Stable liquid detergent compositions

Heavy-duty liquid detergents containing sulfonate and alcohol ethoxylate sulfate anionic surfactants, ethoxylated nonionic surfactant, optional quaternary ammonium, amine or amine oxide surfactants, saturated fatty acid, polycarboxylate builder, a neutralization system comprising sodium, potassium and preferably low levels of alkanolamines, and a solvent system comprising ethanol, polyol and water. The compositions are isotropic liquids providing a high level of detergency performance and improved chlorine bleach compatibility.

TECHNICAL FIELD 
The present invention relates to heavy-duty liquid detergent compositions 
containing sulfonate surfactant, alcohol ethoxylate sulfate surfactant, 
ethoxylated nonionic surfactant, an optional quaternary ammonium, amine or 
amine oxide surfactant, saturated fatty acid, polycarboxylate builder, a 
neutralization system comprising sodium, potassium and preferably low 
levels of alkanolamines, and a solvent system comprising ethanol, polyol 
and water. The compositions are isotropic liquids which provide a high 
level of detergency performance and improved chlorine bleach 
compatibility. 
There has been considerable demand for liquid detergents capable of 
providing superior cleaning under a wide variety of laundering conditions. 
Such compositions generally require a number of ingredients which tend to 
separate into discrete phases. Isotropic liquid detergents are desired for 
both consistency of performance and aesthetic reasons. The compositions 
should remain isotropic during shipping and storage, where temperatures of 
55.degree. F. (12.8.degree. C.) or lower are often encountered. They 
preferably are also formulated to recover, after freezing and thawing, to 
an isotropic phase prior to consumer use. 
Liquid detergents often contain high levels of alkanolamines to enhance 
performance and product stability. However, alkanolamines readily react 
with and destroy chlorine bleaches. Consumers who add chlorine bleaches to 
wash solutions containing alkanolamine-based detergents consequently do 
not obtain optimum bleaching performance. Thus, there is a continuing need 
for the development of a liquid detergent capable of providing superior 
cleaning, bleach compatibility and product stability. 
BACKGROUND ART 
Pending U.S. patent application Ser. No. 380,988, Wertz et al, filed May 
24, 1982, now abandoned, discloses detergent compositions containing 
anionic surfactants, quaternary ammonium, amine or amine oxide 
surfactants, and fatty acids, and formulated to provide a near-neutral 
wash pH. The compositions are preferably liquid detergents which 
additionally contain ethoxylated nonionic surfactants and polycarboxylate 
builders. 
U.S. Pat. No. 4,285,841, Barrat et al, issued Aug. 25, 1981, discloses 
liquid detergents containing anionic surfactants, nonionic surfactants and 
from about 8% to about 20% by weight of a fatty acid. The compositions 
have a pH of from about 6.0 to about 7.5. 
U.S. Pat. No. 4,287,082, Tolfo et al, issued Sept. 1, 1981, discloses 
liquid detergents containing saturated fatty acids, enzymes, 
enzyme-accessible calcium and short-chain carboxylic acid salts, 
preferably formates. 
SUMMARY OF THE INVENTION 
The present invention encompasses heavy-duty liquid detergent compositions 
comprising, by weight: 
(a) from about 5% to about 15%, on an acid basis, of a sulfonate surfactant 
containing a C.sub.10 -C.sub.16 alkyl or alkenyl group; 
(b) from about 8% to about 18%, on an acid basis, of an alcohol ethoxylate 
sulfate surfactant of the formula RO(C.sub.2 H.sub.4 O).sub.m SO.sub.3 M, 
wherein R is a C.sub.10 -C.sub.16 alkyl or hydroxyalkyl group, m is from 
about 0.5 to about 4, and M is a compatible cation; 
(c) from about 2% to about 15% of an ethoxylated nonionic surfactant of the 
formula R.sup.1 (OC.sub.2 H.sub.4).sub.n OH, wherein R.sup.1 is a C.sub.10 
-C.sub.16 alkyl group or a C.sub.8 -C.sub.12 alkyl phenyl group, n is from 
about 3 to about 9, and said nonionic surfactant has an HLB of from about 
10 to about 13; 
(d) from about 0% to about 5% of a cosurfactant selected from the group 
consisting of: 
(i) quaternary ammonium surfactants having the formula: 
EQU [R.sup.2 (OR.sup.3).sub.y ][R.sup.4 (OR.sup.3).sub.y ].sub.2 R.sup.5 
N.sup.+ X.sup.- 
wherein R.sup.2 is an alkyl or alkyl benzyl group having from about 6 to 
about 16 carbon atoms in the alkyl chain; each R.sup.3 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.4 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.5 is the same as R.sup.4 or is an alkyl 
chain wherein the total number of carbon atoms of R.sup.2 plus R.sup.5 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; 
(ii) amine surfactants having the formula: 
EQU [R.sup.2 (OR.sup.3).sub.y ][R.sup.4 (OR.sup.3).sub.y ]R.sup.5 N 
wherein R.sup.2, R.sup.3, R.sup.4, R.sup.5 and y are as defined above; 
(iii) amine oxide surfactants having the formula: 
EQU [R.sup.2 (OR.sup.3).sub.y ][R.sup.4 (OR.sup.3).sub.y ]R.sup.5 N.fwdarw.0 
wherein R.sup.2, R.sup.3, R.sup.4, R.sup.5 and y are as defined above; 
(e) from about 5% to about 20% of a C.sub.10 -C.sub.14 saturated fatty 
acid, the weight ratio of C.sub.10 -C.sub.12 fatty acid to C.sub.14 fatty 
acid being at least 1; 
(f) from about 3% to about 8%, on an acid basis, of a water-soluble 
polycarboxylate builder material; 
(g) from about 0 to about 0.04 moles per 100 grams of composition of an 
alkanolamine selected from the group consisting of monoethanolamine, 
diethanolamine and triethanolamine; 
(h) potassium and sodium ions in a potassium to sodium molar ratio of from 
about 0.1 to about 1.3; 
(i) from about 2% to about 10% ethanol; 
(j) from about 2% to about 15% of a polyol containing from 2 to 6 carbon 
atoms and from 2 to 6 hydroxy groups; and 
(k) from about 25% to about 40% water; 
said composition containing from about 20% to about 35% of (a), (b), (c) 
and (d); from about 8% to about 28% of (e) and (f); from about 33% to 
about 50% of (a), (b), (c), (d), (e) and (f); from about 8% to about 20% 
of (i) and (j); and from about 35% to about 55% of (i), (j) and (k); the 
weight ratio of (a) to (b) being from about 0.3 to about 1.7; the weight 
ratio of (a) plus (b) to (c) being from about 1 to about 10; and all of 
said components being selected to provide an isotropic liquid at 
55.degree. F. (12.8.degree. C.) having an initial pH of from about 7.5 to 
about 9.0 at a concentration of about 10% by weight in water at 68.degree. 
F. (20.degree. C.).

DETAILED DESCRIPTION OF THE INVENTION 
The liquid detergent of the present invention contain sulfonate and alcohol 
ethoxylate sulfate anionic surfactants, ethoxylated nonionic surfactant, 
optional quaternary ammonium, amine or amine oxide surfactants, saturated 
fatty acid, polycarboxylate builder, a neutralization system comprising 
sodium, potassium and preferably low levels of alkanolamines, and a 
solvent system comprising ethanol, polyol and water. 
The compositions herein are formulated to provide a high level of 
detergency performance under a wide variety of laundering conditions. They 
also provide improved chlorine bleach compatibility due to the limited 
amount of alkanolamines. Since the compositions contain a relatively high 
level of active components and little or no alkanolamine to enhance 
product stability, the types, levels and ratios of the components must be 
carefully balanced to provide isotropic liquids at 55.degree. F. 
(12.8.degree. C.). Preferred compositions herein are isotropic liquids at 
50.degree. F. (10.degree. C.). They preferably also recover, after 
freezing and thawing, to an isotropic form by 55.degree. F. (12.8.degree. 
C.), more preferably by 50.degree. F. (10.degree. C.). 
In order to meet these stability constraints, the present compositions 
require a neutralization system comprising mixed potassium and sodium 
ions. Complete sodium neutralization causes crystallization of the 
polycarboxylate builder, whereas all potassium neutralization results in 
an unacceptably high gel point. The total level of organic and inorganic 
bases must also be selected to provide a sufficiently high product pH to 
minimize the level of poorly-soluble free fatty acids, without being so 
high that pH sensitive strain removal, enzyme stability, and greasy/oily 
soil removal are compromised. 
The compositions also require a solvent system comprising water and a 
mixture of ethanol and polyol. Crystallization occurs without the polyol 
and unacceptably high gel points are obtained without the ethanol. The 
amount of ethanol and polyol must also be sufficient to prevent organic 
phase separation (i.e., keep free fatty acids and poorly-soluble 
surfactants in solution), and yet not be so high as to cause lye phase 
separation and/or crystallization by limiting the amount of water 
available. 
SULFONATE SURFACTANT 
The detergent compositions herein contain from about 5% to about 15%, 
preferably from about 6% to about 10%, by weight (on an acid basis) of an 
anionic sulfonate surfactant containing a C.sub.10 -C.sub.16 alkyl or 
alkenyl group. Anionic sulfonate surfactants useful herein are disclosed 
in U.S. Pat. No. 4,285,841, Barrat et al, issued Aug. 25, 1981, and in 
U.S. Pat. No. 3,919,678, Laughlin et al, issued Dec. 30, 1975, both 
incorporated herein by reference. 
Preferred sulfonate surfactants are the water-soluble salts, particularly 
the alkali metal, and alkanolammonium (e.g., monoethanolammonium or 
triethanolammonium) salts of alkylbenzene sulfonates in which the alkyl 
group contains from about 10 to about 15 carbon atoms, in straight chain 
or branched chain configuration, e.g., those of the type described in U.S. 
Pat. Nos. 2,220,099 and 2,477,383, incorporated herein by reference. 
Especially valuable are linear straight chain alkylbenzene sulfonates in 
which the average number of carbon atoms in the alkyl group is from about 
11 to about 13. 
Also useful herein are the water-soluble salts of paraffin sulfonates, 
olefin sulfonates, alkyl glyceryl ether sulfonates, esters of 
.alpha.-sulfonated fatty acids containing from about 1 to 10 carbon atoms 
in the ester group, 2-acyloxy-alkane-1-sulfonates containing from about 2 
to 9 carbon atoms in the acyl group, and .beta.-alkyloxy alkane sulfonates 
containing from about 1 to 3 carbon atoms in the alkyl group. 
Mixtures of the above-described sulfonates, particularly with the 
C.sub.11-13 linear alkylbenzene sulfonates, can also be used. 
ALCOHOL ETHOXYLATE SULFATE SURFACTANT 
The present compositions also contain an alcohol ethoxylate sulfate 
surfactant of the formula RO(C.sub.2 H.sub.4 O).sub.m SO.sub.3 M, wherein 
R is a C.sub.10 -C.sub.16 alkyl (preferred) or hydroxyalkyl group, m is 
from about 0.5 to about 4, and M is a compatible cation. This surfactant 
represents from about 8% to about 18%, preferably from about 9% to about 
14%, by weight (on an acid basis) of the composition. 
Preferred alcohol ethoxylate sulfate surfactants of the above formula are 
those wherein the R substituent is a C.sub.12-15 alkyl group and m is from 
about 1.5 to about 3. Examples of such materials are C.sub.12-15 alkyl 
polyethoxylate (2.25) sulfate (C.sub.12-15 E.sub.2.25 S); C.sub.14-15 
E.sub.2.25 S; C.sub.12-13 E.sub.1.5 S; C.sub.14-15 E.sub.3 S; and mixtures 
thereof. The sodium, potassium, monoethanolammonium, and 
triethanolammonium salts of the above are preferred. 
ETHOXYLATED NONIONIC SURFACTANT 
The compositions also contain from about 2% to about 15%, preferably from 
about 4% to about 10%, by weight of an ethoxylated nonionic surfactant of 
the formula R.sup.1 (OC.sub.2 H.sub.4).sub.n OH, wherein R.sup.1 is a 
C.sub.10 -C.sub.16 alkyl group or a C.sub.8 -C.sub.12 alkyl phenyl group, 
n is from about 3 to about 9, and said nonionic surfactant has an HLB 
(hydrophile-lipophile balance) of from about 10 to about 13. These 
surfactants are more fully described in U.S. Pat. Nos. 4,285,841, Barrat 
et al, issued Aug. 25, 1981, and 4,284,532, Leikhim et al, issued Aug. 18, 
1981, both incorporated herein by reference. Particularly preferred are 
condensation products of C.sub.12 -C.sub.14 alcohols with from about 3 to 
about 7 moles of ethylene oxide per mole of alcohol, e.g., C.sub.12 
-C.sub.13 alcohol condensed with about 6.5 moles of ethylene oxide per 
mole of alcohol. 
COSURFACTANT 
The compositions herein can contain from about 0% to about 5%, preferably 
from about 0.5% to about 3%, by weight of a cosurfactant selected from 
certain quaternary ammonium, amine, and amine oxide surfactants. The 
quaternary ammonium surfactants are particularly preferred. 
The quaternary ammonium surfactants useful herein are of the formula: 
EQU [R.sup.2 (OR.sup.3).sub.y ][R.sup.4 (OR.sup.3).sub.y ].sub.2 R.sup.5 
N.sup.+ X.sup.- 
wherein R.sup.2 is an alkyl or alkyl benzyl group having from about 6 to 
about 16 carbon atoms in the alkyl chain; each R.sup.3 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.4 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.5 is the same as R.sup.4 or is an alkyl 
chain wherein the total number of carbon atoms of R.sup.2 plus R.sup.5 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.5 is selected from the same groups as R.sup.4. The most 
preferred quaternary ammonium surfactants are the chloride, bromide and 
methylsulfate C.sub.8-16 alkyl trimethylammonium salts, C.sub.8-16 alkyl 
di(hydroxyethyl)methylammonium salts, the C.sub.8-16 alkyl 
hydroxyethyldimethylammonium salts, C.sub.8-16 alkyloxypropyl 
trimethylammonium salts, and the C.sub.8-16 alkyloxypropyl 
dihydroxyethylmethylammonium salts. Of the above, the C.sub.10 -C.sub.14 
alkyl trimethylammonium salts are preferred, e.g., decyl trimethylammonium 
methylsulfate, lauryl trimethylammonium chloride, myristyl 
trimethylammonium bromide and coconut trimethylammonium chloride and 
methylsulfate. 
Under cold water washing conditions, i.e., less than about 65.degree. F. 
(18.3.degree. C.), the C.sub.8-10 alkyl trimethylammonium surfactants are 
particularly preferred since they have lower Kraft boundaries and 
crystallization temperatures than the longer chain quaternary ammonium 
surfactants. 
Amine surfactants useful herein are of the formula: 
EQU [R.sup.2 (OR.sup.3).sub.y ][R.sup.4 (OR.sup.3).sub.y ]R.sup.5 N 
wherein the R.sup.2, R.sup.3, R.sup.4, R.sup.5 and y substituents are as 
defined above for the quaternary ammonium surfactants. Particularly 
preferred are the C.sub.12-16 alkyl dimethyl amines. 
Amine oxide surfactants useful herein are of the formula: 
EQU [R.sup.2 (OR.sup.3).sub.y ][R.sup.4 (OR.sup.3).sub.y ]R.sup.5 N.fwdarw.0 
wherein the R.sup.2, R.sup.3, R.sup.4, R.sup.5 and y substituents are also 
as defined above for the quaternary ammonium surfactants. Particularly 
preferred are the C.sub.12-16 alkyl dimethyl amine oxides. 
Amine and amine oxide surfactants are preferably used at higher levels than 
the quaternary ammonium surfactants since they are only partially 
protonated in the present systems. For example, preferred compositions 
herein can contain from about 0.5% to about 1.5% of the quaternary 
ammonium surfactant, or from about 1% to about 3% of the amine or amine 
oxide surfactants. 
FATTY ACID 
The compositions of the present invention contain from about 5% to about 
20%, preferably from about 8% to about 18%, most preferably from about 10% 
to about 16%, by weight of a saturated fatty acid containing from about 10 
to about 14 carbon atoms. In addition, the weight ratio of C.sub.10 
-C.sub.12 fatty acid to C.sub.14 fatty acid should be at least 1, 
preferably at least 1.5. 
Suitable saturated fatty acids can be obtained from natural sources such as 
plant or animal esters (e.g., palm kernel oil, palm oil and coconut oil) 
or synthetically prepared (e.g., via the oxidation of petroleum or by 
hydrogenation of carbon monoxide via the Fisher-Tropsch process). Examples 
of suitable saturated fatty acids for use in the compositions of this 
invention include capric, lauric, myristic, coconut and palm kernel fatty 
acid. Preferred are saturated coconut fatty acids, from about 5:1 to 1:1 
(preferably about 3:1) weight ratio mixtures of lauric and myristic acid, 
mixtures of the above with minor amounts (e.g., 10%-50% of total fatty 
acid) of oleic acid; and palm kernel fatty acid. 
POLYCARBOXYLATE BUILDER 
The compositions herein also contain from about 3% to about 8%, preferably 
from about 3% to about 6%, more preferably from about 3.5% to about 5% by 
weight on an acid basis, of a water-soluble polycarboxylate detergent 
builder material. Polycarboxylate builders are described in U.S. Pat. No. 
4,284,532, Leikhim et al, issued Aug. 18, 1981, incorporated herein by 
reference. 
The various aminopolycarboxylates, cycloalkane polycarboxylates, ether 
polycarboxylates, alkyl polycarboxylates, epoxy polycarboxylates, 
tetrahydrofuran polycarboxylates, benzene polycarboxylates, and polyacetal 
polycarboxylates are suitable for use herein. 
Examples of such polycarboxylate builders are sodium and potassium 
ethylenediaminetetraacetate; sodium and potassium nitrilotriacetate; the 
water-soluble salts of phytic acid, e.g., sodium and potassium phytates, 
disclosed in U.S. Pat. No. 1,739,942, Eckey, issued Mar. 27, 1956, 
incorporated herein by reference; the polycarboxylate materials described 
in U.S. Pat. No. 3,364,103, incorporated herein by reference; and the 
water-soluble salts of polycarboxylate polymers and copolymers described 
in U.S. Pat. No. 3,308,067, Diehl, issued Mar. 7, 1967, incorporated 
herein by reference. 
Useful detergent builders also include the water-soluble salts of polymeric 
aliphatic polycarboxylic acids having the following structural and 
physical characteristics: 
(a) a minimum molecular weight of about 350 calculated as to the acid form; 
(b) an equivalent weight of about 50 to about 80 calculated as to acid 
form; (3) at least 45 mole percent of the monomeric species having at 
least two carboxyl radicals separated from each other by not more than two 
carbon atoms; (d) the site of attachment of the polymer chain of any 
carboxyl-containing radical being separated by not more than three carbon 
atoms along the polymer chain from the site of attachment of the next 
carboxyl-containing radical. Specific examples of such builders are the 
polymers and copolymers of itaconic acid, aconitic acid, maleic acid, 
mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid. 
Other suitable polycarboxylate builders include the water-soluble salts, 
especially the sodium and potassium salts, of mellitic acid, citric acid, 
pyromellitic acid, benzene pentacarboxylic acid, oxydiacetic acid, 
carboxymethyloxysuccinic acid, carboxymethyloxymalonic acid, 
cis-cyclohexanehexacarboxylic acid, cis-cyclopentanetetracarboxylic acid 
and oxydisuccinic acid. 
Other polycarboxylates for use herein are the polyacetal carboxylates 
described in U.S. Pat. No. 4,144,226, issued Mar. 13, 1979 to Crutchfield 
et al, and U.S. Pat. No. 4,146,495, issued Mar. 27, 1979 to Crutchfield et 
al, both incorporated herein by reference. 
Citric acid is a highly preferred polycarboxylate builder. 
NEUTRALIZATION SYSTEM 
The present compositions can contain from about 0 to about 0.04 moles, 
preferably from about 0.01 to about 0.035 moles, more preferably from 
about 0.015 to about 0.03 moles, per 100 grams of composition of an 
alkanolamine selected from the group consisting of monoethanolamine, 
diethanolamine, triethanolamine, and mixtures thereof. Low levels of the 
alkanolamines, particularly monoethanolamine, are preferred to enhance 
product stability, detergency performance, and odor. However, the amount 
of alkanolamine should be minimized for best chlorine bleach 
compatibility. While the present compositions can contain mixtures of the 
alkanolamines, best color stability is obtained using single 
alkanolamines. 
In addition, the compositions contain potassium and sodium ions in a 
potassium to sodium molar ratio of from about 0.1 to about 1.3, preferably 
from about 0.6 to about 1. 
SOLVENT SYSTEM 
The solvent system for the compositions is comprised of ethanol, a polyol 
and water. Ethanol is present at a level of from about 2% to about 10%, 
preferably from about 5% to about 9%, by weight of the composition. 
Any polyol containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy 
groups can be used in the present compositions. Examples of such polyols 
are ethylene glycol, propylene glycol and glycerine. Propylene glycol is 
particularly preferred. The polyol represents from about 2% to about 15%, 
preferably from about 3% to about 10%, by weight of the composition. 
The compositions also contain from about 25% to about 40%, preferably from 
about 28% to about 37%, by weight of water. 
In addition to the above, the ethanol and polyol together represent from 
about 8% to about 20%, preferably about 11% to about 16%, by weight of the 
composition. The ethanol, polyol and water should total from about 35% to 
about 55%, preferably about 40% to about 50%, by weight of the 
composition. 
The compositions of the present invention are further constrained by the 
following limits, in which all percentages and ratios are calculated on an 
acid basis where anionic materials are involved. The sulfonate, alcohol 
ethoxylate sulfate, ethoxylated nonionic and quaternary ammonium, amine or 
amine oxide surfactants, together, represent from about 20% to about 35%, 
preferably from about 23% to about 30%, by weight of the composition. The 
weight ratio of the sulfonate surfactant to the alcohol ethoxylate sulfate 
surfactant should also be from about 0.3 to about 1.7, preferably from 
about 0.6 to about 1. The weight ratio of these anionic surfactants to the 
ethoxylated nonionic surfactant should also be from about 1 to about 10, 
preferably from about 2 to about 5. 
The fatty acid and polycarboxylate builder together represent from about 8% 
to about 28%, preferably from about 13% to about 22%, by weight of the 
composition. In addition, the fatty acid, polycarboxylate builder and 
above surfactants represent a total of from about 33% to about 50%, 
preferably from about 36% to about 48%, by weight of the composition. 
Finally, all of the above components are selected to provide an isotropic 
liquid detergent at 55.degree. F. (12.8.degree. C.), preferably at 
50.degree. F. (10.degree. C.). The components are also selected to provide 
an initial pH of from about 7.5 to about 9.0, preferably from about 7.8 to 
about 8.8, at a concentration of 10% by weight in water at 68.degree. F. 
(20.degree. C.). 
OPTIONAL COMPONENTS 
Optional components for use in the liquid detergents herein include 
enzymes, enzyme stabilizing agents, polyacids, soil removal agents, 
antiredeposition agents suds regulants, hydrotropes, opacifiers, 
antioxidants, bactericides, dyes, perfumes, and brighteners described in 
the U.S. Pat. No. 4,285,841, Barrat et al, issued Aug. 25, 1981, 
incorporated herein by reference. Such optional components generally 
represent less than about 15%, preferably from about 2% to about 10%, by 
weight of the composition. 
Enzymes are highly preferred optional ingredients and are incorporated in 
an amount of from about 0.025% to about 2%, preferably from about 0.05% to 
about 1.5%. Preferred proteolytic enzymes should provide a proteolytic 
activity of at least about 5 Anson units (about 1,000,000 Delft units) per 
liter, preferably from about 15 to about 70 Anson units per liter, most 
preferably from about 20 to about 40 Anson units per liter. A proteolytic 
activity of from about 0.01 to about 0.05 Anson units per gram of product 
is desirable. Other enzymes, including amylolytic enzymes, are also 
desirably included in the present compositions. 
Suitable proteolytic enzymes include the many species known to be adapted 
for use in detergent compositions. Commercial enzyme preparations such as 
"Alcalase" sold by Novo Industries and "Maxatase" sold by Gist-Brocades, 
Delft, The Netherlands, are suitable. Other preferred enzyme compositions 
include those commercially available under the tradenames SP-72 
("Esperase") manufactured and sold by Novo Industries, A/S, Copenhagen, 
Denmark and "AZ-Protease" manufactured and sold by Gist-Brocades, Delft, 
The Netherlands. 
Suitable amylases include "Rapidase" sold by Gist-Brocades and "Termamyl" 
sold by Novo Industries. 
A more complete disclosure of suitable enzymes can be found in U.S. Pat. 
No. 4,101,457, Place et al, issued July 18, 1978, incorporated herein by 
reference. 
When enzymes are incorporated in the detergent compositions of this 
invention, they are desirably stabilized by using a mixture of a short 
chain carboxylic acid salt and calcium ion, such as disclosed in U.S. Pat. 
No. 4,318,818, Letton et al, issued Mar. 9, 1982, incorporated herein by 
reference. 
The short chain carboxylic acid salt is preferably water-soluble, and most 
preferably is a formate, e.g., sodium formate. The short chain carboxylic 
acid salt is used at a level from about 0.25% to about 10%, preferably 
from about 0.3% to about 3%, more preferably from about 0.5% to about 
1.5%. Any water-soluble calcium salt can be used as a source of calcium 
ion, including calcium acetate, calcium formate and calcium propionate. 
The composition should contain from about 0.1 to about 30 millimoles of 
calcium ion per liter, preferably from about 0.5 to about 15 millimoles of 
calcium ion per liter. When materials are present which complex calcium 
ion, it is necessary to use high levels of calcium ion so that there is 
always some minimum level available for the enzyme. 
Enzymes are preferably stabilized in the present compositions by the 
addition of from about 0.25% to about 10%, preferably from about 0.5% to 
about 5%, more preferably from about 0.75% to about 3%, by weight of boric 
acid or a compound capable of forming boric acid in the composition 
(calculated on the basis of the boric acid). Boric acid is preferred, 
although other compounds such as boric oxide, borax and other alkali metal 
borates (e.g., sodium ortho-, meta- and pyroborate, and sodium 
pentaborate) are suitable. Substituted boric acids (e.g., phenylboronic 
acid, butane boronic acid, and p-bromo phenylboronic acid) can also be 
used in place of boric acid. 
The combination of boric acid and formate provides improved protease 
stability, although amylase stability appears to be slightly less than 
that obtained using boric acid alone. 
Preferred compositions also contain from about 0.01% to about 1% of a 
polyacid or salt thereof, to enhance pretreatment performance. Preferred 
polyacids for use herein are ethylenediamine tetramethylenephosphonic 
acid, diethylene triamine pentamethylenephosphonic acid, and 
diethylenetriamine pentaacetic acid, or the salts thereof. These 
polyacids/salts are preferably used in an amount from about 0.1% to about 
0.8%. 
Preferred compositions herein further contain from about 0.5% to about 3%, 
preferably from about 1% to about 2%, by weight of a highly ethoxylated 
polyethyleneamine or polyethyleneimine soil removal and antiredeposition 
agent, such as those described in pending U.S. patent application Ser. No. 
452,463, Vander Meer, filed Dec. 23, 1982. A particularly preferred 
material is tetraethylene pentaimine ethoxylated with about 15-18 moles of 
ethylene oxide at each hydrogen site. 
The following examples illustrate the compositions of the present 
invention. 
All parts, percentages and ratios used herein are by weight unless 
otherwise specified. 
EXAMPLE I 
Liquid detergent compositions of the present invention are as follows: 
______________________________________ 
Wt. % 
Component A B 
______________________________________ 
C.sub.13 linear alkylbenzene sulfonic acid 
7.2 7.2 
C.sub.14-15 alkyl polyethoxylate (2.25) 
10.8 10.8 
sulfuric acid 
C.sub.12-13 alcohol polyethoxylate (6.5)* 
6.5 6.5 
C.sub.12 alkyl trimethylammonium chloride 
1.2 0.6 
C.sub.12-14 fatty acid 
13.0 -- 
Oleic acid 2.0 -- 
Palm kernel fatty acid (stripped) 
-- 15.0 
Citric acid (anhydrous) 
4.0 4.0 
Diethylenetriamine pentaacetic acid 
0.23 0.23 
Protease enzyme (2.0 AU/g) 
0.75 0.75 
Amylase enzyme (375 Am. U/g) 
0.16 0.16 
TEPA-E.sub.15-18 ** 1.5 1.5 
Monoethanolamine 2.0 -- 
(moles of alkanolamine) 
(0.033) (0) 
Sodium ion 1.66 2.75 
Potassium ion 2.65 2.55 
(molar K.sup.+ :Na.sup.+) 
(0.94) (0.55) 
Propylene glycol 6.8 5.0 
Ethanol 7.8 8.5 
Formic acid 0.66 0.66 
Calcium ion 0.03 0.03 
Minors and water Balance to 100 
pH at concentration of 10% 
8.65 8.5 
in water at 68.degree. F. (20.degree. C.) 
______________________________________ 
*Alcohol and monoethoxylated alcohol removed. 
**Tetraethylene pentaimine ethoxylated with 15-18 moles (avg.) of ethylen 
oxide at each hydrogen site. 
Composition A was prepared by adding the components, with continuous 
mixing, in the following order: paste premix of alkylbenzene sulfonic 
acid, sodium hydroxide, propylene glycol and ethanol; paste premix of 
alkyl polyethoxylate sulfuric acid, sodium hydroxide and ethanol; 
pentaacetic acid; alcohol polyethoxylate; premix of water, brighteners, 
alkanolamine, and alcohol polyethoxylate; ethanol; sodium and potassium 
hydroxide; fatty acid; citric acid; formic acid and calcium; alkyl 
trimethylammonium chloride; TEPA-E.sub.15-18 ; adjust pH to about 8.1; and 
balance of components. 
Composition B was prepared by adding the components, with continuous 
mixing, in the following order: paste premix of alkyl polyethoxylate 
sulfuric acid and ethanol; 2.5 parts water; propylene glycol; premix of 
ethanol and brightener; ethanol; premix of water, propylene glycol and 
brightener; alcohol polyethoxylate; sodium hydroxide; potassium hydroxide; 
fatty acid; alkylbenzene sulfuric acid; premix of citric acid and calcium; 
pentaacetic acid; formic acid; alkyl trimethylammonium chloride; 
TEPA-E.sub.15-18 ; potassium hydroxide and water; and balance of 
components. 
Compositions A and B were isotropic liquids as made and remained isotropic 
down to about 50.degree. F. (10.degree. C.). They also recovered to an 
isotropic form, after freezing and thawing, by about 55.degree. F. 
(12.8.degree. C.). 
EXAMPLE II 
The following liquid detergents of the invention were made using the same 
order of addition as for Composition A of Example I. The compositions were 
stable isotropic liquids at 55.degree. F. (12.8.degree. C.). 
______________________________________ 
Wt. % 
Components A B C 
______________________________________ 
C.sub.13 linear alkylbenzene 
7.5 10.5 -- 
sulfonic acid 
C.sub.11.4 linear alkylbenzene 
-- -- 4.7 
sulfonic acid 
C.sub.14-15 alkyl polyethoxylate 
7.5 7.5 -- 
(2.25) sulfuric acid 
C.sub.12-14 alkyl polyethoxylate 
-- -- 4.8 
(1.0) sulfuric acid 
C.sub.12-13 alcohol polyethoxylate 
12.0 6.5 9.5 - (6.5)* 
C.sub.12 alkyl trimethylammonium 
1.2 -- 1.2 
chloride 
C.sub.12-16 alkyl dimethyl amine 
-- 0.6 -- 
oxide 
C.sub.12-14 fatty acid 
12.0 13.0 11.0 
Oleic acid -- 2.0 -- 
Citric acid 3.0 4.0 5.0 
Diethylenetriamine penta- 
0.23 0.23 0.23 
acetic acid 
Protease enzyme (2.0 AU/g) 
0.75 0.75 0.75 
Amylase enzyme (375 Am. U/g) 
0.16 0.16 0.16 
TEPA-E.sub.15-18 ** 
1.5 1.5 1.5 
Monoethanolamine -- 1.0 2.2 
(moles of alkanolamine) 
(0) (0.016) (0.036) 
Sodium ion 1.81 2.50 1.41 
Potassium ion 2.58 2.58 2.58 
(molar K.sup.+ :Na.sup.+) 
(0.84) (0.61) (1.08) 
Propylene glycol 8.0 10.0 5.0 
Ethanol 7.0 6.0 4.0 
Formic acid 0.66 0.66 0.66 
Calcium ion 0.038 0.038 0.038 
Minors and water Balance to 100 
pH at concentration of 10% 
8.60 8.45 8.75 
in water at 68.degree. F. (20.degree. C.) 
______________________________________ 
EXAMPLE III 
The following liquid detergents of the invention were made using the same 
order of addition as for Composition A of Example I. The compositions were 
stable isotropic liquids at 50.degree. F. (10.degree. C.). They also 
recovered, after freezing and thawing, to an isotropic form by 50.degree. 
F. (10.degree. C.). 
______________________________________ 
Wt. % 
Components A B 
______________________________________ 
C.sub.13 linear alkylbenzene sulfonic acid 
8.0 8.0 
C.sub.14-15 alkyl polyethoxylate (2.25) 
12.0 12.0 
sulfuric acid 
C.sub.12-13 alcohol polyethoxylate (6.5)* 
5.0 5.0 
C.sub.12 alkyl trimethylammonium chloride 
0.6 0.6 
C.sub.12-14 fatty acid 
10.0 7.7 
Oleic acid 0.5 -- 
Palm kernel fatty acid 
-- 3.3 
Citric acid 4.0 4.0 
Diethylenetriamine pentaacetic acid 
0.23 0.23 
Protease enzyme (2.0 AU/g) 
0.75 0.75 
Amylase enzyme (375 Am. U/g) 
0.16 0.16 
TEPA-E.sub.15-18 ** 2.0 2.0 
Monoethanolamine 2.0 2.0 
(moles of alkanolamine) 
(0.033) (0.033) 
Sodium ion 2.53 2.53 
Potassium ion 1.11 1.11 
(molar K.sup.+ :Na.sup.+) 
(0.26) (0.26) 
Propylene glycol 3.5 3.5 
Ethanol 8.5 8.5 
Formic acid 0.08 0.08 
Boric acid 1.25 1.25 
Calcium ion 0.03 0.03 
Minors and water Balance to 100 
pH at concentration of 10% in water at 
8.45 8.45 
68.degree. F. (20.degree. C.) 
______________________________________