Liquid or gel dishwashing detergent containing a polyhydroxy fatty acid amide, calcium ions and an alkylpolyethoxypolycarboxylate

Liquid or gel dishwashing detergent compositions containing anionic surfactant, polyhydroxy fatty acid amide, calcium ions and alkyl polyethoxypol ycarboxylate for improved stability are described. A preferred embodiment comprises: PA1 (a) from about 3% to about 40% of polyhydroxy fatty acid amide having the formula: ##STR1## wherein R.sup.1 is hydrogen, C.sub.1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or mixtures thereof; R.sup.2 is C.sub.5 -C.sub.31 hydrocarbyl; mid Z is a polyhydroxy-hydrocarbyl having a linear hydrocarbyl chain with at least three hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof; PA1 (b) from about 0.1% to about 4% of calcium ions; PA1 (c) from about 0.001% to about 15% of alkylpolyethoxypolycarboxylate surfactant having the general formula: ##STR2## wherein R is a C.sub.6 to C.sub.18 alkyl group, x is from about 1 to about 25, R.sub.1 and R.sub.2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, wherein at least one R.sub.1 or R.sub.2 is a succinic acid radical, hydroxysuccinic acid radical, and R.sub.3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof; and PA1 (d) from about 3 to about 95% of an anionic surfactant; wherein said composition has a pH in a 10% solution in water of between about 7 and about 9.

TECHNICAL FIELD 
The present invention relates to liquid or gel dishwashing detergent 
compositions containing polyhydroxy fatty acid amide, calcium ions, and 
alkylpolyethoxypolycarboxylate surfactant. 
BACKGROUND OF THE INVENTION 
Liquid or gel dishwashing detergents exhibiting good grease removal 
benefits are much desired by consumers. The addition of calcium or 
magnesium ions to liquid or gel dishwashing detergent can under certain 
conditions improve the grease cleaning benefits of the composition. 
However, it may be necessary to limit the pH and/or add chelating agents 
or lime soap dispersants to stabilize the product. As concentrated 
products become increasingly more popular, ingredients which can 
contribute a variety of benefits is very important in formulating a 
product. 
It has been found that certain alkylpolyethoxypolycarboxylate surfactants 
when added to a liquid or gel dishwashing detergent composition containing 
calcium ions, anionic surfactant, and poly hydroxy fatty acid amide and 
having a pH of from about 7 to about 11, prevent insoluble salt 
precipitation and also act as a hydrotrope and a surfactant (if used in 
sufficient quantities). 
SUMMARY OF THE INVENTION 
A light-duty liquid or gel dishwashing detergent composition comprising, by 
weight: 
(a) from about 3% to about 40% of polyhydroxy fatty acid amide having the 
formula: 
##STR3## 
wherein R.sup.1 is hydrogen, C.sub.1-4 hydrocarbyl, 2-hydroxyethyl, 
2-hydroxypropyl, or mixtures thereof; R.sup.2 is C.sub.5 -C.sub.31 
hydrocarbyl; and Z is a polyhydroxy-hydrocarbyl having a linear 
hydrocarbyl chain with at least three hydroxyl groups directly connected 
to the chain, or an alkoxylated derivative thereof; 
(b) from about 0.1% to about 4% of calcium ions; 
(c) from about 0.001% to about 15% of alkylpolyethoxypolycarboxylate 
surfactant having the general formula: 
##STR4## 
wherein R is a C.sub.6 to C.sub.18 alkyl group, x is from about 1 to about 
25, R.sub.1 and R.sub.2 are selected from the group consisting of 
hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid 
radical, and mixtures thereof, wherein at least one R.sub.1 or R.sub.2 is 
a succinic acid radical, hydroxysuccinic acid radical, and R.sub.3 is 
selected from the group consisting of hydrogen, substituted or 
unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and 
mixtures thereof; and 
(d) from about 3 to about 95% of an anionic surfactant; wherein said 
composition has a pH in a 10% solution in water of between about 7 and 
about 9. 
A particularly preferred embodiment also comprises from about 0.5% to about 
10% of suds booster selected from the group consisting of alkylamidopropyl 
amine oxide, alkyl amine oxide, alkyldimethylbetaine, 
alkylamidopropylbetaine, alkylmonoethanol amide, and alkyldiethanol amide.

DETAILED DESCRIPTION OF THE INVENTION 
The liquid or gel, preferably liquid, dishwashing detergent compositions of 
the present invention contain a polyhydroxy fatty acid amide, an anionic 
surfactant, a source of calcium ions and an alkylpolyethoxypolycarboxylate 
surfactant. The compositions herein may also contain suds booster. These 
and other complementary optional ingredients typically found in liquid or 
gel dishwashing compositions are set forth below. 
The term "light duty dishwashing detergent compositions" as used herein 
refers to those compositions which are employed in manual (i.e. hand) 
dishwashing. 
Polyhydroxy Fatty Acid Amide 
The compositions of the present invention comprise from about 3% to about 
40%, preferably from about 5% to about 30%, more preferably from about 8% 
to about 25%, by weight of the composition of one or more polyhydroxy 
fatty acid amides having the structural formula: 
##STR5## 
wherein: R.sup.1 is H, C.sub.1 -C.sub.4 hydrocarbyl, 2-hydroxy ethyl, 
2-hydroxy propyl, or a mixture thereof, preferably C.sub.1 -C.sub.4 alkyl, 
more preferably C.sub.1 or C.sub.2 alkyl, most preferably C.sub.1 alkyl 
(i.e., methyl); and R.sup.2 is a C.sub.5 -C.sub.31 hydrocarbyl, preferably 
straight-chain C.sub.7 -C.sub.19 alkyl or alkenyl, more preferably 
straight-chain C.sub.9 -C.sub.17 alkyl or alkenyl, most preferably 
straight-chain C.sub.11 -C.sub.17 alkyl or alkenyl, or mixture thereof; 
and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with 
at least 3 hydroxyls directly connected to the chain, or an alkoxylated 
derivative (preferably ethoxylated or propoxylated) thereof. Z preferably 
will be derived from a reducing sugar in a reductive amination reaction; 
more preferably Z is a glycityl. Suitable reducing sugars include glucose, 
fructose, maltose, lactose, galactose, mannose, and xylose. As raw 
materials, high dextrose corn syrup, high fructose corn syrup, and high 
maltose corn syrup can be utilized as well as the individual sugars listed 
above. These corn syrups may yield a mix of sugar components for Z. It 
should be understood that it is by no means intended to exclude other 
suitable raw materials. Z preferably will be selected from the group 
consisting of --CH.sub.2 (CHOH).sub.n --CH.sub.2 OH, --CH(CH.sub.2 
OH)--(CHOH).sub.n-1 --CH.sub.2 OH, --CH.sub.2 (CHOH).sub.2 
(CHOH')(CHOH)--CH.sub.2 OH, where n is an integer from 3 to 5, inclusive, 
and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated 
derivatives thereof. Most preferred are glycityls wherein n is 4, 
particularly --CH.sub.2 --(CHOH).sub.4 --CH.sub.2 OH. 
In Formula (I), R.sup.1 can be, for example, N-methyl, N-ethyl, N-propyl, 
N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl. 
R.sup.2 --CO--N&lt; can be, for example, cocamide, stearamide, oleamide, 
lauramide, myristamide, capricamide, palmitamide, tallowamide, etc. 
Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 
1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 
1-deoxymaltotriotityl, etc. 
The most preferred polyhydroxy fatty acid amide has the general formula 
##STR6## 
wherein R.sup.2 is a straight chain C.sub.11 -C.sub.17 alkyl or alkenyl 
group. 
Method of Preparation 
In general, polyhydroxy fatty acid amides can be made by reacting an alkyl 
amine with a reducing sugar in a reductive amination reaction to form a 
corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl 
polyhydroxyamine with a fatty aliphatic ester or triglyceride in a 
condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid 
amide product. Processes for making compositions containing polyhydroxy 
fatty acid amides are disclosed, for example, in G.B. Patent Specification 
809,060, published Feb. 18, 1959, U.S. Pat. No. 2,965,576, issued Dec. 20, 
1960 to E. R. Wilson, and U.S. Pat. No. 2,703,798, Anthony M. Schwartz, 
issued Mar. 8, 1955, and U.S. Pat. No. 1,985,424, issued Dec. 25, 1934 to 
Piggott, each of which is incorporated herein by reference. 
In one process for producing N-alkyl or N-hydroxyalkyl, N-deoxyglycityl 
fatty acid amides wherein the glycityl component is derived from glucose 
and the N-alkyl or N-hydroxy- alkyl functionality is N-methyl, N-ethyl, 
N-propyl, N-butyl, N-hydroxyethyl, or N-hydroxypropyl, the product is made 
by reacting N-alkyl- or N-hydroxyalkyl-glucamine with a fatty ester 
selected from fatty methyl esters, fatty ethyl esters, and fatty 
triglycerides in the presence of a catalyst selected from the group 
consisting of alkali metal alkoxide, trilithium phosphate, trisodium 
phosphate, tripotassium phosphate, tetrasodium pyrophosphate, 
pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, 
potassium hydroxide, calcium hydroxide, lithium carbonate, sodium 
carbonate, potassium carbonate, disodium tartrate, dipotassium tartrate, 
sodium potassium tartrate, trisodium citrate, tripotassium citrate, sodium 
basic silicates, potassium basic silicates, sodium basic aluminosilicates, 
and potassium basic aluminosilicates, and mixtures thereof. The amount of 
catalyst is preferably from about 0.5 mole % to about 50 mole %, more 
preferably from about 2.0 mole % to about 10 mole %, on an N-alkyl or 
N-hydroxyalkyl -glucamine molar basis. The reaction is preferably carried 
out at from about 138.degree. C. to about 170.degree. C. for typically 
from about 20 to about 90 minutes. When triglycerides are utilized in the 
reaction mixture as the fatty ester source, the reaction is also 
preferably carried out using from about 1 to about 10 weight % of a phase 
transfer agent, calculated on a weight percent basis of total reaction 
mixture, selected from saturated fatty alcohol polyethoxylates, 
alkylpolyglucosides, linear glucamide surfactant, and mixtures thereof. 
Preferably, this process is carried out as follows: 
(a) preheating the fatty ester to about 138.degree. C. to about 170.degree. 
C.; 
(b) adding the N-alkyl or N-hydroxyalkyl glucamine to the heated fatty acid 
ester and mixing to the extent needed to form a two-phase liquid/liquid 
mixture; 
(c) mixing the catalyst into the reaction mixture; and 
(d) stirring for the specified reaction time. 
Also preferably, from about 2% to about 20% of preformed linear 
N-alkyl/N-hydroxyalkyl, N-linear glucosyl fatty acid amide product is 
added to the reaction mixture, by weight of the reactants, as the phase 
transfer agent if the fatty ester is a triglyceride. This seeds the 
reaction, thereby increasing reaction rate. 
The polyhydroxy "fatty acid" amide materials used herein also offer the 
advantages to the detergent formulator that they can be prepared wholly or 
primarily from natural, renewable, non-petrochemical feedstocks and are 
degradable. They also exhibit low toxicity to aquatic life. 
It should be recognized that along with the polyhydroxy fatty acid amides 
of Formula (I), the processes used to produce them will also typically 
produce quantities of nonvolatile by-product The level of these 
by-products will vary depending upon the particular reactants and process 
conditions, but are preferably kept to a minimum. 
Alternate Method 
An alternate method for preparing the polyhydroxy fatty acid amides used 
herein is as follows. A reaction mixture consisting of 84.87 g. fatty acid 
methyl ester (source: Procter & Gamble methyl ester CE1270), 75 g. 
N-methyl-D-glucamine (source: Aldrich Chemical Company M4700-0), 1.04 g. 
sodium methoxide (source: Aldrich Chemical Company 16,499-2), and 68.51 g. 
methyl alcohol is used. The reaction vessel comprises a standard reflux 
set-up fitted with a drying tube, condenser and stir bar. In this 
procedure, the N-methyl glucamine is combined with methanol with stirring 
under argon and heating is begun with good mixing (stir bar; reflux). 
After 15-20 minutes, when the solution has reached the desired 
temperature, the ester and sodium methoxide catalyst are added. Samples 
are taken periodically to monitor the course of the reaction, but it is 
noted that the solution is completely clear by 63.5 minutes. It is judged 
that the reaction is, in fact, nearly complete at that point. The reaction 
mixture is maintained at reflux for 4 hours. After removal of the 
methanol, the recovered crude product weighs 156.16 grams. After vacuum 
drying and purification, an overall yield of 106.92 grams purified product 
is recovered. However, percentage yields are not calculated on this basis, 
inasmuch as regular sampling throughout the course of the reaction makes 
an overall percentage yield value meaningless. The reaction can be carried 
out at 80% and 90% reactant concentrations for periods up to 6 hours to 
yield products with extremely small by-product formation. 
The following is not intended to limit the invention herein, but is simply 
to further illustrate additional aspects of the technology which may be 
considered by the formulator in the manufacture of a wide variety of 
detergent compositions using the polyhydroxy fatty acid amides. 
It will be readily appreciated that the polyhydroxy fatty acid amides are, 
by virtue of their amide bond, subject to some instability under highly 
basic or highly acidic conditions. While some decomposition can be 
tolerated, it is preferred that these materials not be subjected to pH's 
above about 11, preferably 10, nor below about 3 for unduly extended 
periods. Final product pH (liquids) is typically 6.0-9.0. 
During the manufacture of the polyhydroxy fatty acid amides it will 
typically be necessary to at least partially neutralize the base catalyst 
used to form the amide bond. While any acid can be used for this purpose, 
the detergent formulator will recognize that it is a simple and convenient 
matter to use an acid which provides an anion that is otherwise useful and 
desirable in the finished detergent composition. For example, citric acid 
can be used for purposes of neutralization and the resulting citrate ion 
(ca. 1%) be allowed to remain with a ca. 40% polyhydroxy fatty acid amide 
slurry and be pumped into the later manufacturing stages of the overall 
detergent-manufacturing process. The acid forms of materials such as 
oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, 
tartrate/succinate, and the like, can be used similarly. 
The polyhydroxy fatty acid amides derived from coconut alkyl fatty acids 
(predominantly C.sub.12 -C.sub.14) are more soluble than their tallow 
alkyl (predominantly C.sub.16 -C.sub.18) counterparts. Accordingly, the 
C.sub.12 -C.sub.14 materials are somewhat easier to formulate in liquid 
compositions, and are more soluble in cool-water laundering baths. 
However, the C.sub.16 -C.sub.18 materials are also quite useful, 
especially under circumstances where warm-to-hot wash water is used. 
Indeed, the C.sub.16 -C.sub.18 materials may be better detersive 
surfactants than their C.sub.12 -C.sub.14 counterparts. Accordingly, the 
formulator may wish to balance ease-of-manufacture vs. performance when 
selecting a particular polyhydroxy fatty acid amide for use in a given 
formulation. 
It will also be appreciated that the solubility of the polyhydroxy fatty 
acid amides can be increased by having points of unsaturation and/or chain 
branching in the fatty acid moiety. Thus, materials such as the 
polyhydroxy fatty acid amides derived from oleic acid and iso-stearic acid 
are more soluble than their n-alkyl counterparts. 
Likewise, the solubility of polyhydroxy fatty acid amides prepared from 
disaccharides, trisaccharides, etc., will ordinarily be greater than the 
solubility of their monosaccharide-derived counterpart materials. This 
higher solubility can be of particular assistance when formulating liquid 
compositions. Moreover, the polyhydroxy fatty acid amides wherein the 
polyhydroxy group is derived from maltose appear to function especially 
well as detergents when used in combination with conventional alkylbenzene 
sulfonate ("LAS") surfactants. While not intending to be limited by 
theory, it appears that the combination of LAS with the polyhydroxy fatty 
acid amides derived from the higher saccharides such as maltose causes a 
substantial and unexpected lowering of interfacial tension in aqueous 
media, thereby enhancing net detergency performance. (The manufacture of a 
polyhydroxy fatty acid amide derived from maltose is described 
hereinafter.) 
The polyhydroxy fatty acid amides can be manufactured not only from the 
purified sugars, but also from hydrolyzed starches, e.g., corn starch, 
potato starch, or any other convenient plant-derived starch which contains 
the mono-, di-, etc. saccharide desired by the formulator. This is of 
particular importance from the economic standpoint. Thus, "high glucose" 
corn syrup, "high maltose" corn syrup, etc. can conveniently and 
economically be used. De-lignified, hydrolyzed cellulose pulp can also 
provide a raw material source for the polyhydroxy fatty acid amides. 
As noted above, polyhydroxy fatty acid amides derived from the higher 
saccharides, such as maltose, lactose, etc., are more soluble than their 
glucose counterparts. Moreover, it appears that the more soluble 
polyhydroxy fatty acid amides can help solubilize their less soluble 
counterparts, to varying degrees. Accordingly, the formulator may elect to 
use a raw material comprising a high glucose corn syrup, for example, but 
to select a syrup which contains a modicum of maltose (e.g., 1% or more). 
The resulting mixture of polyhydroxy fatty acids will, in general, exhibit 
more preferred solubility properties over a broader range of temperatures 
and concentrations than would a "pure" glucose-derived polyhydroxy fatty 
acid amide. Thus, in addition to any economic advantages for using sugar 
mixtures rather than pure sugar reactants, the polyhydroxy fatty acid 
amides prepared from mixed sugars can offer very substantial advantages 
with respect to performance and/or ease-of-formulation. In some instances, 
however, some loss of grease removal performance (dishwashing) may be 
noted at fatty acid maltamide levels above about 25% and some loss in 
sudsing above about 33% (said percentages being the percentage of 
maltamide-derived polyhydroxy fatty acid amide vs. glucose-derived 
polyhydroxy fatty acid amide in the mixture). This can vary somewhat, 
depending on the chain length of the fatty acid moiety. Typically, then, 
the formulator electing to use such mixtures may find it advantageous to 
select polyhydroxy fatty acid amide mixtures which contain ratios of 
monosaccharides (e.g., glucose) to di- and higher saccharides (e.g., 
maltose) from about 4:1 to about 99:1. 
The manufacture of preferred, uncyclized polyhydroxy fatty acid amides from 
fatty esters and N-alkyl polyols can be carried out in alcohol solvents at 
temperatures from about 30.degree. C.-90.degree. C., preferably about 
50.degree. C.-80.degree. C. It has now been determined that it may be 
convenient for the formulator of, for example, liquid detergents to 
conduct such processes in 1,2-propylene glycol solvent, since the glycol 
solvent need not be completely removed from the reaction product prior to 
use in the finished detergent formulation. Likewise, the formulator of, 
for example, solid, typically granular, detergent compositions may find it 
convenient to run the process at 30.degree. C.-90.degree. C. in solvents 
which comprise ethoxylated alcohols, such as the ethoxylated (EO 3-8) 
C.sub.12 -C.sub.14 alcohols, such as those available as NEODOL 23 EO6.5 
(Shell). When such ethoxylates are used, it is preferred that they not 
contain substantial amounts of unethoxylated alcohol and, most preferably, 
not contain substantial amounts of mono-ethoxylated alcohol. ("T" 
designation.) 
Fatty Acids 
For compositions where especially high sudsing is desired (e.g., light-duty 
dishwashing), it is preferred that less than about 5%, preferably less 
than about 2%, most preferably no C.sub.14 or higher fatty acids be 
present, since these can suppress sudsing. Liquid detergent compositions 
herein are preferably substantially free of a suds-suppressing amount of 
C.sub.14 and higher fatty acid. Accordingly, the formulator of high 
sudsing compositions will desirably avoid the introduction of 
suds-suppressing amounts of such fatty acids into high sudsing 
compositions with the polyhydroxy fatty acid amide, and/or avoid the 
formation of C.sub.14 and higher fatty acids on storage of the finished 
compositions. One simple means is to use C.sub.12 ester reactants to 
prepare the polyhydroxy fatty acid amides herein. Fortunately, the use of 
alkylpolyethoxypolycarboxylate, amine oxide or sulfobetaine surfactants 
can overcome some of the negative sudsing effects caused by the fatty 
acids. Most preferably, fatty acids should be avoided (less than about 
2.5% by weight is preferred). 
Calcium Ions 
From about 0.1% to about 4%, more preferably from about 0.2% to about 2%, 
most preferably from about 0.3% to about 1.5% by weight of the 
composition, of calcium ions are included in the detergent compositions 
herein. It has been found for compositions containing the present 
polyhydroxy fatty acid amide that the presence of calcium greatly improves 
the cleaning of greasy soils. This is especially true when the 
compositions are used in softened water, which contains few divalent ions. 
Furthermore, it has been found that formulating such calcium ion-containing 
compositions in alkaline pH matrices is difficult due to the 
incompatability of the calcium ions with hydroxide ions. When both calcium 
ions and alkaline pH are combined with the surfactant mixture of this 
invention, grease cleaning is achieved that is superior to that obtained 
by either alkaline pH or calcium ions alone. Yet, during storage, the 
stability of these compositions becomes poor due to the formation of 
hydroxide precipitates. 
Preferably, the calcium ions are added as a chloride, hydroxide, oxide, 
acetate, formate, or nitrate salt, most preferably formate salt, to 
compositions containing an alkali metal or ammonium salt of the anionic 
sulfate, most preferably the ammonium salt (see methods of incorporation 
in Section E below). The calcium salts are preferably soluble. 
The amount of calcium ions present in compositions of the invention may be 
dependent upon the amount of total anionic surfactant present therein. The 
molar ratio of calcium ions to total anionic surfactant is preferably from 
about 0.25:1 to about 1:2 for compositions of the invention. 
Composition pH 
Traditionally, liquid dishwashing compositions have a pH of about 7. 
Dishwashing compositions of the invention will be subjected to acidic 
stresses created by food soils when put to use, i.e., diluted and applied 
to soiled dishes. If a composition with a pH greater than 7 is to be most 
effective in improving performance, it should contain a buffering agent 
capable of maintaining the alkaline pH in the composition and in dilute 
solutions, i.e., about 0.1% to 0.4% by weight aqueous solution, of the 
composition. The pKa value of this buffering agent should be about 0.5 to 
1.0 pH units below the desired pH value of the composition (determined as 
described above). Preferably, the pKa value of the buffering agent should 
be between about 7 and about 8.5. Under these conditions the buffering 
agent most effectively controls the pH while using the least amount 
thereof. Preferably the composition of the present invention has a pH in a 
10% solution of water at 20.degree. C. between about 7 and about 11, more 
preferably from about 7.5 to about 10, most preferably from about 7.5 to 
about 8.5. 
The buffering agent may be an active detergent in its own right, or it may 
be a low molecular weight, organic or inorganic material that is used in 
this composition solely for maintaining an alkaline pH. Preferred 
buffering agents for compositions of this invention are 
nitrogen-containing materials. Some examples are amino acids or lower 
alcohol amines like mono-, di-, and tri-ethanolamine. Other preferred 
nitrogen-containing buffering agents are 2-amino-2-ethyl-1,3-propanediol, 
2-amino-2-methylpropanol, and 2-amino-2-methyl-1,3-propanediol, 
tris-(hydroxymethyl)aminomethane (a.k.a. tris). N-methyl diethanolamine, 
1,3-diamino-2-propanol N,N'-tetramethyl-1,3-diamino-2-propanol, 
N,N-bis(2-hydroxyethyl)glycine (a.k.a. bicine), and 
N-tris(hydroxymethyl)methyl glycine (a.k.a. tricine) are also preferred. 
Mixtures of any of the above are acceptable. 
The buffering agent is present in the compositions of the invention hereof 
at a level of from about 0.1% to 15%, preferably from about 1% to 10%, 
most preferably from about 2% to 8%, by weight of the composition. 
Alkylpolyethoxypolycarboxylate Surfactant 
The compositions of this invention contain alkylpolyethoxypolycarboxlyate 
surfactants of the general formula 
##STR7## 
wherein R is a C.sub.6 to C.sub.18 alkyl group, x ranges from about 1 to 
about 24, R.sub.1 and R.sub.2 are selected from the group consisting of 
hydrogen, methyl radical or succinic acid radical, and mixtures thereof, 
wherein at least one R.sub.1 or R.sub.2 is a succinic acid and/or 
hydroxysuccinic acid radical. An example of a commercially available 
alkylpolyethoxpolycarboxylate which can be employed in the present 
invention is POLY-TERGENT C, Olin Corporation, Cheshire, Conn. 
The alkylpolyethoxypolycarboxylate surfactant is selected on the basis of 
its degree of hydrophilicity. A balance of carboxylation and ethoxylation 
is required in the alkylpolyethoxypolycarboxylate in order to achieve 
maximum chelating benefits without affecting the cleaning benefits which 
is associated with the divalent ions or the sudsing of the liquid or gel 
dishwashing detergent compositions. The number of carboxylate groups 
dictates the chelating ability, too much carboxylation will result in too 
strong a chelator and prevent the cleaning benefits of the calcium ions. A 
high degree of ethoxylation is desired for mildness and solubility; 
however, too high a level will affect sudsing. Therefore, an 
alkylpolyethoxypolycarboxylate with a modest degree of ethoxylation and 
minimal carboxylation is preferable. Preferably the 
alkylpolyethoxypolycarboxylate surfactant comprises from about 1 to about 
4, more preferably from about 1 to about 2, of succinic head groups and/or 
hydroxysuccinic acid (from about 2 to about 8 carboxyl groups, from about 
2 to about 4 carboxyl groups, respectively), and from about 4 to about 12, 
more preferably from about 7 to about 11, ethoxy groups. 
Alkylpolyethoxypolycarboxylate surfactants can be classified based upon the 
% hydrophilicity. This is calculated using the following formula: 
##EQU1## 
Preferably the alkylpolyethoxypolycarboxylate surfactant comprises from 
about 60% to about 90%, more preferably from about 65% to about 85%, most 
preferably from about 70% to about 85% hydrophilicity. 
The desired alkylpolyethoxylpolycarboxylate surfactant can be obtained by a 
free radical addition reaction wherein the addition products of maleic 
acid, fumaric acid, itaconic acid or mixtures thereof, with a select 
poly(alkoxylated)alcohol produce a surfactant with excellent chelating 
properties. A process for producing such alkylpolyethoxypolycarboxylate 
surfactants is disclosed in U.S. Pat. Nos. 5,030,245 and 5,120,326, both 
of which are incorporated herein by reference. 
Without being bound to theory it is believed that the carboxyl groups in 
the molecule preferentially bind the calcium ions in the composition 
resulting in the formation of calcium salts of 
alkylpolyethoxycarboxylates. The ethoxy groups in the molecule help in 
solubilizing the resultant salts, thus, a clear, stable composition is 
formed. In the absence of alkylpolyethoxypolycarboxylates, precipitates 
such as calcium fatty acids (from free, unreacted fatty acids of the 
polyhydroxy fatty acid amide), are formed, particularly at low 
temperatures. As the level of free fatty acids decreases so does the level 
of alkylployethoxypolycarboxylates needed to obtain clear stable 
composition; therefore, the benefits associated with the alkylpoly 
ethoxypolycarboxylate are most clearly evident in compositions containing 
fatty acids (i.e. unreacted fatty acids of the polyhydroxy fatty acid 
amide). 
The compositions of the invention comprise from about 0.01% to about 15%, 
more preferably from about 0.1% to about 10%, most preferably from about 
1% to about 5%, by weight of the composition, of 
alkylpolyethoxypolycarboyxlate surfactant. 
Anionic Surfactant 
The detergent compositions of the present invention comprise from about 3% 
to about 95%, more preferably from about 5% to about 60%, most preferably 
from about 10% to about 40%, by weight of the composition of one or more 
anionic surfactants. 
The most preferred anionic surfactants are anionic sulfate surfactants 
which may be any organic sulfate surfactant. It is preferably selected 
from the group consisting of C.sub.10 -C.sub.16 alkyl sulfate which has 
been ethoxylated with from about 0.5 to about 20 moles of ethylene oxide 
per molecule, C.sub.9 -C.sub.17 acyl-N-(C.sub.1 -C.sub.4 alkyl) glucamine 
sulfate, -N-(C.sub.2 -C.sub.4 hydroxyalkyl) glucamine sulfate, and 
mixtures thereof. More preferably, the anionic sulfate surfactant is a 
C.sub.10 -C.sub.16 alkyl sulfate which has been ethoxylated with from 
about 0.5 to about 20, preferably from about 0.5 to about 12, moles of 
ethylene oxide per molecule. 
Alkyl ethoxy sulfate surfactants comprise a primary alkyl ethoxy sulfate 
derived from the condensation product of a C.sub.10 -C.sub.16 alcohol with 
an average of from about 0.5 to about 20, preferably from about 0.5 to 
about 12, ethylene oxide groups. The C.sub.10 -C.sub.16 alcohol itself is 
commercially available. C.sub.12 -C.sub.14 alkyl sulfate which has been 
ethoxylated with from about 3 to about 10 moles of ethylene oxide per 
molecule is preferred. 
Conventional base-catalyzed ethoxylation processes to produce an average 
degree of ethoxylation of 12 result in a distribution of individual 
ethoxylates ranging from 1 to 15 ethoxy groups per mole of alcohol, so 
that the desired average can be obtained in a variety of ways. B1 ends can 
be made of material having different degrees of ethoxylation and/or 
different ethoxylate distributions arising from the specific ethoxylation 
techniques employed and subsequent processing steps such as distillation. 
Anionic sulfate surfactants include the C.sub.9 -C.sub.17 acyl-N-(C.sub.1 
-C.sub.4 alkyl) and -N-(C.sub.1 -C.sub.2 hydroxyalkyl) glucamine sulfates, 
preferably those in which the C.sub.9 -C.sub.17 acyl group is derived from 
coconut or palm kernel oil. Lime soap dispersing agent can be added, 
especially to the longer chain length glucamine sulfates for improved 
product stability (e.g., where C.sub.9 -C.sub.17 acyl is palm kernel oil). 
These materials can be prepared by the method disclosed in U.S. Pat. No. 
2,717,894, Schwartz, issued Sep. 13, 1955, incorporated herein by 
reference. 
The counterion for the anionic surfactant component is preferably selected 
from calcium, sodium, potassium, magnesium, ammonium or alkanol-ammonium, 
and mixtures thereof, with calcium and magnesium being preferred for 
cleaning and sudsing, respectively. 
Other anionic surfactants useful for detersive purposes can also be 
included in the compositions hereof. Exemplary, non-limiting useful 
anionics include salts (e.g., sodium, potassium, ammonium, and substituted 
ammonium salts such as mono-, di- and triethanolamine salts) of soap, 
C.sub.8 -C.sub.22 alkylsulfates, C.sub.8 -C.sub.24 alkylpolyethersulfates 
(containing up to 10 moles of ethylene oxide); fatty acyl glycerol 
sulfates, alkyl phenol ethylene oxide ether sulfates, alkyl phosphates, 
isethionates such as the acyl isethionates, acyl taurates, fatty acid 
amides, alkyl succinates and sulfosuccinates, acyl sarcosinates, sulfates 
of alkylpolysaccharides such as the sulfates of alkylpolyglucoside, alkyl 
ether carbonates, alkyl ethoxy carboxylates, fatty acids esterified with 
isethionic acid and neutralized with sodium hydroxide, and fatty acids 
amides of methyl tauride. Further examples are described in "Surface 
Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and 
Berch). A variety of such surfactants are also generally disclosed in U.S. 
Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al. at Column 23, 
line 58 through Column 29, line 23 (herein incorporated by reference). 
Additional Optional Surfactants 
Suitable nonionic detergent surfactants are generally disclosed in U.S. 
Pat. No. 3,929,678, Laughlin et al., issued Dec. 30, 1975, at column 13, 
line 14 through column 16, line 6, incorporated herein by reference. 
Exemplary, non-limiting classes of useful nonionic surfactants are listed 
below. 
1. The polyethylene, polypropylene, and polybutylene oxide condensates of 
alkyl phenols. In general, the polyethylene oxide condensates are 
preferred. These compounds include the condensation products of alkyl 
phenols having an alkyl group containing from 6 to 12 carbon atoms in 
either a straight- or branched-chain configuration with the alkylene 
oxide. Commercially available nonionic surfactants of this type include 
Igepal.TM. CO-630, marketed by the GAF Corporation; and Triton.TM. X-45, 
X-114, X-100, and X-102, all marketed by the Rohm & Haas Company. 
2. The condensation products of aliphatic alcohols with from about 1 to 
about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol 
can either be straight or branched, primary or secondary, and generally 
contains from 8 to 22 carbon atoms. Particularly preferred are the 
condensation products of alcohols having an alkyl group containing from 
about 10 to about 20 carbon atoms with from about 2 to about 10 moles of 
ethylene oxide per mole of alcohol. 
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 preferably has a molecular weight 
of from about 1500 to about 1800 and exhibits water insolubility. 
4. The condensation products of ethylene oxide with the product resulting 
from the reaction of propylene oxide and ethylenediamine. 
5. Semi-polar nonionic surfactants are a special category of nonionic 
surfactants which include water-soluble amine oxides containing one alkyl 
moiety of from 10 to 18 carbon atoms and 2 moieties selected from the 
group consisting of alkyl groups and hydroxyalkyl groups containing from 1 
to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl 
moiety of from 10 to 18 carbon atoms and 2 moieties selected from the 
group consisting of alkyl groups and hydroxyalkyl groups containing from 1 
to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl 
moiety of from 10 to 18 carbon atoms and a moiety selected from the group 
consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms. 
Semi-polar nonionic detergent surfactants include the amine oxide 
surfactants 
6. Alkylpolysaccharides disclosed in U.S. Pat. No. 4,565,647, Llenado, 
issued Jan. 21, 1986, having a hydrophobic group containing from about 6 
to about 30 carbon atoms, preferably from about 10 to about 16 carbon 
atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group 
containing from about 1.3 to about 10, preferably from about 1.3 to about 
3, most preferably from about 1.3 to about 2.7 saccharide units. 
7. Fatty acid amide surfactants having the formula: 
##STR8## 
wherein R.sup.6 is an alkyl group containing from 7 to 21, preferably from 
9 to 17, carbon atoms and each R.sup.7 is selected from the group 
consisting of hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 
hydroxyalkyl, and --(C.sub.2 H.sub.4 O).sub.x H where x varies from about 
1 to about 3. 
Ampholytic surfactants may also be incorporated into the detergent 
compositions hereof. These surfactants can be broadly described as 
aliphatic derivatives of secondary or tertiary amines, or aliphatic 
derivatives of heterocyclic secondary and tertiary amines in which the 
aliphatic radical can be straight-branched chains. One of the aliphatic 
substituents contains at least 8 carbon atoms, typically from 8 to 18 
carbon atoms, and at least one contains an anionic water-solubilizing 
group, e.g., carboxy, sulfonate, sulfate. See U.S. Pat. No. 3,929,678 to 
Laughlin et al., issued Dec. 30, 1975, at column 19, lines 18-35 (herein 
incorporated by reference) for examples of useful ampholytic surfactants. 
Zwitterionic surfactants may also be incorporated into the detergent 
compositions hereof. These surfactants can be broadly described as 
derivatives of secondary and tertiary amines, derivatives of heterocyclic 
secondary and tertiary amines, or derivatives of quaternary ammonium, 
quaternary phosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 
3,929,678 to Laughlin et al., issued Dec. 30, 1975, at column 19, line 38 
through column 22, line 48 (herein incorporated by reference) for examples 
of useful zwitterionic surfactants. 
Such ampholytic and zwitterionic surfactants are generally used in 
combination with one or more anionic and/or nonionic surfactants. 
If included in the compositions of the present invention, these optional 
additional surfactants or mixtures thereof are typically present at a 
concentration of from about 1% to about 15%, preferably from about 2% to 
about 10% by weight of the composition. 
Suds Booster 
Another component which may be included in the composition of this 
invention is a suds stabilizing surfactant (suds booster) at a level of 
less than about 15%, preferably from about 0.5% to 12%, more preferably 
from about 1% to 10% by weight of the composition. Optional suds 
stabilizing surfactants operable in the instant composition are of five 
basic types--betaines, ethylene oxide condensates, fatty acid amides, 
amine oxide semi-polar nonionics, and cationic surfactants. 
The composition of this invention can contain betaine detergent surfactants 
having the general formula: 
##STR9## 
wherein R is a hydrophobic group selected from the group consisting of 
alkyl groups containing from about 10 to about 22 carbon atoms, preferably 
from about 12 to about 18 carbon atoms, alkyl aryl and aryl alkyl groups 
containing a similar number of carbon atoms with a benzene ring being 
treated as equivalent to about 2 carbon atoms, and similar structures 
interrupted by amido or ether linkages; each R.sup.1 is an alkyl group 
containing from 1 to about 3 carbon atoms; and R.sup.2 is an alkylene 
group containing from 1 to about 6 carbon atoms. 
Examples of preferred betaines are dodecyl dimethyl betaine, cetyl dimethyl 
betaine, dodecyl amidopropyldimethyl betaine, tetradecyldimethyl betaine, 
tetradecylamidopropyldimethyl betaine, and dodecyldimethylammonium 
hexanoate. 
Other suitable amidoalkylbetaines are disclosed in U.S. Pat. Nos. 
3,950,417; 4,137,191; and 4,375,421; and British Patent GB No. 2,103,236, 
all of which are incorporated herein by reference. 
It will be recognized that the alkyl (and acyl) groups for the above 
betaine surfactants can be derived from either natural or synthetic 
sources, e.g., they can be derived from naturally occurring fatty acids; 
olefins such as those prepared by Ziegler, or Oxo processes; or from 
olefins separated from petroleum either with or without "cracking". 
The ethylene oxide condensates are broadly defined as compounds produced by 
the condensation of ethylene oxide groups (hydrophilic in nature) with an 
organic hydrophobic compound, which can be aliphatic or alkyl aromatic in 
nature. The length of the hydrophilic or polyoxyalkylene radical which is 
condensed with any particular hydrophobic group can be readily adjusted to 
yield a water-soluble compound having the desired balance between 
hydrophilic and hydrophobic elements. 
Examples of such ethylene oxide condensates suitable as suds stabilizers 
are the condensation products of aliphatic alcohols with ethylene oxide. 
The alkyl chain of the aliphatic alcohol can either be straight or 
branched and generally contains from about 8 to about 18, preferably from 
about 8 to about 14, carbon atoms for best performance as suds 
stabilizers, the ethylene oxide being present in amounts of from about 8 
moles to about 30, preferably from about 8 to about 14 moles of ethylene 
oxide per mole of alcohol. 
Examples of the amide surfactants useful herein include the ammonia, 
monoethanol, and diethanol amides of fatty acids having an acyl moiety 
containing from about 8 to about 18 carbon atoms and represented by the 
general formula: 
EQU R.sub.1 --CO--N(H).sub.m-1 (R.sub.2 OH).sub.3-m 
wherein R is a saturated or unsaturated, aliphatic hydrocarbon radical 
having from about 7 to 21, preferably from about 11 to 17 carbon atoms; 
R.sub.2 represents a methylene or ethylene group; and m is 1, 2, or 3, 
preferably 1. Specific examples of said amides are mono-ethanol amine 
coconut fatty acid amide and diethanol amine dodecyl fatty acid amide. 
These acyl moieties may be derived from naturally occurring glycerides, 
e.g., coconut oil, palm oil, soybean oil, and tallow, but can be derived 
synthetically, e.g., by the oxidation of petroleum or by hydrogenation of 
carbon monoxide by the Fischer-Tropsch process. The monoethanol amides and 
diethanolamides of C.sub.12-14 fatty acids are preferred. 
Amine oxide semi-polar nonionic surfactants comprise compounds and mixtures 
of compounds having the formula 
##STR10## 
wherein R.sub.1 is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 
3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, 
respectively, contain from about 8 to about 18 carbon atoms, R.sub.2 and 
R.sub.3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 
2-hydroxypropyl, or 3-hydroxypropyl, and n is from 0 to about 10. 
Particularly preferred are amine oxides of the formula: 
##STR11## 
wherein R.sub.1 is a C.sub.12-16 alkyl and R.sub.2 and R.sub.3 are methyl 
or ethyl. The above ethylene oxide condensates, amides, and amine oxides 
are more fully described in U.S. Pat. No. 4,316,824 (Pancheri), 
incorporated herein by reference. 
The composition of this invention can also contain certain cationic 
quarternary ammonium surfactants of the formula: 
EQU [R.sup.1 (OR.sup.2).sub.y ][R.sup.3 (OR.sup.2).sub.y].sub.2 R.sup.4 N.sup.+ 
X.sup.- 
or amine surfactants of the formula: 
EQU [R.sup.1 (OR.sup.2).sub.y ][R.sup.3 (OR.sup.2).sub.y ]R.sup.4 N 
wherein R.sup.1 is an alkyl or alkyl benzyl group having from about 6 to 
about 16 carbon atoms in the alkyl chain; each R.sup.2 is selected from 
the group consisting of --CH.sub.2 CH.sub.2 --, --CH.sub.2 CH(CH.sub.3)--, 
--CH.sub.2 CH(CH.sub.2 OH)--, --CH.sub.2 CH.sub.2 CH.sub.2 --, and 
mixtures thereof; each R.sup.3 is selected from the group consisting of 
C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 hydroxyalkyl, benzyl, and 
hydrogen when y is not 0; R.sup.4 is the same as R.sup.3 or is an alkyl 
chain wherein the total number of carbon atoms of R.sup.1 plus R.sup.4 is 
from about 8 to about 16; 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 R.sup.4 is selected from the same groups as R.sup.3. The most 
preferred quaternary ammonium surfactants are the chloride, bromide, and 
methylsulfate C.sub.8-16 alkyl trimethyl ammonium salts, C.sub.8-16 alkyl 
di(hydroxyethyl)methylammonium salts, the C.sub.8-16 alkyl 
hydroxyethyldimethyl ammonium salts, C.sub.8-16 alkyloxypropyl trimethyl 
ammonium salts, and the C.sub.8-16 alkyl oxypropyl 
dihydroxyethylmethylammonium salts. Of the above, the C.sub.10-14 alkyl 
trimethylammonium salts are preferred, e.g., decyl trimethyl ammonium 
methyl sulfate, lauryl trimethyl ammonium chloride, myristyl 
trimethylammonium bromide and coconut trimethylammonium chloride, and 
methylsulfate. 
The suds boosters used in the compositions of this invention can contain 
any one or mixture of the suds boosters listed above. 
Magnesium 
From about 0.05% to about 1.5%, most preferably from about 0.3% to about 
0.9%, by weight of the composition, of magnesium ions may preferably be 
added to the liquid detergent compositions of the invention for improved 
product stability, as well as improved sudsing and skin mildness. 
The preferred calcium ion:magnesium ion ratio is between about 1:10 and 
about 1:2, preferably between about 1:4 and about 1:2. It is preferred 
that the calcium ions are introduced by adding calcium chloride dihydrate 
or calcium formate to the composition and that the magnesium ions are 
introduced by adding magnesium chloride hexahydrate to the composition. 
From about 1% to about 5% by weight of calcium chloride dihydrate or 
calcium formate, and optionally from about 3% to about 7% of magnesium 
chloride hexahydrate, are preferred for a light duty liquid composition 
herein. 
If the anionic surfactants are in the acid form, then the magnesium can be 
added by a second method: neutralization of the acid with a magnesium 
oxide or magnesium hydroxide slurry in water. Calcium can be treated 
similarly. The use of calcium hydroxide is preferred. This technique 
avoids the addition of chloride ions, which improves chill point and 
reduces corrosive properties. The neutralized surfactant salts and the 
hydrotrope are then added to the final mixing tank and any optional 
ingredients are added before adjusting the pH. 
Other Optional Components 
Other desirable ingredients include diluents, solvents, dyes, perfumes, 
opacifiers, and hydrotropes. Diluents can be inorganic salts, such as 
sodium and potassium sulfate, ammonium chloride, sodium and potassium 
chloride, sodium bicarbonate, etc. Diluents useful in the compositions of 
the present invention are typically present at levels of from about 1% to 
about 10%, preferably from about 2% to about 5% by weight of the 
composition. 
Solvents useful herein include water and lower molecular weight alcohols, 
such as ethyl alcohol, isopropyl alcohol, etc. Solvents useful in the 
compositions of the present invention are typically present at levels of 
from about 1% to about 60%, preferably from about 5% to about 50% by 
weight of the composition. 
Hydrotropes such as sodium, potassium, and ammonium xylene sulfonate 
(preferred), sodium, potassium and ammonium toluene sulfonate, sodium, 
potassium and ammonium cumene sulfonate (most preferred), and mixtures 
thereof, and related compounds (as disclosed in U.S. Pat. No. 3,915,903, 
the disclosure of which is incorporated herein) may be utilized in 
addition to the alylpolyethoxypolycarboxylate surfactants in the interests 
of achieving a desired product phase stability and viscosity. Hydrotropes 
useful in the compositions of the present invention are typically present 
at levels of from about 1% to about 10%, preferably from about 2% to about 
5%, by weight of the composition. 
Optional ingredients useful when the compositions of the present invention 
are used in liquid dishwashing detergent applications include drainage 
promoting ethoxylated nonionic surfactants of the type disclosed in U.S. 
Pat. No. 4,316,824, issued Pancheri, issued Feb. 23, 1982, the disclosure 
of which is incorporated herein by reference. 
Opacifiers such as Lytron (Morton Thiokol, Inc.), a modified polystyrene 
latex, or ethylene glycol distearate can be added, preferably as a last 
step. Lytron can be added directly as a dispersion with mixing. Ethylene 
glycol distearate can be added in a molten state with rapid mixing to form 
pearlescent crystals. Opacifiers useful herein, particularly for light 
duty liquids, are typically present at levels of from about 0.2% to about 
10%, preferably from about 0.5% to about 6% by weight of the composition. 
In a preferred embodiment, the detergent compositions of the present 
invention are liquid detergent compositions. These preferred liquid 
detergent compositions comprise from about 94% to about 35% by weight, 
preferably from about 90% to about 50% by weight, most preferably from 
about 80% to about 60% by weight of a liquid carrier, e.g., water, 
preferably a mixture of water and a C.sub.1 -C.sub.4 monohydric alcohol 
(e.g., ethanol, propanol, isopropanol, butanol, and mixtures thereof), 
with ethanol being the preferred alcohol. A preferred way to make light 
duty liquids of the present invention is to combine the polyhydroxy fatty 
acid amide and the alkyl (ethoxy) sulfate with water and ethanol. pH is 
adjusted and then calcium and optionally magnesium ions are mixed into the 
composition as aqueous solutions of chlorine salts. The mixture is blended 
and hydrotrope may be added to adjust the viscosity. Perfume, dye, 
opacifier, and other optional ingredients may then be added. 
The detergent compositions of the present invention may also be in the form 
of a gel. Such compositions are typically formulated without alcohol and 
contain levels from about 10% to about 30% of urea and/or conventional 
thickeners. 
The claimed compositions of the present invention are beneficial in that 
they provide unexpectedly a stable composition with improved grease 
cleaning performance and clean dishes without imparting a "greasy" feel to 
the cleaned dish. 
Method Aspect 
In the method aspect of this invention, soiled dishes are contacted with an 
effective amount, typically from about 0.5 ml. to about 20 ml. (per 25 
dishes being treated), preferably from about 3 ml. to about 10 ml., of the 
detergent composition of the present invention. The actual amount of 
liquid detergent composition used will be based on the judgement of user, 
and will typically depend upon factors such as the particular product 
formulation of the composition, including the concentration of active 
ingredient in the composition, the number of soiled dishes to be cleaned, 
the degree of soiling on the dishes, and the like. The particular product 
formulation, in turn, will depend upon a number of factors, such as the 
intended market (i.e., U.S., Europe, Japan, etc.) for the composition 
product. The following are examples of typical methods in which the 
detergent compositions of the present invention may be used to clean 
dishes. These examples are for illustrative purposes and are not intended 
to be limiting. 
In a typical U.S. application, from about 3 ml. to about 15 ml., preferably 
from about 5 ml. to about 10 ml. of a liquid detergent composition is 
combined with from about 1,000 ml. to about 10,000 ml., more typically 
from about 3,000 ml. to about 5,000 ml. of water in a sink having a 
volumetric capacity in the range of from about 5,000 ml. to about 20,000 
ml., more typically from about 10,000 ml. to about 15,000 ml. The 
detergent composition has a surfactant mixture concentration of from about 
21% to about 44% by weight, preferably from about 25% to about 40% by 
weight. The soiled dishes are immersed in the sink containing the 
detergent composition and water, where they are cleaned by contacting the 
soiled surface of the dish with a cloth, sponge, or similar article. The 
cloth, sponge, or similar article may be immersed in the detergent 
composition and water mixture prior to being contacted with the dish 
surface, and is typically contacted with the dish surface for a period of 
time ranging from about 1 to about 10 seconds, although the actual time 
will vary with each application and user. The contacting of the cloth, 
sponge, or similar article to the dish surface is preferably accompanied 
by a concurrent scrubbing of the dish surface. 
In a typical European market application, from about 3 ml. to about 15 ml., 
preferably from about 3 ml. to about 10 ml. of a liquid detergent 
composition is combined with from about 1,000 ml. to about 10,000 ml., 
more typically from about 3,000 ml. to about 5,000 ml. of water in a sink 
having a volumetric capacity in the range of from about 5,000 ml. to about 
20,000 ml., more typically from about 10,000 ml. to about 15,000 ml. The 
detergent composition has a surfactant mixture concentration of from about 
20% to about 50% by weight, preferably from about 30% to about 40%, by 
weight. The soiled dishes are immersed in the sink containing the 
detergent composition and water, where they are cleaned by contacting the 
soiled surface of the dish with a cloth, sponge, or similar article. The 
cloth, sponge, or similar article may be immersed in the detergent 
composition and water mixture prior to being contacted with the dish 
surface, and is typically contacted with the dish surface for a period of 
time ranging from about 1 to about 10 seconds, although the actual time 
will vary with each application and user. The contacting of the cloth, 
sponge, or similar article to the dish surface is preferably accompanied 
by a concurrent scrubbing of the dish surface. 
In a typical Latin American and Japanese market application, from about 1 
ml. to about 50 ml., preferably from about 2 ml. to about 10 ml. of a 
detergent composition is combined with from about 50 ml. to about 2,000 
ml., more typically from about 100 ml. to about 1,000 ml. of water in a 
bowl having a volumetric capacity in the range of from about 500 ml. to 
about 5,000 ml., more typically from about 500 ml. to about 2,000 ml. The 
detergent composition has a surfactant mixture concentration of from about 
to about 40% by weight, preferably from about 10% to about 30% by weight. 
The soiled dishes are cleaned by contacting the soiled surface of the dish 
with a cloth, sponge, or similar article. The cloth, sponge, or similar 
article may be immersed in the detergent composition and water mixture 
prior to being contacted with the dish surface, and is typically contacted 
with the dish surface for a period of time ranging from about 1 to about 
10 seconds, although the actual time will vary with each application and 
user. The contacting of the cloth, sponge, or similar article to the dish 
surface is preferably accompanied by a concurrent scrubbing of the dish 
surface. 
Another method of use will comprise immersing the soiled dishes into a 
water bath without any liquid dishwashing detergent. A device for 
absorbing liquid dishwashing detergent, such as a sponge, is placed 
directly into a separate quantity of undiluted liquid dishwashing 
composition for a period of time typically ranging from about 1 to about 5 
seconds. The absorbing device, and consequently the undiluted liquid 
dishwashing composition, is then contacted individually to the surface of 
each of the soiled dishes to remove said soiling. The absorbing device is 
typically contacted with each dish surface for a period of time range from 
about 1 to about 10 seconds, although the actual time of application will 
be dependent upon factors such as the degree of soiling of the dish. The 
contacting of the absorbing device to the dish surface is preferably 
accompanied by concurrent scrubbing. 
EXAMPLES 
The following examples illustrate the compositions of the present 
invention, but are not necessarily meant to limit or otherwise define the 
scope of the invention. All parts, percentages and ratios used herein are 
by weight unless otherwise specified. 
Example I 
The following light duty liquid compositions of the present invention are 
prepared according to the descriptions set forth below. 
A surfactant paste is initially formed by combining any desired surfactants 
with water and alcohol. The surfactants in this surfactant paste include 
the polyhydroxy fatty acid amides of the present invention. Ideally the 
surfactant paste should be pumpable at room or elevate temperatures. 
Separately, in a large mixing vessel having a propeller mixer, 
three-quarters of the water of the formulated product, one-half of the 
alcohol of the formulated product, one-half of the alcohol of the 
formulated product, and any optional hydrotropes (e.g. xylene, cumene, 
toluene sulfonates) and alkylpolyethoxypolycarboxylate surfactant (i.e. 
Polytergent C) are combined with mixing to give a clear solution. The 
surfactant paste is added and the pH of the mixture is adjusted to 
7.0-7.5, before the calcium ions are added. 
The calcium ions may be added directly to the mixing vessel as calcium 
chloride, calcium formate, or as calcium oxide or hydroxide powder. The 
calcium oxide or hydroxide powder is added to the acid form of the 
surfactant salts (e.g. alkyl benzene sulfonates, alkyl sulfates, alkyl 
ethoxylated sulfates, methyl ester sulfonates, etc.) in the surfactant 
paste. When calcium is added as a oxide or hydroxide powder, a less than 
stoichimometrically required amount is added with mixing to ensure 
complete dissolution. The pH of the calcium-containing surfactant paste is 
then adjusted by using NaOH or KOH solutions. 
The mixture is mixed until a homogenous, clear solution product is 
obtained. Additional water, alcohol, and any desired additional 
hydrotropes (added as a solution) may then be added to trim the solution 
product viscosity to the desired level, ideally between 50 and 1000 cps, 
as measured by a Brookfiled viscometer at 70.degree. F. The pH of the 
final product is then adjusted with either HCl or NaOH to a level of 
7.0.+-.0.7 for formulas containing ammonium ions, and 8.5.+-.1.5 for 
formulas which do not contain ammonium ions. 
Perfume, dye and other ingredients, e.g., opacifying agents such as Lytron 
and ethylene glycol distearate, are added as the last step. Lytron can be 
added directly as a dispersion with mixing. Ethylene glycol distearate 
must be added in a molten state with rapid mixing to form the desired 
pearlescent crystals. 
______________________________________ 
% By Weight 
Component A B C D 
______________________________________ 
C.sub.12-14 alkyl N-methyl glucamide.sup.1 
10.5 10.5 10.5 10.5 
Sodium C.sub.13-14 alkyl ethoxy 
17.00 17.00 17.00 
17.00 
(1-3) sulfate 
C.sub.9-11 alkyl ethoxy (ave. 10) 
5.00 5.00 5.00 5.00 
alcohol 
C.sub.12 alkyl fatty acid.sup.1 
1.4 1.4 1.4 1.4 
C.sub.12-13 alkyl dimethyl amine oxide 
2.00 2.00 2.00 2.00 
Magnesium chloride hexahydrate 
0.1 0.1 0.1 0.1 
Calcium formate 1.6 1.6 1.6 1.6 
Sodium cumene sulfonate 
2.00 2.00 2.00 2.00 
Sodium C.sub.12-14 alkylpoly- 
ethoxy polycarboxylate 
65% hydrophilicity -- 2.00 0 0 
82% hydrophilicity -- 0 2.00 0 
88% hydrophilicity -- 0 0 2.00 
Water and minors q.s. to 100% 
______________________________________ 
.sup.1 The C.sub.12-14 alkyl Nmethyl glucamide contains about 88% of 
C.sub.12-14 alkyl Nmethyl glucamide and 12% C.sub.12 alkyl fatty acid. 
The following procedure shows how the above formulations are evaluated in 
terms of how well they maintain their stability. The method used to 
evaluate stability of the compositions of this invention involves storing 
a portion of the product without opacifier at 40.degree. F. (4.4.degree. 
C.), room temperature, and 120.degree. F. (48.9.degree. C.) for several 
days. At the end of the period the product is evaluated visually for 
stability and/or clarity. 
TABLE I 
______________________________________ 
Stability Evaluation 
7 Days 
Composition 
4.4.degree. C. 
Room Temperature 
48.9.degree. C. 
______________________________________ 
A Unstable Unstable Unstable 
B Stable Stable Unstable* 
C Stable Stable Stable 
D Unstable Stable Unstable* 
______________________________________ 
*Recovers at room temperature. 
Results: Composition C containing an alkylpolyethoxypolycarboxylate 
surfactant with 82% hydrophilicity remains the most stable over a range of 
temperatures. Composition A with no alkylpolyethoxypolycarboxylate 
surfactant is not stable at any of the storage temperatures. Compositions 
B and D containing alkylpolyethoxypolycarboxylate surfactant with lower 
and higher % hydrophilicity, respectively, than Composition C are in 
between the results for Compositions A and C. 
Conclusion: The stability evaluation shows that the 
alkylpolyethoxypolycarboxylate-containing formulas, are more stable over a 
range of temperatures than compositions without alkyl 
polyethoxypolycarboxylate. Balancing the degree of carboxylation and 
ethoxylation (hydrophilicity), Composition C, is also effective in 
yielding a stable product. 
Example II 
The following liquid compositions are formulated. The compositions are 
prepared in the same manner as the compositions of Example I. 
______________________________________ 
% By Weight 
Component E F G 
______________________________________ 
C.sub.12-14 alkyl N-methyl glucamide.sup.1 
11.6 11.6 11.6 
Sodium C.sub.13-14 alkyl ethoxy (1-3) sulfate 
17 17 17 
C.sub.9-11 alkyl ethoxy (10 ave.) alcohol 
5 5 5 
C.sub.12 alkyl fatty acid.sup.1 
0.04 0.04 0.04 
C.sub.12-13 alkyl dimethyl amine oxide 
3 3 3 
Calcium formate 1.6 1.6 1.6 
Sodium C.sub.12-14 alkylpolyethoxy poly- 
-- 0.5 -- 
carboxylate, 82% hydrophilicity 
Citric acid -- -- 0.5 
Water and minors q.s. to 100% 
______________________________________ 
.sup.1 The C.sub.12-14 alkyl Nmethyl glucamide contains about 96.6% of 
C.sub.12-14 alkyl Nmethyl glucamide and about 3.3% C.sub.12 alkyl fatty 
acid. 
Product stability is evaluated as in Example I, results follow in Table II. 
TABLE II 
______________________________________ 
Stability Evaluation 
7 Days 
Composition 
4.4.degree. C. 
Room Temperature 
48.9.degree. C. 
______________________________________ 
E Unstable Unstable Stable 
F Stable Stable Stable 
G Stable Unstable Unstable 
______________________________________ 
Results: Composition F containing alkypolyethoxypolycarboyxlate remains 
stable over a range of temperatures. Composition G containing citric acid 
(a chelator) does not remain stable at the higher temperature (i.e. 
120.degree. F., 48.9.degree. C.) whereas Composition E containing no 
alkypolyethoxypolycarboxylate surfactant or citric acid is not stable at 
40.degree. F. (4.4.degree. C.) or room temperature. 
Conclusion: The stability evaluation shows that 
alkypolyethoxypolycarboxylate containing formulas are more stable over a 
range of temperatures than a composition containing citric acid, 
Composition F, or a composition containing no 
alkylpolyethoxypolycarboxylate or citric acid, Composition E. 
Example III 
The following compositions are formulated as in Example I. 
______________________________________ 
% By Weight 
Component H I 
______________________________________ 
C.sub.12 alkyl N-methyl glucamide 
8.7 8.7 
Sodium C.sub.13-14 alkyl ethoxy 
15.0 20.0 
(1-3) sulfate 
C.sub.9-11 alkyl ethoxy (10 ave.) alcohol 
4.0 2.0 
C.sub.12 alkyl fatty acid.sup.1 
0.3 0.3 
C.sub.13-14 alkyl dimethyl amine oxide 
3.0 2.0 
Calcium formate 1.6 2.1 
Sodium C.sub.12-14 alkylpolyethoxy poly- 
1.5 0.5 
carboxylate, 82% hydrophilicity 
Water and minors q.s. to 100% 
q.s. to 100 
______________________________________ 
.sup.1 The C.sub.12-14 alkyl Nmethyl glucamide contains about 96.7% of 
C.sub.12 alkyl Nmethyl glucamide and about 3.3% of C.sub.12 alkyl fatty 
acid. 
The compositions remain stable for at least 14 days at 40.degree. F. 
(4.4.degree. C.), room temperature and 120.degree. F. 
Example IV 
The following clear, stable, concentrated liquid composition are 
formulated. The compositions are prepared in the same manner as the 
compositions of Example I. 
______________________________________ 
% By Weight 
Component J K 
______________________________________ 
C.sub.12 alkyl N-methyl glucamide 
11.1 9.0 
Sodium C.sub.13-14 alkyl ethoxy (ave. 0.8) 
19.1 9.0 
sulfate 
Sodium C.sub.13-14 alkyl ethoxy (ave. 3) 
3.1 8.0 
sulfate 
C.sub.11 alkyl ethoxy (ave. 10) alcohol 
-- 5.0 
C.sub.10 alkyl ethoxy (ave. 8) alcohol 
4.6 -- 
Dodecyl dimethyl betaine 
2.6 3.0 
C.sub.13-14 alkyl dimethyl amine oxide 
1.6 2.0 
Calcium formate 0.15 0.6 
Magnesium chloride hexahydrate 
0.75 0.3 
Sodium C.sub.12-14 alkylpolyethoxypoly- 
1.0 0.5 
carboxylate, 82% hydrophilicity 
Water and minors q.s. to 100% 
q.s. to 100 
______________________________________