
+ TsCl 15 ~ S < + H~ (CH CH,O) Ts O OCH2CH2)n N~ ~ OH ~/ ~ ~ n + OCNC6NCO ~) _ ( CH2CH20) n Bu2Sn ( 2CCll ) 2 --0/\/11/~OCNC6~ -- HCl ` ' > u ~1 ~ ~ O
oA~ ~OCNC6NI~ --( CH2CH20)n-H
u 31Z~ Q~

Step 1: Ethoxylation The monotetrahydropyronyl ether of diethylene glycol (1.77 moles) [Compt. Rend., 260, 1399-1401 (1965)] is ethoxylated us;ng 5 mo1e ~ NaH to generate a catalytlc amount of the corresponding alkoxide. Ethoxylation is conducted at 90-120C until about 22 moles (n = 22) of ethylene oxide is taken up for each mole of the starting alcohol to form the ethoxylated C(.,~"fl.
Step 2: Tosylation The ethoxylated compound from step 1 is dissolved in 1000 ml.
of acetonitrile and then cooled to about 10C. To this solution is added 2.6 moles of tosyl chloride dissolved in 500 ml. of acetonitrile and cooled to 10C and then 2.9 moles of triethyl-amine is added. After the reaction is complete, H20 is added to decompose the remaining tosyl chloride.
Step 3: Amination To the reaction mixture from step 3 is added 3.4 moles of diethanolamine. After heating for 18 hrs. at 80C, the reaction mixture is cooled and carefully acidified with HCl, keeping the pH
~just above 7, and then extracted with ether. The aqueous phase is then extracted with a mixture of ether:acetonitrile (ratio of about 5:2) twice. The aqueous phase is separated and then made basic with 50% NaOH. This aqueous phase is extracted with dichloro~ethane (2000 ml.). The lower layer is separated and then extracted 3 times with 2000 ml. portions of 1/4 saturated NaCl soluticn while adding enough 50X NaOH to make the aqueous phase strongly basic (p~ of about 11). The lower organic layer is stripped to give the desired aminated compound. Toluene (200 ml.) is added and the mixture s~ripped again to give the desired aminated monomer.
Step 4: Polymerization and Removal of Protecting Groups The aminated monome~ from step 3 is dissolved in chloroform free of ethanol stabil~er. The monomer is previously evacuated in a Kugelrohr at 80-90C under a vacuum (pressure of 1 mm.) for at least 18 hours. The monomer in the chloro~orm is then dried overnight with 3A molecular sièves and then transferred to a dry flask (equipped with mechanical stirrer) under argon. To the monomer is added dibutyltin dilaurate catalyst (0.058 mole equiv.) ~,~

\
~l21~Q~

in chloroform under argon. To the stirred reaction m;xture is then added 0.7 moles of hexamethylenedi;socyanate per mole of aminated monomer over a 5 minute period. The reaction mixture is stirred at room temperature for 18 hours. The chloroform is removed under a vacuum at about 70C to give the resulting polymer. This polymer is dissolved in methanol, the pH is ad-justed to about 4 with aqueous HCl and is then allowed to stand overnight to solvolyze the tetrahydropyranyl protecting group.
The solution is then neutralized with NaO~ and stripped to give the crude polyurethane. This crude polyurethane is dissolved in chloroform and filtered to remove any salts. The chloroform is stripped away to give the desired, largely salt-free polymer.
B. Random Copolymer of Ethoxylated Methacrylate and an Amino Methacrylamide The random copolymer versions of the present invention can be prepared according to the following general scheme:

J ~ . .

~2~

\ I ~ ~ (CH2CH20)nH

~\ C~ N ~NMe2 ( (~ -)2 AIBN >~/

C=O~ v .=Q
, NH
(~HZCH20)nH
`NMe~

;.

.
s~
,, ~

The synthesis of one such random copolymer is described as follows:
Decaethyleneylycol monomethacrylate monomer (0.008 moles) and N-(3-dimethylaminopropyl)-methacrylamide monomer (0.011 moles) are dissolved in 40 ml. of acetonitrile. The reactlon mixture is purged of oxygen by bubbling argon through ~t. A 0.23 g. portion of benzoyl peroxide is separately dissolved ln acetonitrile and similarly purged. The reaction mixture is heated to reflux and the benzoyl peroxide solut;on then added dropwise over 0.5 hours.
Next, 0.28 g. of azobisisobutyronitrile in 5 ml. of acetonitrile is added to the reaction mixture and heating is continued cvernight.
The desired random copolymer is isolated by stripping off the solvent.
C. Ethoxylated PEI
The ethoxylated PEIs of the present ~nvention can be prepared by standard methods for ethoxylating amines. ~here is preferably an initial step of condensing sufficient ethylene oxide to provide 2-hydroxyethyl groups at each reactlve site. The appropriate amount of ethylene oxide is then condensed with these 2-hydroxyethylamines using an alkall metal ~e.g., sodium, potas-sium) hydride of hydroxide as the catalyst to provide the respec-tive ethoxylated amines. The total degree of ethoxylation per reactive site (n) can be determined accord~ng to the following formula:
Degree of Ethoxylation = Et(A x R) wherein E is the total number of moles of ethylene oxide condensed (including hydroxyethylation~, A ;s the number of moles of the starting PEI9 and R is the number of reactive sites (typically 3 +
y + z) for the starting PEI.
A representative synthesis of an ethoxylated PEI of the present invention is as follows:
Example 3 Dried PEI (M.W 600, 14.19 9., 0.0236 moles) was hydroxy-ethylated with ethylene oxide at 130-140C ~or 3 hours with stirring. 0.5 9. (0.0125 moles) of 60X sodium hydride in mineral oil was then added and the reaction mixture xwept with argon.

~' -~z~

After hydrogen evolution ceased, E0 was then added under atmos-pheric pressure with stirr;ng at 130-140C. After 14 hours, 711.6 g. of E0 had been added to give a calculated total degree of ethoxylation of 41.5^. The ethoxylated PEI 600 obtalned was a tan waxy solid.
D. Diallylamine Polymers Diallylamine polymer versions of the present invention can be prepared according to the following general scheme.

~J

~lZl~

(~,3~ NH ~ (~ ~ NCHzC~l2 ¦ NaH
j~ J N ( CH2CH20 ) n~H

+GOH
r~ /
(CH2CH20)n h' 2û

~5 OE~Q~

The synthesis of one such polymer is described as follows:
Example 4 Step 1: Ethoxylation Diallylamine (1.7 moles) is dissolved in methanol (160 ml.) under argon and then heated to 45C. Ethylene oxide is then added for 2.5 hours. Methanol is then removed by heating the reaction mixture to 100C _ vacuo. To the residue is added sodium hydride (0.17 moles) with stirring until the evolution of hydrogen ceased.
Ethylene oxide is then added until the degree of ethoxylation (n) is about 7.
Step 2: Polymerization A portion of the ethoxylated monomer from step 1 (25 9.) is mixed with D20 (20 ml.) and heated to 95C under argon for 1 hour.
Tertbutylhydroperoxide (0.5 ml.) is then added dropwise and the reaction continued at 90C for 18 hours. Then additional hydroperoxide (0.5 ml.) is added dropwise. After heating 3 more days, water is then removed in vacuo (50-60C at pressure of 0.1 mm) to yield the crude polymer.
Clay Soil Removal/Anti-Redeposition Properties of Various Ethoxylated Amine Polymers 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 Ca :Mg ) 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.
65~ 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 subse-quently baked to remove the water. The dipping and baking was repeated 5 times.
One wash employed 2000 ppm o~ a control liquid detergent composition containing the following surfactants:

~2~

Surfactant Amount (X) Sodium C14-C15 alkyl ethoxysulfate 10.8 C13 linear alkylbenzene sulfonic ac~d 7.2 C12-C13 alcohol poly-ethoxylate (6.5) 6.5 C12 alkyl trimethyl-ammonium chloride 1.2 A second wash used the same detergent composition but also con-taining an ethoxylated amine polymer at 20 ppm. Neither composi-tion contained optical brighteners. The prod~ct washes approxi-mated a conventional home use laundry situation. After launder-ing, the swatches were dried in a mini-dryer.
The swatches were graded before and after washing on a Gardner Whiteness meter reading the L, a, and b coordinates.
Whiteness (W) was calculated as:
7L2 40Lb W =

The clay soil removal performance of each detergent composition was determined by finding the difference in whiteness ~W) before and after washing as:
~ W = W after ~ W before The improvement ~n clay so~l removal performance of the composi-tion containing the ethoxylated amine polymer was measured as the difference in ~W values ~2W) relat~ve to the control composition.
2. Anti-Redeposition Anti-redeposition compar~sons were conducted in a 5 pot Automatic Miniwasher (AMW) employing 7 grain hardness water and temperature of 95F. Test swatches were washed for lO minutes and rinsed twice with water (7 grain hardness) at 75F for 2 minutes.
After the AMW pots were f~lled with 6 liters of water each, the detergent composition to be tested (control or containing 20 ppm ethoxylated amlne polymer as in clay soil removal test) was ~21~

added and agitated for 2 mtnutes. A background soll m1xture (200 ppm artif~c~al body soil, 100 ppm vacuum cleaner soil and 200 ppm clay soil) was then added and agitated for an add~tional 3 mtn-utes. Three 5 inch square test swatches (50~ polyester/50% cotton 5 T-shir~ material) were then added, along with two 80~ cotton/20%
po1yester terry clothes and two 11 inch square swatches of 100%
polyester knit fabric. The 10 m~nute wash cycle commenced at this point.
Following the rinse cycle, the test swatches were dried in a mini-dryer. Gardner Whiteness meter read~ngs (L, a and b) were then determined for the three test swatches. Antl-redeposition performance (ARD) was then calculated according to the following equation.
ARD = 7 L2 40 Lb 70~
The ARD values for the three test swatches were then averaged.
The improvement in anti-redeposition per~ormance of the composi-tion containing the ethoxylated amine was measured as the differ-ence in ARD values (~ ARD) relati~e to the control composition.
B. Test Results The results from testing the clay-soil removal and anti-rede-position performance of various ethoxylated amine polymers is shown in the following Table:
Amine *Amine Degree of 25 Type M.W. Ethoxylation ~ 2W ~ARD
PEI 600 3 0.6 1709 12 5.6 20.5 24 6.0 20.9 ^ 42 7.7 20.5 PEI 1800 S 1.6 14.4 13 3.1 17.7 29 5.5 16.6 PPI 20,000 6 0.6 5.0 24 -1.3 11.6 42 - 13.8 * PEI = polyethyleneimine, PPI r polypropyleneimine ~Z~L~Q~9 ~ 30 -For comparison, PEG 6000 (polyethylene glyçol hav1ng M.W. of 6000) has a a2w value of 4.9 and a a ARD value of 8.9.
Detergent Surfactants The amount of detergent surfactant included ~n the detergent compositions of the present invent~on can vary from about 1 to about 75% by we~ght of the compos~tion depending upon the deter-gent surfactant(s) used, the type of compos~tion to be formulated (e.g. granular, liqu~d) and the effects desired. Preferably, the detergent surfactant(s) comprises from about 10 to about ~0% by weight of the composition. The detergent surfactant can be nonionic, anionic, ampholytlc, zwitter~on~c, cationic, or a mixture thereof:
A. Nonion k Surfactants Suitable nonionic surfactants for use ln detergent composi-tions of the present invention are generally disclosed in U.S.Patent 3,929,678 to Laughlin et al., ~ssued December 30, 1975 at column 13, line 14 through column 1~, lin~ 6. Classes of nrr,ion;~
~rfactants ;n~ rl~l are:
1. The polyethyleneoxide condensates of alkyl phenols.
ThesP compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in e~ther a straight chain or branched cha1n configuration with ethylene oxide, the ethylene ox~de being present in an amount equal to 5 to 25 moles of ethylene ox~de per mole of alkyl phenol.
The alkyl subst~tuent ln such compounds can be derived, for example, from polymeri~ed propylene, d~sobutylene, 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 wlth about 15 moles of ethylene oxide per mole of phenol; and diisooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol. Com~er-cially available noniontc surfactants of this type include Igepal C0-63~* marketed by the GAF Corporation, and Tr~ton X-4~,* X-114*
X-100* and X-102* all marketed by the Rohm 8 Haas Company.

* Tr~e Mark ~2~L~Q~9 ~ 31 2. The condensation products of aliphat~c alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be stralght or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol; and the condensation product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains vary1ng in length from to 14 carbon atoms~. Examples of commercially available nonlonic surfactants of this type include Tergitol 15-S-9, mar-keted by Union Carbide Corporat~on, Neodol 45-9, Neodol 23-6.5, Neodol 45-7,* and Neodol 45-4, marketed by Shell Chemical Company, and Kyro EOB, 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 1500 to 1800 and exhiblts water insolubility. The addf~ion of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the llquid 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 of this type include certain of the commerc~ally available Pluron~c*surfactants, marketed by Wyandotte Chemical Corporation.

4. The condensation products of ethy1ene oxide with the product resulting from the react~on of propylene oxide and ethyl-enediamine. The hydrophobic mo~ety of these products consists afthe reaction product of ethylenediamine and excess propylene oxide, the moiety having a molecular weight of from about 250~ to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40g to about 80X by we~ght of polyoxyethylene and has a molecular weight of from about S,OOO to about 11,000. Examples of * Trade ~rk . . ..
,~ ,!, ~2~Q~9 thls type of nonionic surfactant ~nclude certain of the commer-cially available Tetronic compounds, marketed by Wyandotte Cheml-cal Corporation.

5. Semi-polar nonionic detergent surfactants which include water-soluble amine oxldes containing one alkyl molety of from about 10 to 18 carbon atoms and 2 moieties selectcd from the group consisting of alkyl groups and hydroxyalkyl groups cont,aining from 1 to about 3 carbon atoms; water-soluble phosph~ne oxides conta;n-ing one alkyl moiety of from about 10 to 18 carbon atoms and 2 moiettes selected from the group consist~ng of alkyl groups and hydroxyalkyl groups con~aining from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 1~ carbon atoms and a molety selected from the group con sisting of alkyl and hydroxyalkyl moiekies of from about 1 to 3 carbon atoms.
Preferred semi-po1ar nonionic detergent surfactants are the amine oxide detergent surfactants having the formula R3(oR4)~NR52 wherein R is an akkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms;
R4 is an alkylene or hydroxyalkylene group conta~ning,from 2 to 3 carbon atoms or mlx.tures thereof; x ~s from 0 to about 3; and each R5 is an alkyl or hydroxyalkyl group containing from 1 to about 3 carbon atoms or a polyethylene oxide group contalning from one to about 3 ethylene oxide groups. The R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom to form a ring structure.
Preferred amine oxide detergent surfactants are C10-Cl8 alkyl dimethyl amine oxide and C8-C12 alkoxy ethyl dihydroxy ethyl amine oxide.

6. Alkylpolysaccharides disclosed in ~An~ n ~atent No. 1,180~973 issu~d an January 15, 1985, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a * Trade Mark ~,1 ~z~

polysaccharide, e.g., a polyglycoside, hydrophilic group con-taining from about 1~ to about 101 preferably from about 1~ to about 3, most preferably from about 1.6 to about 2.7 saccharide units. Any reducing saccharide 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 hydrG-phobic group is attached at the 2, 3, 4, etc. pos;tions thus giving a glucose or galactose as opposed to a glucoside or galac-toside.) The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6 positions on the preceding saccharide units.
Optionally, 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 alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms.
Rreferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group can contain up to 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, most preferably 0, alkyleneoxide moieties. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl~ pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galacto-sides, lactosides, glucoses, fructosides, fructoses, and/or galactoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
The preferred alkylpolyglycosides have the formula R20tCnH2nO)t(glycosyl)x wherein R is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain ~rom 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 O to about 10, preferably 0; and x is from 11 to about 10 9 preferably ~rom about 1~ to about 3, most preferably 3l2~ 9 from about 1.6 to about 2.7. The glycosyl 1s preferably derived from glucose. To prepare these oompou~ds, the alcohol or alkyl-polyethoxy alcohol is formed flrst and then reacted with glucose, or a source of glucose, to form the glucos~de (a~tachment at the s 1-position). The additlonal glycosyl units can then be attached between their 1-positlon and the preceding glycosyl units 2-, 3-, 4- and/or 6- position, preferably predominately the 2-posltion.

7. Fatty acid amide detergent surfactants having the for-mula:
p wherein R6 ~s an alkyl 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 cons~sting of hydrogen~ C1-C4 alkyl, C1-C4 hydroxyalkyl~ and -(C2H40)xH where x varies from about 1 to about 3.
Preferred amides are C8-C20 am~on~a amides, monoethanol-amides, diethanolamldes, and isopropanol amides.
B. An~on~c Surfactants Anionic sur~actants suitable in detergent compositions of the present invention are general1y disolosed in U.S. Patent 3,929,678 to Laughlin et al., issued December 30, 1975 at column 23, line 58 through column 29, llne 23. C1~P~ of Anl~n;~ ~uU~d~L~lL9 in~luded are:
~5 1. Ordinary al~ali metal soaps such as the sodium, potas-sium, ammon;um and alkylolammon~um salts of higher fatty acids containing from about 8 to about 24 carbon atoms, preferably from about 10 to about 20 carbon atoms.
2. Water-soluble salts, preferably the alkali metal, ammon-ium and alkylolammonium salts, of organic sulfuric reaction products having in the~r molecular structure an a1kyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or su1furic acid ester group. ~Included in the term "alkyl"
is the alkyl portion of acyl groups.) Examples of this group of anionic surfactants are the sodium and potassium alkyl sulfates, espec~ally those obtained by ~t?

sulfating the higher alcohols (C~-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl 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 U.S. Patents 2,220,099 and 2,477,383. Espe-cially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C11-C13LAS.
Preferred anionic surfactants of this type are the alkyl polyethoxylate sulfates, particularly those in which the alkyl group contains from about 10 to about 22, preferably from about 12 to about 18 carbon atoms, and wherein the polyethoxylate chain contains from about 1 to about 15 ethoxylate moieties preferably from about 1 to about 3 ethoxylate moieties. These anionic detergent surfactants are particularly desirable for formulating heavy-duty liquid laundry detergent compositions.
Other anionic surfactants of this type include sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil, sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group con-tains from about 10 to about 20 carbon atoms.
Also included are water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atomsin 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 acids containing from about 2 to 9 carbon atoms in the acyl group and from abGut 9 to about 23 carbon atoms in the alkane moiety;
alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide;

~2~

water-soluble salts of olefin sulfonates conta1n~ng from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containlng from about 1 to 3 carbon atoms 1n the alkyl group and from about 8 to 20 carbon atoms ~n the alkane ~oiety.
S 3. Anionic phosphate surfactants.
4. N-alkyl substituted succ1namates.
C. Ampholyt1c Surfactants Ampholytic surfactants can be broadly described as aliphatic derivatives of secondary or tert~ary am1nes, or aliphat1c deriva-tives of heterocyclic secondary and tert1ary amines in wh1ch the aliphatic radical can be straight cha1n or ~branched and wherein one of the aliphat~c substituents contains from about 8 to 18 carbon atoms and at least one conta~ns an anionic water-solubil-izing group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent 3,929,678 to Laughlin et ~l., issued December 30, 1975 at column 19, 11nes 18-35 for ~ nlP.~ of ampholytic surfactants.

D. Zw~tterlon~c Surfactants Zwltterionic surfactants can be broadly descrlbed as deri-vatives of secondary and tertiary amines, derivatives of hetero-cyclic secondary and tertiary amines, or der1vatives of quaternary ammonium, quaternary phosphonium or tert1ary sulfonium compounds.
See U.S. Patent 3,929,678 to Laughlin et al., issued December 30, l975 at column 19, line 38 through column 227 line 48 for examples of ~it~ri~ni~ s~l~ac~lLs.

E. Cationic Surfactants Cationic surfac$ants can also be included in detergent compositions of the present invention. Suitable cat1Onic surfac-tants include the quaternary ammonium surfactants having theformula:
tR2(oR3)y]rR4(oR3)y]2R~N X
wherein R is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms 1n the alkyl chain; each R3 ls selected from the group consisting of -CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH20H)-, -CH2CH2CH2-, and mixtures thereof; each ~4 is ~' ~2~ Q~

selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxy-alkyl, benzyl, ring structures formed by joining the two R4 groups9 -CH2CHOHCHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R5 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 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 alkyl quaternary ammonium surfactants, especially the mono-long chain alkyl surfactants described in the above formula when R5 is selected from the same groups as R4. The most preferred quaternary ammonium surfactants are the chloride, bromide and methylsulfate C8-C16 alkyl tri-methylammonium salts, C8-C16 alkyl di(hydroxyethyl)methylammonium salts, the C8-C16 alkyl hydroxyethyldimethylammonium slats, and C8-C16 alkyloxypropyl trimethylammonium salts. Of the above, decyl trimethylammonium methylsulfate, lauryl trimethylammonium chloride, myristyl trimethylammonium bromide and coconut tri-methylammonium chloride and methylsulfate are particularly pre-ferred.
Detergent Builders Detergent compositions Ol' the present invention can optional-ly comprise inorganic or organic detergent builders to assist in m1neral hardness control. These builders can comprise from 0 to about 80% by weight o~ the composition. When included, these builders typically comprise up to about 60% by weight o~ the detergent composition. Built liquid formulations preferably comprise from about 10 to about 25% detergent builder while built granular formulations preferably comprise from about lO to about 50% by weight detergent builder.
Suitable detergent builders include crystalline aluminosili-cate ion exchange materials having the formula:
Naz[(Alo2)z (sio2)y XH20 wherein z and y are at least about 6, the mole ratio of z to y is from about 1.0 to about 0.5, and x is from about 10 to about 264.

~2~ 9 - Amorphous hydrated aluminosilicate materials useful herein have the empirical formula M (zA10 ySiO ) wherein M ;s 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 CaC03 hardness per gram of anhydrous aluminosili-cate.
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 aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix. The preferred crystalline aluminosili-cate ion exchange materials are further characterized by a parti-cle size diameter of from about 0.1 micron to about 10 microns.
Amorphous materials are often smaller, e.g. 9 down to less than about 0.01 micron. More preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns. The term "particle size diameter" represents the average particle size diameter of a giYen ion exchange material as deter-mined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron micro-scope. The crystalline aluminosilicate ion exchange materials are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg. equivalent of CaC03 water hardness/g. of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg.
eq./g. to about 352 mg. eq./g. The aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca /gallon/min-ute/gram/gallon of aluminosilicate (anhydrous basis), and gener-ally lies within the range of from about 2 grains/gallon/min-ute/gram/gallon to about 6 grains/gallon/minute/gram/gallon, based on calcium ion hardness. Optimum aluminosilicates for builder purposes exh~bit a calcium 10n exchange rate of at least about 4 grains/gallon/minute/gram/gallon.
The amorphous alum~nos~l kate lon exchange mater~als usually have a Mg exchange capacity of at least about 50 mg, eq.
CaC03/g. (12 mg. Mg /g.) and a Mg exchange rate of at least about 1 grain/gallon/m~nute/gram/gallon. Amorphous materlals do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).
Useful aluminoslilicate ion exchange materials are commercial-ly available. These aluminosil~cates can be crystalline oramorphous in structure and can be naturally-occurring aluminosili-cates or synthetically derived. A method for producing alumino-silicate ion exchange mater~als ~s dlsclosed in U.S. Patent 3,985,669 to Krummel, et al. iss~ed October 12, 1976. Preferred synthetic crystalline al- 'nn~i~icate ion exchange materials useful herein are available under the designation~ Zeolite A, Zeolite P (B), and Zeolite X, In an especially preferred embodi-ment, the cxy~11ine aluminosili~ate ion eA~ e material has the fonmula Nal2[(Al02)l2(s~o2)l2} XH2 wherein x is from about 20 to about 30~ especially about 27.
Other examples of detergency bullders inctude the various water-soluble~ alkal~ metal, ammonium or substltuted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonatest s~licates, borates, polyhydroxysulfQnates, polyace-tates, carboxylates, and polycarboxylates. Preferred are the alkali metal, espec~ally sod~um, salts o~ the above.
Specific examples o~ Inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphate having a degree of polymerizat~on of from about 6 to 21, and orthophosphate. Examples of polyphosphonate bullders are the sodium and potassium salts of ethylene~ d~phosphonic acid, the sodium and potassium salts of `ethane l~hydroxy~131-diphosphonic acid and the sodium and potasslum salts of ethane~ 1,1,2-triphos phon~c acid. Other phosphorus bullder compounds are disclosed in ~ !~

~2~

U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148.
Examples of nonphosphorus, inorganic butlders are sodium and potassium carbonate, b~carbonate, sesquicarbonate, tetraborate decahydrate, and silicate hav~ng a mole ratlo of S~02 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, nonphosphorus organic bu~lders include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy-sulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium lithium, ammonium and substltuted ammonium salts o~ ethylened~amine tetraacetic acid, nitrilotri-acetic acid, oxydisucclnic acid, mell~tic acid, benzene polycar-boxylic acids, and citric acid.
Highty preferred polycarboxylate builders are disclosed inU.S. Patent No. 3,308,067 to Diehl, issued M~oh 7, 1967. Such materials include the water-sQlllh7~ salts of homc- and oopolymers of aliphatic carboxylic acids such as maleic acid, itaoonic acid, -~ onn;c acid, fumaric acid, ac~nitic acid, citrao~nic acid and methyl~n ~ ic acid.
Other builders include the carboxylated carbohydrates dis-closed in U.S. Patent 3,723,322 to Diehl issued March 28, 1973 Other useful builders are sodium and potassium carboxymethyl-oxymalonate, carboxymethyloxysuccinate~ cis-cyclohexanehexacar-boxylate, c;s-cyclopentanetetracarboxylate phloroglucinol trisul-fonate, water-soluble polyacrylates (having molecular weights of from about 2,000 to about 200,000 for example), and the copolymers of maleic anhydride w;th vinyl methyl ether or ethylene.
Other suitable polycarboxylates are the polyacetal carboxy-lates disclosed in U.S. Patent 4,144,226, to Crutchfield et al.
issued March 13, 1979, and U.S. Patent 4,246,435, to Crutchfield et al., issued March 27, 1979. These polyacetal carkoxylates can ke ~ aled by hringing ~ogeUle~ under polymerization conditions an ester of glyoxylic ~.1 ~z~ g ac~d and a polymerization ~nitiator. The result~ng polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate aga~nst rap;d depolymerl zation in alkaline solution, converted to the corresponding salt, and added to a surfactant.
Other useful detergency builder materials are the "seeded builder" compositions disclosed ~n Belgian Patent No. 798,856, issued October 29, 1973. Specific examples of such seeded builder mixtures are 3:1 wt. mixtures of sodium carbonate and calcium caLbonate having 5 micron particle diameter; 2.7:1 wt. mixtures of sodium sesquicarbonate and calcium carbonate having a particle diameter of 0.5 microns; 20:1 wt. mixtures of sodium sesquicar-bonate and calcium hydroxide having a particle diameter of 0.01 micron; and a 3:3:1 wt. mixture of sodium carbonate, sodium aluminate and calcium oxide having a particle diameter of 5 microns.
Other Optional Detergent Ingredlents 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 act~vators, soil sus-pending agents, corrosion inhibitors, dyes, fillers, optical brighteners, germ~cides, pH ad;usting agents (monoethanolamine~
sodium carbonate, sodium hydroxide, etc.), enzymes, enzyme-stabil-izing agents, perfumes, fabr~c softening components, staticcontrol 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 slurrying the individual components in water and then atomizing and spray drying the resultant mixture, or by pan or drum granulation of ~he ingredientsO Granular formulations preferably comprise from about 10 to about 30% detergent surfac-tant, usually anionic.
Liquid formulations embodying the detergent compositions can be built or unbuilt. If unbuilt, these compositions conventionally contain approximately 15 to 50% total surfactant, from 0 to 10~ of an organic base such as a mono-, di-, or tri alkanol amine, a neutral kation system such as an alkali metal hydroxide and a lower primary alcohol such as ethanol or isopropanol, and approxi~ately 20 to 80% water. Such compositions are normally homogeneous single phase l~qu~ds of low viscos~ty (approximately 100 to 150 centipoise at 75F).
Built liquid detergent compositions can be ~n the form of single phase liquids prov~ded 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 inorgan~c, 3 to 10~ of a hydrotrope system and 40 to 77% water Liquids of this type also have a low v~scosity (100 to 150 centipoise at 75F). Built llquid detergents incorporating components that form heterogeneous mi~tures (or levels of builder that cannot be completely dissolved) can also comprise detergent compositions of the present invention. Such liquids conventional-ly employ viscosity modifiers to produce systems having plastic shear characteristics to maintaln stable dispersions and to prevent phase separation or soltd settlement.
Near Neutral Wash pH Detergent Formulations ~ hile the detergent compos~tions of the present invention are operative within a w~de range of wash pHs (e.g. from about 5 to about 12), they are particularly suitable when formulated to provide a near neutral wash pH, l.e. an initial pH of from about 6.0 to abou~ 8.5 a~ a concen~rat~on of from about 0.1 to about 2%
by weight in water at 20C. Near neutral wash pH formulations are better for enzyme stability and for prevent~ng stains from set-ting. In such formulations, the wash pH is preferably from about 30 7.0 to about 8.5, and more preferably from about 7.5 to about 8Ø
Preferred near neutral ~ash pH detergen~ formulations are disclosed in ~AnA~;~n PatPnt Application Serial N~. 428,642 to J. H. M. Wertz and P. C. E. ~ff;nPt, filed May 20, 1983. These ~refPrred fcrmulations c~mrr;~e ,,~. . i .
.,,~ :

~2~ Q~

(a) from about 2 to about 60X (preferably from about 10 to about 25X) by weight of an anionic synthet~c surfactant as pre-viously defined;
(b) from about 0.25 to about 12% (preferably from about 1 to about 4g) by weight of a cosurfactant selected from the group consisting of:
(i) quaternary ammonium surfactants having the formula:
[R2(oR3)yJ[R4(0R3)y]2RSN X
wherein R2, each R3, R4, R5, X and y are as previously defined;

(ii) diquaternary ammon~um surfactants having the formula:
[R2(oR3)y~rR4(0R3)y~2N+R3N+RS~R4(oR3)y]2 (X )2 }s wherein R2, R , R4, y and X are as defined above; particu-larly preferred are the C8-C16 alkyl pentamethylethylene-diamine chloride, bromide and methylsulfate salts;
(iii) am~ne surfactants havlng the formula:
tR~(oR3) ][R4(oR3) ]RSN
wherein R2, R3, R~, R5 and y are as defined above; particu-larly preferred are the C12-C16 alkyl dimethyl amines;
(lv) diamine surfactants having the formula:
~R2~oR3) ]~R4(oR3~yJNR3NR5~R4(oR3)y]
wherein R2, R~, R4, R5 an~ y are as defined above; particu-larly preferred are the C12-C16 alkyl d~methyl diamines;
(v) am~ne oxide surfactants havlng the formula ~R2(oR3) ~[R4(oR3)y]R5N~~~~0 wherein R2, R~, R4, R5 and y are as defined above; particu-larly preferred are the C12-C16 alkyldimethyl amine oxides;
and (vi) di(amine oxide) surfactants having the formula:
[~2~oR3) ]tR4(oR3~ ]NR3NR5rR4(oR )y]

wherein R2, R3, R4, R5 and y are as defined above; preferred are the C12-C16 alkyl trimethylethylene di(amine oxides) and -QQ~

(c) from about 5X to about 40% by we;ght (preferably 7 to about 30~ by weight, and most preferably from about 10 to 20~ by weight) of a fatty acid containing from about 10 to about 22 carbon atoms (preferably a ClO-Cl4 saturated fatty ac~d or mixture thereof); the mole ratio of the anlonic surfactant to the cosur-factant being at least 1 and preferably from about 2:1 to about 20:1.
Such compositions also preferably contain from about 3 to about 15~ by weight of an ethoxylated alcohol or ethoxylated alkyl phenol (nonionic surfactants) as previously defined. Highly pre~erred compositions of thls type also preferably contain from about 2 to about 10% by weight of citric acid and minor amounts (e.g., less than about 20X by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzymes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, ant;-oxidants, bactericides, dyes, perfumes and brighteners, such as those described in U.S. Patent 4,2859841 to Barrat et al., issued August 25, 1981~
Specific Embodiments of Detergent Compositions According to the Present Invention Embodlment I
The following embodiments lllustrate, but are not limiting of, detergent compositions of the present inYention:
A granular detergent composition is as ~ollows:
25 Component Wt. %
Polyurethane of Example 1 l.0 Sodlum C14~Cl5 alkylethoxysulfate 10.7 C13 linear alkyl benzene sulfonic acid 4.3 C12-C14 alkylpolyethoxylate (6) 0 5 30 Sodium toluene sulfonate 1.0 Sodium tripolyphosphate 32.9 Sodium sarbonate 20.3 Sodium silicate 5.8 Minors and water Balance to 100 The components are added together with continuous mixing to form an aqueous slurry which is then spray dried to form the -composition. Instead of the polyurethane, the random copolymer of Example 2, the PEI of Example 3 or the diallylamine polymer of Example 4 can be substituted therefor.
Embodiment II
A liquid detergent composition is as follows:
Cornponent Wt. %
Random Copolymer of Example 2 1.0 Sodium C14-C15 alkyl p~lyethoxy (2.5) sulfate 8.3 C12-C14 alkyl dimethyl amine oxide 3.3 10 Sodium toluene 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. Instead of the random copolymer, the polyurethane of Example 1, the PEI of Example 3 or the diallyl-amine polymer of Example 4 can be substituted therefor.
Embodiments III and IV
Liquid detergent compositions are as follows:
20 Component Wt. %
III IV
PEIof Example 3 1.5 1.5 C14-C15 alkylethoxysulfuric acid 10.8 C14-C15 alkylpolyethoxy (2.25) sulfuric acid - 10.8 C13 linear alkylbenzene sulfonic acid 7.2 7.2 C12 alkyl trimethylammonium chloride 1.2 1.2 C12 13 alcohol polyethoxylate (6.5) 6.5 6.5 Coconut fatty acid 15.0 15.0 Citric acid monohydrate 6.9 4.0 30 Diethylenetriamine pentaacetic acid 0.9 0.9 Protease enzyme 0.8 0.8 Amylase enzyme 0.3 0.3 Monoethanolamine 13.6 2.0 Triethanolamine 3.0 4.0 35 ~odium hydroxide - 2.0 Potassium hydroxide - 2.8 1,2-Propanediol 5.0 5 0 Ethanol 3.0 7.0 Sodium formate 1.0 1.0 Sodium toluene sulfonate 5.0 Minors and water Balance to 100 Embodiment IY is prepared by adding the components together with continuous mixing~ in the following order to produce a clear liquid: a paste premix of the alkylbenzene sulfonic acid, 0.9 parts of the sodium hydroxlde, propylene glycol, and 2.3 parts of the ethanol; a paste premix of the alkylpolyethoxysulfuric acid, 1.1 par~s of the sodium hydroxide and 3.1 parts of the ethanol;
alcohol polyethoxylate; premix of monoethanolamine, triethanol-amine and brighteners, 1.5 parts potassium hydroxlde; balance of the ethanol; citric acid; formate; 1.4 parts potass~um hydroxide;
fatty acid; pentaacetic acid; alkyl trimethylammonium chloride;
adjust pH to about 8.4 with potassium hydroxide, water or citric acid; enzymes~ PEI (50% aqueous solution); and perfume. Embodi-ment III can be prepared in a similar manner.
Embodiment V
A liquid detergent composition is formulated as follows:
Component Wt. %
PEI of Example 3 1.0 Sodium C12 alkylpolyethoxy (3) sulfate 12.6 C12-C13 alcohol polyethoxylate (6.5) 23.4 25 Monoethanolamine 2.0 Ethanol 9.0 Citrlc acid monohydrate 0.8 Minors and water 3alance to 100 The components are added together with continuous mixing to form the composition. Instead of the PEI, the polyurethane of Example 1, the random copolymer of Example 2, or the diallylamine polymer of Example 4 can be substituted therefor.

,, ....

Claims (23)

Claims

1. A water-soluble ethoxylated amine polymer having clay soil removal/anti-redeposition properties which comprises a polymer backbone other than a polyalkyleneamine backbone, at least 2 M groups and at least one L-X group, wherein M is a tertiary amine group attached to or integral with said backbone; X is a nonionic group, anionic group or mixture thereof; and L is a hydrophilic chain connecting groups M and X or connecting X to the backbone, L also containing the polyoxyalkylene moiety -[(R'O)m(CH2CH2O)n]-, wherein R' is C3-C4 alkylene or hydroxyalkylene, m and n are numbers such that the moiety -(CH2CH2O)n- comprises at least about 50% by weight of said polyoxyalkylene moiety, and n is at least about 3, except when said backbone is a polyethyleneimine backbone, and n is at least about 12 when said backbone is a polyethyleneimine backbone.

2. A polymer according to Claim 1 wherein said backbone is selected from the group consisting of the polyurethanes, the polyesters, the polyethers, the polyamides, the polyimides, the polyacrylates, the polyacrylamides, the polyvinylethers, the polyalkylenes, the polyalkarylenes, the polyalkyleneimines, the polyvinylamines, the polyallylamines, the polydiallylamines, the polyvinylpyridines, the polyaminotriazoles, polyvinyl alcohol, the aminopolyureylenes and mixtures thereof.

3. A polymer according to Claim 2 wherein the number of said M and L-X groups are each from 3 to about 40.

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

5. A polymer according to Claim 4 wherein m is O and n is at least about 12.

6. A polymer according to Claim 5 wherein X is a mixture of from 0 to about 30% anionic groups and from about 70 to 100%
nonionic groups.

7. A polymer according to Claim 6 wherein said anionic group is SO3?.

8. A polymer according to Claim 7 wherein said nonionic group is H.

9. A polymer according to Claim 1 which comprises units selected from those having formulas I, II and III:

I
II

III

wherein x is 0 or 1; R is H or C1-C4 alkyl or hydroxyalkyl; R1 is C2-C12 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units, provided that no O-O or O-N bonds are formed with A1; when x is 1, R2 is -R5- except when A1 is , or is -(OR7)y- or -OR5-provided that no O-O or N-O bonds are formed with A1, and R3 is -R5- except when A1 is , or is -(R7O)y- or -R5O- provided that no O-O or O-N bonds are formed with A1; when x is O, R2 is R5 is C1-C12 alkylene, hydroxyalkylene, cycloalkylene, alkenylene, arylene, or alkarylene; R6 is H or R4; R7 is C2-C3 alkylene or hydroxyalkylene; X is R, SO3-, or a mixture thereof; k is 0 or 1;
m is from 0 to about 5; n is at least about 3; m and n are numbers such that the moiety -(CH2CH2O)n- comprises at least about 85% by weight of the moiety -[(C3H6O)m(CH2CH2O)n]-; y is from 2 to about 20; the number of u , v and w are such that there are at least 2 N
groups and at least 2 X groups.

10. A polymer according to Claim 9 wherein

11. A polymer according to Claim 10 wherein v and w are 0 and u is from about 3 to about 40.

12. A polymer according to Claim 11 wherein m is 0 and n is at least about 12.

13. A polymer according to Claim 1 which comprises units selected from those having formulas IV, V and VI

IV

V VI
wherein A1 is R is H or C1-C4 alkyl or hydroxyalkyl; R1 is substituted C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene, or alkarylene or C2-C3 oxyalkylene; each R2 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; R3 is C1-C4 alkyl or hydroxy-alkyl, or the moiety -(R2)k-[(C3H6O)m(CH2CH2O)n]-X; each R4 is C1-C4 alkyl or hydroxyalkyl, or together form the moiety -(CH2)r-A2-(CH2)s-, wherein A2 is -0- or -CH2-; R5 is C2-C3 alkylene or hydroxyalkylene; X is R, SO3-, or a mixture thereof; j is 1 or 0;
k is 1 or 0; m is from 0 to about 5; n is at least about 3; m and n are numbers such that the moiety -(CH2CH2O)n- comprises at least about 85% by weight of the moiety -[(C3H6O)m(CH2CH2O)n]-; r is 1 or 2, s is 1 or 2 and r + s is 3 or 4; the number u, v and w are such that there are at least 2 N groups and at least 2 X groups.

14. A polymer according to Claim 13 wherein A1 is is methyl; each R4 is methyl; X is H or methyl, j is 1; k is 0.

15. A polymer according to Claim 14 wherein v and w are 0 and u is from about 3 to about 40.

16. A polymer according to Claim 15 wherein m is 0 and n is at least about 12.

17. A polymer according to Claim 1 which comprises units selected from those having the general formula VII:

VII
wherein R1 is C2 - C12 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C2-C3 polyoxyalkylene moiety having from 2 to about 20 oxyalkylene units;
R2 is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R3)k-[(C3H6O)m(CH2CH2O)n]-x; R3 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alk-arylene; X is H, SO?, or mixture thereof; k is 1 or 0, m is from 0 to about 5; n is at least about 12; m and n are numbers such that the moiety -(CH2CH2O)n- com-prises at least about 85% by weight of the moiety [(C3H6O)m(CH2CH2O)n]-; x + y + z is at least 10.

18. A polymer according to Claim 17 wherein R1 is C2-C3 alkylene; R2 is methyl or the moiety -[(C3H60)m(CH2CH2O)n]-x; X is H; k is 0.

19. A polymer according to Claim 18 wherein m is 0.

20. A polymer according to Claim 1 which comprises units selected from those having formulas IX and X:

IX

X
wherein R1 is C1-C4 alkyl or hydroxyalkyl; R2 is C1-C12 alkylene, hydroxyalkylene, alkylene, arylene or alkarylene; X is H, SO3?, or mixture thereof; k is 1 or 0; m is from 0 to about 5; n is at least about 3; m and n are numbers such that the moiety -(CH2CH2O)n- comprises at least about 85% by weight of the moiety -[(C3H60)m(CH2CH2O)n-]; x is 1 or 0; y is 1 when x is 0 and 0 when x is 1; the number of u and v is such that there are at least 2 N
groups and at least 2 X groups.

21. A polymer according to Claim 20 wherein R1 is methyl; R3 is methyl; X is H; k is 0.

22. A polymer according to Claim 21 wherein v is 0 and u is from about 3 to about 40.

23. A polymer according to Claim 22 wherein m is 0 and n is at least about 12.