STABLE CLEAR ISOTROPIC LIQUID DETERGENT COMPOSITIONS CONTAINING SODIUM CARBONATE

COMPOSITIONS DETERSIVES LIQUIDES ISOTROPES, TRANSPARENTS ET STABLES, A TENEUR DE CARBONATE DE SODIUM

English Abstract

A clear, single phase, carbonate built liquid
detergent composition, which is freeze/thaw stable, comprising
(a) an anionic surfactant; (b) an oxyalkylate nonionic
surfactant of the general formula:
<IMG>
wherein R is an alkyl chain of from C8 to C15, x is a number
from about 4 to 15, y is a number from about o to 15, z is a
number from 0 to 5, the molecular weight is from about 300 to
2,200; (c) an alkali metal carbonate builder, (d) a
hydrotrope, and (e) the balance water.

Claims

The embodiments of the invention in which an
exclusive property or privilege is claimed are defined as
follows:
1. A clear, single phase, carbonate built
liquid detergent composition, which is freeze/thaw stable,
comprising:
(a) an anionic surfactant
(b) an oxyalkylate nonionic surfactant of the
general formula:
<IMG>
wherein R is an alkyl chain of from C8 to C15, x is a number
from about 4 to 15, y is a number from about 0 to 15, z is
a number from 0 to 5, and the molecular weight is from
about 300 to 2,200;
(c) an alkali metal carbonate builder,
(d) a single hydrotrope, and
(e) the balance water.
2. The composition of claim 1, further
including a copolymer of the general formula:
<IMG> ( I)
wherein X = H, Na or similar alkali metal; A = an alkyl
group having a chain length of 2 to 20 carbon atoms and
preferably 6 to 10 carbon atoms, and m and n are numbers
such that the monomer ratio is in the range of about 9:1
to 1:9 and a total average molecular weight of the
copolymer is from 1,000 to 70,000; a copolymer of the
26

general formula:
<IMG> (II)
wherein X = H, Na or similar alkali metal and m and n are
numbers such that the monomer ratio is in the range of
about 9:1 to 1:9 and a total average molecular weight of
the copolymer is from 1,000 to 70,000; or a homopolymer of
the general formula:
<IMG>
(III)
wherein X = H, Na or similar alkali metal, and n is a
number such that the total molecular weight of the polymer
is from 1000 to 70,000; and mixtures thereof.
3. The composition of claim 1, wherein said
carbonate builder is an alkali metal carbonate.
4. The composition of claim 3, wherein the
alkali metal carbonate builder is selected from the group
consisting of sodium carbonate, sodium bicarbonate, sodium
sesquicarbonate, potassium carbonate, potassium
bicarbonate, potassium sesquicarbonate, and mixtures
thereof.
5. The composition of claim 1, wherein said
anionic surfactant is selected from the group consisting
of C8 to C11 alkylbenzene sulfonates, C12 to C16
alkylsulfates, C12 to C16 alkylsulfosuccinates, sulfates
ethoxylated C12 to C16 alkanols, and mixtures thereof.
6. The composition of claim 1, wherein the
27

hydrotrope is selected from the group alkali metal and
ammonium salts of alkyl benzene sulfonic acid, toluene
sulfonic acid and xylene sulfonic acid.
7. The composition of claim 1, wherein the
hydrotrope is selected from the group consisting of sodium
cumene sulfonates and potassium salts of phosphate esters.
8. The composition of claim 1, wherein the
polymer I has a molecular weight of from about 1000 to
25,000.
9. The composition of claim 1, wherein the
copolymer (II) has a molecular weight of from about 1000
to 10,000.
10. The composition of claim 1, wherein the
homopolymer (III) has a molecular weight of from about
1000 to 8000.
11 A clear, single phase, carbonate built
liquid detergent composition, which is freeze/thaw stable,
comprising:
(a) from about 1.0 to 15.0 percent by weight
anionic surfactant
(b) from about 0.1 to 7.0 percent by weight of
an oxyalkylate nonionic surfactant of the
general formula:
<IMG>
wherein R is an alkyl chain of from C8 to C15, x is a number
from about 4 to 15, y is a number from about 0 to 15, z is
a number from 0 to 5, and the molecular weight is from
about 300 to 2,200;
28

(c) from about 0.1 to 5.0 percent by weight of
an alkali metal carbonate builder,
(d) from about 1 to 6 percent by weight of a
single hydrotrope, and
(e) the balance water.
12. The composition of claim 11, further
including a polymer of the general formula:
<IMG> ( I)
wherein X = H, Na or similar alkali metal; A = an alkyl
group having a chain length of 2 to 20 carbon atoms and
preferably 6 to 10 carbon atoms, and m and n are numbers
such that the monomer ratio is in the range of about 9:1
to 1:9 and a total average molecular weight of the
copolymer is from 1,000 to 70,000; a copolymer of the
general formula:
<IMG> ( II)
wherein X = H, Na or similar alkali metal and m and n are
numbers such that the monomer ratio is in the range of
about 9:1 to 1:9 and a total average molecular weight of
the copolymers is from 1,000 to 70,000; or a homopolymer
of the general formula:
<IMG>
(III)
wherein X = H, Na or similar alkaline metals, and n is a
number such that the total molecular weight of the polymer
29

is from 1000 to 70,000; and mixtures thereof.
13. The composition of claim 11, wherein the
alkali metal carbonate builder is selected from the group
consisting of sodium carbonate, sodium bicarbonate, sodium
sesquicarbonate, potassium carbonate, potassium
bicarbonate, potassium sesquicarbonate, and mixtures
thereof.
14. The composition of claim 11, wherein said
anionic surfactant is selected from the group consisting
of C8 to C11 alkylbenzene sulfonates, C12 to C16
alkylsulfates, C12 to C16 alkylsulfosuccinates, sulfated
ethoxylated C12 to C16 alkanols, and mixtures thereof.
15. The composition of claim 11, wherein the
hydrotrope is selected from the group alkali metal and
ammonium salts of alkyl benzene sulfonic acid, toluene
sulfonic acid and xylene sulfonic acid.
16. The composition of claim 11, wherein the
hydrotrope is selected from the group consisting of sodium
cumene sulfonates and potassium salts of phosphate esters.
17. The composition of claim 11, wherein the
copolymer I has a molecular weight of from about 1000 to
25,000.
18. The composition of claim 11, wherein the
copolymer II has a molecular weight of from 1000 to
10,000.
19. The composition of claim 11, wherein the
homopolymer III has a molecular weight of from about 1000
to 8000.

Description

` ` 2026911
-
ST~RT~ CLEAR ISOTROPIC LIOUID DETERGENT
CnMPosTTIoNs CONTAINING SODIUM CARBONAT~
BACKGROUND OF THE INVENTION
1. F;el~ Of the I~v~nt;on
The present invention relates to a clear, single
phase liquid detergent composition containing alkali metal
carbonate builders, anionic and nonionic surfactants, a
hydrotrope and optionally polycarboxylate builders which is
freeze/thaw stable.
More specifically, the present invention relates to
a dear, isotropic, liquid detergent composition containing
alcohol ethoxylates1 anionic surfactants such as sodium alkyl
benzene sulfonate, alkali metal carbonates as builders, a
hydrotrope such as sodium cumene sulfonate and optionally
polymers as adjuvant builders. The compositions are
freeze/thaw stable, effective on oily soils and are
significantly l!ess costly than comparable non-built
formulations.
This invention further relates to a carbonate built
liquid detergent composition based on high performing oxy-
alkylate nonionic surfactants vhich are equivalent in
performance to higher levels of commodity alcohol ethoxylates
but which form stable, one-phase liquid compositions.
This invention also relates to a carbonate built
liquid detergent composition which contains polyacrylate
homopolymer and polymaleate copolymers which are added to
enhance the building effects and reduce encrustation of
fabrics from the insoluble carbonate salts.
2. Descr;pt;on of the Pr;or Art
~slop et al, U.S. Patent No. 4,619,446 disclose

2026911
liquid detergent compositions suitable for laundry use which
consist of water, electrolytes, builders and active
ingredients. The liquid detergent composition of Haslop is
actually a slurry composition which may be then formulated
into a liquid or a powdered composition. The builders of
Haslop include polyacrylates and maleic anhydride based
copolymers. The composition formed according to Haslop is
temperature stable and contains sodium carbonate,
polyacrylates, maleic anhydride copolymers and other
adjuvants. However, Haslop et al do not propose a clear,
isotropic phase stable liquid built laundry detergent
composition containing sodium carbonate as a builder,
oxyalkylate nonionic surfactants, anionic surfactants such as
sodium alkyl benzene sulfate, a hydrotrope such as sodium
cumene sulfonate, and optionally, polyacrylate homopolymers
or polymaleate c~polymers.
/

2026911
-
PaYne et al, U.S. Patent No. 3,574,122 disclose
a phase stable heavy duty liquid detergent emulsion
composition comprising a synthetic organic nonionic
detergent and trisodium nitrilo acetate in an aqueous
5 medium containing a ternary emulsion stabilizer system.
The ternary emulsion stabilizer system is a combination of
a hydrolyzed linear copolymer of ethylene and maleic
anhydride plus a hydrolyzed crosslinked copolymer of
ethylene and maleic anhydride, a second stabilizer which
10 is a hydrotrope and a third stabilizer which is an
electrolyte. There is no showing in Payne et al of
forming a clear, isotropic, built, liquid laundry
detergent composition which is freeze/thaw stable and
contains the alkali metal carbonate builders of the
15 present invention.
BrierelY et al, U.S. Patent No. 4,530,775
disclose stable liquid detergent suspensions which stably
suspend undissolved particulate matter. Alcohol
ethoxylates are disclosed as surfactants of choice. There
20 is no showing of the clear isotropic built liquid
detergent composition of the present invention.
Summary of the Invention
It is an object of the present invention to
provide a clear, single phase, carbonate built liquid
detergent composition, which is freeze/thaw stable,
comprising:
(a) an anionic surfactant
(b) an oxyalkylate nonionic surfactant of the
general formula:
lc~3 I H2CH3
RO~CH2-CH2-o ~ CH2CH -O ~ CH2-CH -O ~ H
i~

2026911
wherein R is an alkyl chain of from C8 to C15, x is a number
from about 4 to 15, y is a number from about 0 to 15, z is
a number from 0 to 5, and the molecular weight is from
about 300 to 2,200;
(c) an alkali metal carbonate builder,
(d) a single hydrotrope, and
(e) the balance water.
A further object of the present invention is to
provide a clear, single phase, carbonate built liquid
10 detergent composition, which is freeze/thaw stable,
comprising:
(a) from about 1.0 to 15.0 percent by weight
anionic surfactant
(b) from about 0.1 to 7.0 percent by weight of
an oxyalkylate nonionic surfactant of the
general formula:
fH3 fB2CB3
RO(CH -C~2-O ~ CH2CH-O ~ CH2 z
wherein R is an alkyl chain of from C~ to C~5, X iS a number
from about 4 to 15, y is a number from about 0 to 15, z is
a number from 0 to 5, and the molecular weight is from
about 300 to 2,200;
(c) from about 0.1 to 5.0 percent by weight of
an alkali metal carbonate builder,
(d) from about 1 to 6 percent by weight of a
single hydrotrope, and
(e) the balance water.
Detergent "builders" are used primarily to
improve the soil removal performance of the formulation.
They can act variously through chelation (or
precipitation) of water hardness ions, improvement of
particulate soil dispersion and
-3a-
~'
V

202~911
by raising the pH of the wash liquor in order to saponify
(and/or emulsify) oily soils. Many of these functions (chela-
tion, saponification) cannot be achieved by simply increasing
the amount of nonionic or anionic surfactants in a formula-
tion. Even in cases where high levels of surfactants do
provide the necessary benefit, a strong motivation for includ-
ing builders in the formulation is that they provide equal
performance at significantly lower cost.
Incorporating a builder into a liquid formulation
lo is usually more difficult than for a powder detergent. In the
United States, where heavy duty liquid detergents are usually
clear, single phase compositions, the task is even more
demanding. In addition to these formulation constraints
other limitations of available builders result from government
regulation (for example, non-phosphate legislation). Given
these constraints and the need to formulate liquid detergent
compositions which are cost effective, the use of sodium
carbonate as a builder for clear, freeze/thaw stable, liquid
systems is an important objective.
Liquid detergent formulations based on alkali metal
carbonates have many benefits. Alkali metal carbonates act
as a precipitating builder, preventing the interaction of
calcium and magnesium ions with anionic surfactants which
results in their loss in~efficiency. Additionally, alkali
metal carbonate raises the pH of the wash water which can
enhance the removal Cf oily or fatty soils through the
mechanisms of saponification or emulsification. Because
alkali metal carbonates, particularly sodium carbonate, are
so inexpensive relative to nonionic surfactants, liquid
formulations containing the carbonate are superior to unbuilt
liquid detergents on a cost/performance basis. However,
clear, single phase liquid detergents containing alkali metal
carbonate, such as sodium carbonate, anionic and nonionic

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surfactants are difficult to prepare and are often found to
be unstable when subjected to extremes of temperature like
those found in conditions of storage and use. In particular,
difficulties with nonionic surfactants are encountered owing
to the tendency of the nonionic to "salt out" in the presence
of high sodium ion content.
Surprisingly, it has been found that alkali metal
carbonate built formulations containing oxyalkylate nonionic
surfactants and LAS are freeze/thaw stable and provide excel-
lo lent oily soil removal properties. The efficiency of theseformulations in oily soil removal has been found to be
superior to non-built formulations containing higher levels
of nonionic surfactant, so that the cost of the alkali metal
carbonate based formulation is significantly lower. It has
also been found that alkali metal carbonate built compositions
contA;n;ng oxyalkylate nonionic surfactants outperform anionic
liquid detergents built with higher levels of alkali metal
carbonate. Thirdly, it has also been observed that alkali
metal carbonate built liquids including oxyalkylate nonionic
surfactants perform equal to formulations which contain higher
levels of commodity ethoxylated alcohols. The compositions
contA;n;ng higher levels of commodity ethoxylates are not only
more expensive, but also are not stable through even one
freeze/thaw cycle. Finally, the aforementioned carbonate
built liquid detergents based on oxyalkylate nonionic
surfactants can also contain small amounts of polyacrylate
homopolymers or polymaleate copolymers which are added to
enhance building and inhibit fabric encrustation by calcium
carbonate. Liquid detergent compositions containing such
polymers showed no signs of precipitation or phase separation
when they were subjected to numerous freeze/thaw cycles.
Accordingly, it is an object of this invention to
provide carbonate built liquid detergent compositions which

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are effective on oily soils and which are significantly less
costly than comparable non-built formulations. It is a
further object of this invention to provide alkali metal
carbonate built liquid detergents based on high performing
oxyalkylate nonionic surfactants which are equivalent in
performance to higher levels of commodity ethoxylated alcohol
surfactants but which torm stable, one phase liquid
compositions. It is also an object of this invention to
provide alkali metal carbonate built liquid detergents which
contain polyacrylate homopolymer or polymaleate copolymers
which enhance building effects and reduce encrustation of
fabrics from insoluble carbonate salts.
D~T~TT~n D~CRIPTION OF T~ PEI~F~RR~n ~MRODIMENT
The present invention is directed to a clear, iso-
tropic, built liquid detergent composition which is freeze/
thaw stable and contains an alkali metal carbonate as a
builder. The composition is comprised of from 1.0 to 15.0
percent by weight of an anionic surfactant, from 0.1 to 7.0
percent by weight of the composition of an oxyalkylate
nonionic surfactant, from 0.1 to 5.0 percent by weight of a
builder such as sodium carbonate, from about 1.0 to 10.0
percent by weight hydrotrope, with the balance of the
composition being water. The composition may also include
polyacrylate homopolymers or polymaleate copolymers which are
useful as additional builders and anti-encrustation agents.
The homopolymers contemplated for use in the present
invention include polymers of a monoethylenically unsaturated
monocarboxylic acid of 3 to 10 carbon atoms and its salt.
Additionally, the copolymers used in the invention contain
cqpolymerized monomer units of monoethylenically unsaturated
dicarboxylic acids and monoethylenically unsaturated

` 2026911
nonocarboxylic acids or olef ins. The copolymers are
comprised of:
(a) from 90 to lo percent by weight of a mono-
ethylenically unsaturated dicarboxylic acid of 4 to 6 carbon
atoms, its salt and/or if appropriate, its anhydride, and a
comonomer comprised of
b) from 90 to 10 percent by weight of an alkene
containing 4 to 22 carbon atoms, or
c) from 9o to lo percent by weight of a
monoethylenically unsaturated monocarboxylic acid of 3 to lo
carbon atoms and/or its salt.
The starting monomers useful in the present
invention are monoethylenically unsaturated monocarboxylic
acids and/or their salts. They may contain from about 3 to
10 carbon atoms in the molecule. Acrylic acid and methacrylic
acid are particularly suitable compounds, but it is also
possible to use, for example, vinyl acetic acid, allyl acetic
acid, as well as dimethyl acrylic acid.
The starting comonomers (a) are monoethylenically
unsaturated dicarboxylic acids, their salts and/or, their
anhydrides. Examples of suitable dicarboxylic acids of 4 to
6 carbon atoms are maleic acid, itaconic acid mesaconic acid,
fumaric acid, methylene malonic acid and their salts and, in
the appropriate cases, their anhydrides.
For the purposes of the present invention, salts of
the carboxylic acids already mentioned are, preferably sodium
salts and potassium salts, ammonium salts and organic amine
salts,, such as those of the tri-C1-C4-alkyl amines, of
hydroxyethylamine or of mono-, di- and tri-C1-C4
alkanolamines, and mixtures thereof.
The starting comonomers of (b) are selected from the
group consisting of substituted and unsubstituted alkenes
having from about 4 to 22 carbon atoms. Representative

2026911
`
examples include 2-methylpropene, 1-pentene, 1-decene,diiso-
butylene, 2,4,4-trimethyl-2-pentene and mixtures thereof.
The starting comonomers of (c) are monoethylencially
unsaturated monocarboxylic acids and/or their salts. They may
contain from 3 to lo carbon atoms in the molecule. Acrylic
acid and methacrylic acid are particularly suitable compounds,
but it is possible to use, for example, vinyl acetic acid,
allyl acetic acid as well as dimethyl acrylic acid.
The general structure of a preferred homopolymer
lo thus formed is as follows:
wherein X = H, Na or similar alkaline metals, and
n is a number such that the total molecular weight of the
polymer is from 1000 to 70,000. More preferably from 1000 to
8000.
The general structure of one preferred copolymer
thus formed is as follows:
H IH
_ H COoX n
wherein X, H, Na, or similar alkaline metals; A = an alkyl
group having a chain length of 2 to 20 carbon atoms and
preferably 6 to 10 carbon atoms, and m and n are numbers such
that the monomer ratio is in the range of about 9:1 to 1:9 and
a total average molecular weight of the copolymer is from
1,000 to 70,000. The most preferred monomer ratio for the
copolymer is in the range of 1:1. The preferred molecular
weight range of the copolymer is 1,000 to 25,000 and most
preferably 12,000.
The general structure of a second preferred
copolymer thus formed is as follows:

2026911
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H H H H
C C C- C--
COOX COOX n H A m
wherein X = H, Na, or similar alkaline metals; A = an alkyl
group having a chain length of 2 to 20 carbon atoms and
preferably 6 to 10 carbon atoms, and m and n are numbers such
that the monomer ratio is in the range of about 9:1 to 1:9 and
a total average molecular weight of the copolymer is from
1,oOO to 70,000. The most preferred monomer ratio for the
copolymer is in the range of 1:1. The preferred molecular
weight range of the copolymer is 1,000 to 25,000 and most
preferably 12,000.
The general structure of a second preferred
copolymer thus formed is as follows:
_
7 ~ H
cbox coox H COOX
wherein X = H, Na or similar alkali metals and n and m are
numbers such that the monomer ratio is in the range 9:1 to 1:9
and a total average molecular weight of the copolymer is from
1,000 to 70,000. The most preferred monomer ratio for the
copolymer is in the range 1:1. The preferred molecular weight
range of the copolymer is 1,000 to 10,000 and most preferably
about 3,000.
The nonionic surfactants useful in the present
invention comprise ethylene oxide and/or propylene oxide
and/or butylene oxide condensation products with alcohols,
alkyl phenols, fatty acid amides and mixtures thereof.
Preferably, the nonionic surfactant may be an oxyalkylate of

2026911
_
the general structure:
fH3 CH2-CH3
RO(cH2-cH2-o ~ CH2-CH-O ~ CH2-CH-O ~ H
wherein R is an alkyl chain whose length is from about 8 to
15 carbon atoms, preferably 12 to 15 carbon atoms; x is a
number from about 4 to 15, preferably 8 to 15; y is a number
from about 0 to 15, preferably 1 to 4; and z is a number from
about 0 to 5, and preferably 0.
The preferred range of the molecular weight of the
oxyalkylate surfactant for use in the present invention is
from about 300 to 2,200.
The carbonate builder is an alkali metal carbonate,
and preferably, the alkali metal is sodium or potassium. Most
preferably, the builder is a sodium or potassium carbonate,
bicarbonate or sesquicarbonate, and mixtures thereof.
A wide variety of anionic surfactants may be
utilized. Anionic surfactants can be broadly described as
surface active compounds with negatively charged functional
group(s). An important class within this category are the
water-soluble salts, particularly alkali metal salts, of
organic sulfur reactions products. In their molecular
structure is an alkyl radical containing from about 8 to 22
carbon atoms and a radical selected from the group consisting
of sulfonic or sulfuric acid ester radicals. Such surfactants
are well known in the detergent art. They are described at
length in "Surface Active Agents and Detergents", Vol. II, by
Schwartz, Perry & Berch, Interscience Publishers Inc., 1958.
Particularly suitable anionic surfactants for the
instant invention are the higher alkyl mononuclear aromatic
sulfonates. They contain from 10 to 16 carbon atoms in the
alkyl chain. Alkali metal or ammonium salts of these

` 2026911
sulfonates are suitable, although the sodium salts are
preferred. Specific examples include: sodium linear tridecyl
benzene sulfonate; and sodium p-n-dodecyl benzene sulfonate.
These anionic surfactants are present usually from about 1 to
about 15% by weight of the total composition. More preferably,
they are present from about 8% to about 10%.
The presence of a hydrotrope within the composition
is highlydesirable. Hydrotropes are substances that increase
the solubility in water of another material which is only
partially soluble. Preferred hydrotropes are the alkali metal
or ammonium salts of alkyl benzene sulfonic acid, toluene
sulfonic acid and xylene sulfonic acid. Two highly preferred
hydrotropes are the sodium salt of cumene sulfonic acid and
phosphate esters. Hydrotropes are present from about 1% to
about 10% by weight of the total composition, preferably at
a level of 1 to 6% by weight.
Those skilled in the art recognize that the
detergent compositions described herein may also contain
incrustation inhibitors, perfumes, bleaches, corrosion
inhibitors, antifoamers, optical brighteners, enzymes and
other additives.
Those skilled in the art further understand that the
present invention may optionally include any builde~ suitable
for use in a liquid detergent composition. Examples of
organic builder salts which can be used alone or in admixture
with each other or with the preceding inorganic alkaline
builder salts are alkali metal polycarboxylates, sodium and
potassium citrate, sodium and potassium tartarate, sodium and
potassium N-(2-hydroxyethyl)-ethylene diamine tetraacetates,
sodium and potassium nitrilotriacetates, and sodium and
potassium N-(2-hydroxyethyl)-nitrilo diacetates. These
builders may be used in conjunction with alkali metal
carbonates.
X

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The following examples are presented to illustrate
various aspects of the invention. Those skilled in the art
understand they are not to be construed as limiting the scope
or spirit of the invention.
EXAMPT.~S
St-~hil;ty Stu~;es:
The heavy duty liquid detergent formulations shown
in Tables 1, 2 and 3 were tested for freeze/thaw stability
(i.e. maint~;n;ng clarity without separation or precipitation.
This evaluation was carried out by alternatively subjecting
the sample to -5F for 24 hours followed by warming to 70F
for 48 hours. The formulation was exposed to these
temperature extremes for a total of six cycles. Results of
the freeze/thaw study are also shown in Tables 1, 2 and 3.
In the first set of Examples, we investigated the
effect of different hydrotropes on formula stability. As
shown in Table 1, with formulas containing 5% Plurafac~ B-25-
5, most hydrotropes ~or hydrotrope blends) were unable to
insure stability through even one freeze/thaw cycle: The two
exceptions (Examples 1 and 4) were sodium cumene sulfonate
(Stepanate~ SCS) and a phosphate ester (Triton~ H-55). These
hydrotropes were also effective with 7% Igepal~ C0-630
(Example 8) but not with 7% Neodol~ 25-7 (Example g) or 7%
Neodol~ 25-9 (Example 10).
The hydrotrope study shows the difficulty of
formulating nonionic surfactants into carbonate built liquid
detergents. Salting out of the nonionic is a major difficulty
with these compositions and most hydrotropes are not effective
in preventing it.
12

` 2026911
All of the formulations in table 1 showed some
instability. The coposition containing 5% B-25-5, 5%
carbonate, and 10% Vista C-560 LAS was the most stable
surviving four freeze/thaw cycles. Two approaches were taken
to improve the stability of the formulation. Different types
of LAS were investigated and lower levels of sodium carbonate
or nonionic surfactant were used.
In Table 2 we show the results of a study of
different LAS types and higher sodium carbonate levels. The
data show that longer alkyl chains lead to instability, since
the Biosoft~ D-62 formula (a Na salt of C12 LAS) does not
survive one freeze/thaw cycle. Changing the counterion from
sodium to protonated TEA significantly improves stability,
since the formula with Biosoft~ N-300 (a C12 LAS) is stable
through six freeze/thaw cycles and reconstitutes in only
twenty-four hours. If the sodium carbonate level was
increased to 7% however, formulas containing 5% B-25-5 and 10%
of either (Biosoft~ N-300 or VISTA~ C-560) were found to be
unstable.
In Table 3 we show the compatibility of different
polymers with carbonate built liquid detergents containing
Plurafac~ B-25-5 (an oxyalkylate available from BASF
Corporation). By lowering the level of carbonate to 4% (5~
B-25-5) or the level of B-25-5 to 4% (5% carbonate) stable
compositions can be formulated with Sokalan~ CP-9 copolymer
(Examples 20 and 21) and Sokalan~ PA-30 polymer (Examples 24
and 25) (each polymer was included at 0.5% active).
Formulations containing higher levels of B-25-5 or carbonate
were found to be unstable (Examples 26, 27 and 28).
Because sodium carbonate is a precipitating builder
(forming calcium or magnesium carbonate in the presence of

2026911
"_
water hardness ions) acrylate or maleate based polymers
(Sokalan~ CP-9, CP-12 and PA-30 polymers) are included to
inhibit encrustation of fabrics with insoluble salts. Thus
the formulation of stable carbonate built liquid detergents
containing encrustation inhibiting polymers of these types
represents a significant advance over the present art.
The freeze/thaw stability experiments compiled in
Tables 1-3 are evidence that carbonate built liquid detergents
are difficult to formulate, particularly if they contain
encrustation inhibiting polymers and an LAS with a C12 or
higher alkyl chain. It is therefore surprising that stable
carbonate built compositions can be formulated and that their
oily soil detergency performance, as outlined in the next
section, was equivalent to more expensive formulations
containing higher levels of commodity ethoxylates.
14

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TART~ 1 (T~'~FECT OF VARIOUS HYDROTROPES)
F~XAMPT.~
CO~PON~NT 1 2 3 4 5 6 7 8 9 10
Plurafac~ B-25-5 5 5 5 5 5 5
Neodol~ 25-7 - - - - - - - - 7
Igepal~ C0-630 - - - - - - 7 7 - -
Neodol~ 25-9 - - - - - - - - - 7
Vista C-560 10 10 lo lo 10 10 10 lo 10 lo
Stepanate~ SCS 6 - - - - - - 6 6 6
Stepanate~ SXS - 6 5 5 5 5 6
Petro~ LBA
Triton~ H-55
Propylene Glycol
Dowfax~ 3B2 .
Sodium Carbonate 5 5 5 5 5 5 5 5 5 5
Water 74 74 74 74 74 74 72 72 72 72
Freeze/thaw 4 NS NS l* NS NS NS 2 ,NS NS
Stability
(#cycles)
NS = Not stable: precipitation and/or phase separation
after one freeze/thaw cycle.
0 * = Stable through one freeze/thaw; not evaluated further.

` 2026911
T~RT~ 1 CONT. (~FF~CT OF VARTOUS HYDROTROP~S)
P~XI~MPT.h~
COMPON~NT 11 12 13 14 15
Plurafac~ B-25-5 5 5 5 5 5
10 Igepal~ C0-630
Vista C-560 10 10 10 10 10
Stepanate~ SXS - 5 5 5 5
Petro~ LBA
Petro~ LBA - - - 1 -
Propylene Glycol 6
Dowfax~ 3B2
Sodium Carbonate 5 5 5 5 5
Water 74 74 74 74 74
Freeze/thaw CF CF NS NS NS
Stability
(#cycles)
CF = Cannot formulate: two phase system forms
when components are
mixed.
NS = Not stable: precipitation and/or separa-
tion after one freeze/thaw
cycle.
16

2026gII
TART.F. 2
10 T'.XAMPT.l;. No.
CO~PON~NT 16 17 18 19
Plurafac~ B-25-5 5 5 5 5
Igepal~ C0-630
Vista C-560 10 - - -
Stepanate~ SCS 6 6 6 6
Biosoft~ D-62 - 10
Biosoft~ N-300 - - 10 10
Sodium Carbonate 7 5 5 7
Water 72 74 74 72
Freeze/thaw NS NS 6 NS
Stability
(#cycles)
NS = Not stable
17

- 2026911
TART-~ 3 (CoMpATIBIT~TTy WITH POLYMERS)
~xa~pT-~ No
COMPON~NT 20 21 22 23 24 25 26 27 28
Plurafac~ B-25-5 5 4 5 4 5 4 5 5 5
Igepal~ C0-630 - - - - - - 7
Vista C-560 10 10 10 10 10 10 10 10 10
Stepanate~ SCS 6 6 6 6 6 6 6 6 6
Sodium Carbonate 4 5 3 5 4 5 5 5 5
Sokalan~ CP-9 0.5 0.5 - - - - 0.5
Sokalan~ CP-12 - - 0.5 0.5 - - - 0.5
Sokalan~ PA-30 - - - - 0.5 0.5 - - 0.5
Water 74.5 74.5 75.5 74.5 74.5 74.5 73.5 73.5 73.5
Freeze/thaw 6 6 6 6 6 6 NS NS NS
Stability
(#cycles)
NS = Not stable
18

2026911
.
MTx~n SOIT D~T~R~NCY:
The soil removal performance of liquid detergent
composition containing sodium carbonate, LAS and different
nonionic surfactants was assessed using a mixed soil load.
For the particulate soil, ground in clay swatches were used
(Scientific Services) including three fabric types: cotton
( S-405); polyester (S-767) and D(65) /C(35) ( S-7435) . The oily
soil consisted of Spangler sebum which was applied (Scientific
Services) to the same three fabric types used with the clay
soil. Two swatches of each fabric/stain combination were
added to each Terg-o-Tometer pot along with one clean swatch
of each fabric (a total of fifteen swatches per pot)*.
Wash conditions were 100F and 150 ppm water
hardness (2:1 Ca++/Mg++ ratio). A hunter colorimeter was
employed to monitor reflectance of the swatches before and
after the wash. Changes in reflectance are reported for each
fabric/soil combination along with the 95% confidence interval
associated with each determination.
In Table 4A the sebum soil removal results are shown
for carbonate built liquid detergents and one unbuilt
formulation. As indicated in Table 4A, sebum soil removal
results for the formula containing 5% B-25-5 are equal to
results for compositions containing 7% of a commodity
ethoxylate: Igepal~ C0-630, Neodol~ 25-7 or Neodol~ 25-9.
* After the method of Feighner J.A.O.C.S. 66 (1) 13 (1989).

2 02B91l
-
If this example of the invention (10% LAS, 5~
PLURAFAC~ B-25-5, 5% carbonate) is compared to an unbuilt
formula with twice the level of commodity ethoxylate (10% LAS,
10% C0-630) or to an anionic formula with twice the level of
carbonate and LAS (20% LAS. 10% carbonate), it is found to be
superlor.
Clay soil removal data for the mixed soil detergency
test is shown in Table 4B. At the 95% percent confidence
level, all of the formulations tested performed equally well.
This result indicates that the formula containing 5%
PLURAFAC~ B-25-5 is equivalent in clay soil removal to
formulas cont~;n;ng higher levels of commodity ethoxylates or
to the anionic formula with higher LAS and carbonate.
The Terg-o-Tometer evaluations were reproduced in
a washing machine study. In this work a Whirlpool Imperial
washer was set on regular agitation for a timed ten minute
cycle, followed by an untimed rinse using the regular machine
settings. Seventeen gallons of warm (100F) Wyandotte tap
water (ca. 100 ppm hardness) was used without adding
additional water hardness ions. Five swatches of each
fabric/stain combination were included. In addition to sebum
and clay soiled cloth. EMPA-104/cottom (a carbon black/olive
oil stain) was also evaluated.
Results are shown in Tables 5A (oily stains) and 5B
(particulate stains). This data shows that formulas
containing 5% Plurafac~ B-25-5, give equal performance to
compositions containing 7~ Igepal~ C0-630. Lower levels of
Igepal~ C0-630 (5%) are less effective than 5% Plurafac~
B-25-5 in removing sebum soil from polyester fabric and are
directionally inferior on blend (see table 5A). Thus this
experiment confirms the Terg-o-Tometer studies reported above.

2026911
-
These results show that the formula based on 5%
Plurafac~ B-25-5 provides equal detergency when compared to
formulation cont~;n;ng higher levels-of commodity ethoxylates
(7% Igepal~ C0-630, 7% Neodol~ 2507, 7% Neodol~ 25-9, and
unbuilt 10% Igepal~ C0-630). Stability experiments detailed
in Tables 1-3 also indicate that carbonate built (5%) formulas
containing 5% PLURAFAC~ B-25-5 are freeze/thaw stable through
four cycles, whereas those containing 7% Neodol~ 25-7 or 25-9
separate after one cycle. Formulas containing 7~ Igepal~
C0-630 are stable, but are more expensive owing to the higher
level of nonionic. Taken together the detergency and
stability data suggest that carbonate built liquid detergents
containing Plurafac~ B-25-5 are more economical (because
lower level of surfactants can be used with equal performance)
and are more practical (because they do not separate under
actual conditions of storage) than was previously believed
possible.
21

2026911
- TABLE 4A
Mixed Soil Detergency Performance of Liquid Detergents
Sebum Soil Removal (Mixed Soil Load) at 100F
FO~MUT~TION COTTON poT~y~sT~R BT~ND TOTAT
10% LAS 11.7 (0.7) 14.3 (0.3) 13.2(0.7) 39.2
10% C0-630
10% LAS 12.1 ~3.1) 23.4 (0.3) 21.1 (1.4) 56.6
7% C0-630
5% Na2CO3
10% LAS14.3 (0.8) 22.6 (0.7) 21.1 (1.0) 58.0
7% 25-7
5% Na2CO3
10% LAS14.6 (1.7) 23.9 (0.6) 22.3 (1.0) 60.8
7% 25 9
5% Na2CO3
10% LAS14.0 (2.6) 24.0 (1.3) 22.3 (0.7) 60.3
5% B-25-5
5% Na2CO3
20% LAS 9.4 (3.6) 15.9 (0.7) 17.1 (0.6) 42.4
10% Na2CO3
Notes: 95% Confidence Intervals appear in paren-
thesis. Shorthand designations used for
nonionic surfactants are as follows:
C0-630 = Igepal~ C0-630; 25-7 = Neodol~
25-9 and B-25-5 = Plurafac~ B-25-5.

2026911
-
TART~ 4B
Mixed Soil Detergency Performance of Liquid Detergents
Clay Soil Removal (Mixed Soil Load) at 100F
FO~MUT.~TION COTTON poT.Y~ST~R BLEND TOTAL
10% LAS 17.9 (2.6) 25.3 (0.7) 27.7(0.6) 70.9
10% C0-630
10% LAS 16.8 (2.8) 24.7 (0.6) 27.1 (1.4) 68.6
7% C0-630
5% Na2CO3
10% LAS 15.9 (3.3) 25.0 (0.8) 27.5 (0-4) 68.4
7% 25-7
5% Na2CO3
10% LAS 17.5 (1.8) 25.6 (0.5) 27.1 (0.4) 70.2
7% 25 9
5% Na2CO3
10% LAS 17.2 (2.7) 25.7 (1.3) 27.7 (0.7) 70.6
5% B-25-5
5% Na2CO3
20% LAS 15.8 (1.5) 23.8 (1.0) 26.7 (0.6) 66.3
10% Na2CO3
Notes: 95% Confidence Intervals appear in paren-
thesis. Shorthand designations used for
nonionic surfactants are as follows:
C0-630 = Igepal~ C0-630; 25-7 = Neodol~
25-7 = Neodol~; 25-9 = Neodol~ 25-9 and
B-25-5 = Plurafac~ B-25-5.

202~911
`
TART.~ 5A
Mixed Soil Detergency Performance of Liquid Detergents
oily Soil Removal (Mixed Soil Load) at 100F
FOR~JT~TION COTTON por~y~ TER BLEND TOTAL EMPA-104
10% LAS 9.6 (1.7) 21.8 (1.1) 22.0 (1.1) 53.4 8.4 (0.7)
7% C0-630
5% Na2CO3
10% LAS10.7 (2.0) 19.4 (1.0) 21.8 (0.9) 51.9 9.2 (1.6)
5% C0-630
5% Na2CO3
10% LAS9.2 (0.7) 21.9 (0.7) 23.1 (1.4) 54.2 7.3 (0.8)
5% B-25-5
5% Na2CO3
Notes: 95% Confidence Intervals appear in paren-
thesis. Shorthand designations used for
nonionic surfactants are as follows:
C0-630 = Igepal~ C0-630; B-25-5
Plurafac~ B-25-5.
24

2026911
.
TART~ 5B
Mixed Soil Detergency Performance of Liquid Detergents
Clay Soil Removal (Mixed Soil Load) at 100F
FO~MUT.~TION COTTON pOT.Y~.~T~R BT~ND TOTAL
10% LAS 12.9 (0.5) 20.1 (0.8) 23.2 (0.8) 56.2
7% C0-630
10 5% Na2CO3
10% LAS 13.2 (2.5) 20.7 (0.4) 23.4 (0.6) 57.3
5% C0-630
5% Na2CO3
10% LAS 11.7 (3.2) 20.3 (1.1) 23.0 (1.0) 55.0
5% B-25-5
5% Na2CO3
Notes: 95% Confidence Intervals appear in paren-
thesis. Shorthand designations used for
nonionic surfactants are as follows:
C0-630 = Igepal~ C0-630; 25-7 = Neodol~
25-7 = Neodol~; 25-9 = Neodol~ 25-9 and B-
25-5 = Plurafac~ B-25-5.