Note: Descriptions are shown in the official language in which they were submitted.
-~5qc)
- ` 1315635
STABLE 1IQUID DETERGENT COMPOSITIONS
Ronald L. Jacobsen
Robert Mermelstein
Gregory S. Caravajal
Technical Field
The present invention relates to heavy-duty liquid
detergent compositions containing sulfonate surfactant,
ethoxylated nonionic surfactant, alkyl or alkenyl suc-
cinate and citrate builders, a neutralization system
comprising potassium and sodium ions and, preferably, a
lO low level of alkanolamine, and a solvent system com-
prising propylene glycol and water. The compositions
are stable isotropic liquids providing a high level of
detergency performance and good chlorine bleach com-
patibility. The compositions preferably also contain an
15 alkyl amine anionic surfactant ion-pair complex which
imparts fabric care (i~e., softening andtor static
control) benefits through-the-wash without significantly
impairing cleaning performance. Such compositions
preferably are in the form of stable homogeneous
20 suspensions.
Background of the Invention
There has been con~iderable demand for liquid
detergents capable of providing superior cleaning under
a wide variety of laundering conditions. Such composi
25 tions generally require a number of ingredients which
tend to separate into discrete phases. Yet, isotropic
liquid detergents are desired for both consistency of
performance and aesthetic reasons. The compositions
` should be isotropic as made, e.g., at about 68F (20C),
30 and preferably remain isotropic during shipping and
storage, where temperatures ranging from 90F (32.2C)
or higher to 55F ll2.3C) or lower are often encount-
ered. They should also be formulated to recover, after
freezing and thawing, to an isotropic phase prior to
35 consumer use.
' ~ :
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1 31 5635
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Liquid detergents often contain high levels of
alkanolamines to enhance performance and product sta-
bility. However, alkanolamines readily react with and
destroy chlorine bleaches. Consumers who add chlorine
5 bleaches to wash solutions containing alkanolamine-based
detergents consequently do not obtain optimum bleaching
performance.
Heavy-duty liquid detergent compositions that are
isotropic liquids providing a high level of detergency
10 performance and improved chlorine bleach compatibility
are disclosed in U.S. Patent 4~507,219, Hughes, issued
March 26, 1985. ~he compositions contain sulfonate and
alcohol ethoxylate sulfate anionic surfactants,
ethoxylated nonionic surfactant, optional quaternaxy
15 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.
Numerous attempts have also been made to formulate
laundry detergent compositions which simultaneously
provide good cleaning and fabric care performance.
Attempts have been made to incorporate cationic fabric
softeners in anionic surfactant-based detergent
25 compositions employing various means of overcoming the
natural antagonism between the anionic and cationic
surfactants. For instance, U.S. Patent 3,936,537,
Baskerville et al., issued February 3, 1976, discloses
detergent compositions comprising organic surfactant,
30 builders, and, in particulate form~ a quaternary
ammonium softener combined with a poorly water-soluble
dispersion inhibitor which inhibits premature dispersion
of the cationic in the wash liquor. Even in these
compositions, some compromise between cleaning and
35 softening effectiveness has to be accepted.
1 31 563r~
- 3 -
Other laundry detergent compositions have employed
tertiary amines along with anionic surfactants to act as
fabric softeners. sritish Patent 1,514,276, Kengon,
published June 14, 1978, employs certain tertiary amines
5 with two long chain alkyl or alkenyl groups and one
short chain alkyl group. The amines are useful as
fabric softeners in detergent compositions when their
isoelectric point is such that they are present as a
dispersion of negatively charged droplets in the
10 normally alkaline wash liquor, and are present in a more
cationic form at the lower pH of a rinse liquor, and so
become substantive to fabrics. The use of such amines,
among others, in detergent compositions has also been
previously disclosed in British Patent 1,286,054,
15 assigned to Colgàte-Palmolive, published August 16,
1972, British Patent 1,514,276, assigned to Unilever,
published June-14, 1978, and in U.S. Patent 4,375,416,
Crisp et all, issued March 1, 1983.
Another approach to pro~ide anionic detergent
20 compositions with fabric softening ability has been the
use of smectite-type clays, as described in U.S. Patent
4,062,S47, Storm et al., issued December 13, 1977.
These compositions, although they clean welll require
large contents of clay for effective softening. The use
25 of clay together with a water-insoluble cationic
compound in an electrically conductive metal salt as a
softening composition adapted for use with anionic,
nonionic, zwitterionic and amphoteric surfactants has
been described in British Patent 1,483,627, assigned to
30 Procter & Gamble, published August 24, 1977.
British Patent Applications 1,077,103 and
1,077,104, assigned to Bayer, published July 26, 1967,
disclose amine-anionic surfactant ion~pair complexes
useful as antistatic agents. The complexes are applied
35 directly to the fabric from an aqueous carrier. There
is no suggestion in either of these references that such
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1 31 5635
complexes could be added to detergent composition to
impart fabric care benefits through-the-wash. In fact,
such complexes could not be deliJered through-the-wash.
Fatty acid-amine ion-pair complexes in granular
5 detergents are disclosed in European Patent Application
0,133,804, Burckett-St.Laurent et al., published June 3,
1985. While these compositions delivex fabric
conditioning, the alkyl amine-anionic surfactant
complexes of the present invention deliver superior
lO antistatic performance.
It is therefore an object of the present invention
to provide a heavy-duty liquid detergent composition in
a stable isotropic form which exhibits good cleaning
performance and bleach compatibility.
It is another object of the present invention to
provide a heavy-duty liquid detergent composition in the
form of a stable homogeneous suspension comprising the
above composition and an alkyl amine-surfactant ion-pair
complex which delivers through-the-wash fabric care
20 benefits without significantly impairing cleaning
performance.
Summary of the I~vention
The present invention encompasses a heavy-duty
25 liquid detergent composition comprising, by weight:
(a) from about 10% to about 30~, on an acid basis,
of a sulfonate surfactant containing a C10-Cl6 alkyl or
alkenyl group;
(b) from about 1% to about 15~ of an ethoxylated
30 nonionic surfactant of the formula R (OC2H4)nOH, wherein
R1 is a ClO-Cl6 alkyl group or a C8-C12 alkyl phenyl
groupt n averages from about 3 to about 9, and said
nonionic surfactant has an HLB of from about 10 to about
13;
1 3 1 5635
(c) from about 7~ to about 20~, on an acid basis,
of a C12-C14 alkyl or alkenyl succinate ~uilder
material;
(d) from about 1% to about 7~, on an acid basis,
of a citrate builder material;
(e) from about 0 to about 0.04 moles per 100 gxams
of composition of an alkanolamine selected from the
group consisting of monoethanolamine, diethanolamine and
triethanolamine;
(f) potassium and sodium ions in a molar ratio o
potassium to sodium of from about 1.4 to about 5.0;
Ig) from about 5~ to about 20~ of propylene
glycol; and
(h) from about 15~ to about 45% water;
15 said composition containing from about 15% to about 40%
of (a) and (b); from about 10~ to about 25% of (c~ and
~d); from about 30% to about 55% of (a), (b), (c) and
(d); and from about 30~ to about 55% (g) and (h); the
weight ratio of (a) to (b) being from about 1 to about
20 10; and all of said components being selected to provide
an isotropic liquid at 20C having an initial pH of from
about 6.0 to about 10.0 at a concentration of about 10
by weight in water at 20C.
Preferred compositions further comprise an alkyl
25 amine-anionic surfactant ion-pair complex that provides
fabric care benefits, and optional detergent
ingredients, and are in the form of a stable homogeneous
suspension.
Detailed Description of the Inventio_
The liquid detergents of the present invention
contain sulfonate anionic surfactant, ethoxylated
nonionic surfactant, alkyl or alkenyl succinate and
citrate builders, a neutralization system comprising
potassium and sodium ions and, preferably, a low level
35 of alkanolamine, and a solvent system comprising
propylene glycol and water.
: ~
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The compositions herein are formulated to provide a
high level of detergency performance under a wide vari-
ety of laundering conditions. They also provide good
chlorine bleach compatibility due to the limited amount
5 of alkanolamine. Since the compositions con~ain a
relatively high level of active components and little or
no alkanolamine to enhance product stability, the types,
lev~els and ratios of the components must be carefully
balanced to provide isotropic liquids as made, and
10 preferably at storage temperatures as high as 90F
(32.2C) and as low as 55F (12.8C). They preferably
also recover, after freezing and thawing, to an
isotropic form by 55F (12.8C), more preferably by 50F
(10C).
~15 In order to meet these stability constraints, the
present compositions require a neutralization system
comprising potassium and sodium ions in a specified
molar ratio. Greater sodium neutralization than
required results in gelling of the product during the
20 addition of the succinate builder material, whereas
greater potassium neutralization results in an
unacceptably hazy product. The total level of organic
and inorganic bases must also be selected to provide a
sufficiently high product pH to obtain a wash pH desired
~5 for detergency performance, without the pH being so high
that pH sensitive stain removal and enzyme stability are
compromised.
The compositions also require a solvent system
comprising propylene glycol and water, in an amount
30 sufficient to prevent organic phase separation (i.e.,
keep poorly-soluble surfactants in solution).
Sulfonate Surfactant
The detergent compositions herein contain from
about 10% to about 30%, preferably from about 15% to
35 about 25%, by weigh~ (on an acid basis) of a water
soluble anionic sulfonate surfactant containing a
....,.. .. .. ., ...
.
,
1 3 1 5635
-- 7 --
Clo~C16 alkyl or alkenyl group. Anionic sulfonate
surfactants useful herein are d1sclosed in U.S. Patent
4,285,841, Barrat et al, issued August 25, 1981, and in
U.S. Patent 3,91~,678, Laughlin et alt issued December
30, 1975
Preferred sulfonate surfactants are the water-
soluble salts, particularly thP alkali metal, and alka-
nolammonium (e.~., monoethanolammonium or triethanolam-
monium) salts of alkylbenzene sulfonates in which the
10 alkyl group contains from about 10 to about 15 carbon
atoms, in straight chain or branched chain configura-
tion, e.g., those of the type described in U. S. Patents
2,220,0g9 and 2,477,383
Especially valuable are linear straigh~ chain
15 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 glycéryl
20 ether sulfonates, esters of ~-sulfonated fatty acids
containing from about 1 to 10 carbon atoms in the ester
group, 2-acyloxy-alkane-lAsulfonates containing from
about 2 to 9 carbon atoms in the acyl group, and
~-alkyloxy alkane sulfonates containing fxom about 1 to
25 3 carbon atoms in the alkyl group.
Mixtures of the above-described sulfonates, partic-
ularly with the Cll_l3 linear alkylbenzene sulfonates,
can also be used.
~thoxylated Nonionic Surfactant
The compositions also contain from about 1% to
about 15%, preferably from about 5% to about 12~, by
weight of an ethoxylated nonionic surfactant of the
formula R (OC2H4)nOH, wherein R is a C10-Cl6 alkyl
group or a C8-C12 alkyl phenyl group, n averages from
35 about 3 to about 9, and said nonionic surfactant has an
HLB (hydrophile-lipophile balance) of from about 10 to
~ r
- - ' ,
,
,:
1 31 5635
about 13. These surfactants are more fully described in
U.S. Patents 4,285,~41, Barrat et al, issued August 25,
1981, and 4,284,532, Leikhim et al, issued August 18,
5 1981. Particularly preferred are condensation products
of cl2-C14 alcohols with from about 3 to about 7 moles of
ethylene oxide per mole of alcohol, e.g., c12-c13 alcohol
condensed with about 6.5 moles of ethylene oxide per
mole of alcohol.
Succinate Builder
The detergent compositions herein also contain from
about 7% to about 20%, preferably from about 10% to
about 15%, by weight on an acid basis, of a succinate
builder of the general formula R-CH(COOH)CH2(COOH),
15 wherein R is C12-C14 alkyl or alkenyl group.
These succinate builders are preferably used in the
form of their water-soluble salts, including the sodium,
potassium, ammonium and alkanolammonium salts (eOg.,
mono-, di-, or tri-ethanolammonium~.
Specific examples of succinate builders include:
lauryl succinate, myrlstyl succinate, 2-dodecenyl
succinate (preferred) and 2-tetradecenyl succinate.
Citrate Builder
The compositions further contain from about 1% to
25 about 7%, preferably from about 2% to about 5.5%, by
weight on an acid basis, of a citrate tpreferably in the
form of an alkali metal or alkanolammonium salt) builder
material. This material is generally added to the
compositions herein as citric acid, but can be added in
30 the form of a fully neutralized salt.
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
35 0.03 moles, per 100 grams of composition of an alkanol-
amine selected from the group consisting of
- .
1 3 1 56~5
g
monoethanolamine, diethanolamine, triethanolamine, and
mixtures thereof. L~w levels of the alkanolamines,
particularly monoethanolamine, are preferred to enhance
product stability and detergency performance. However,
the amount of alkanolamine should be minimized for best
chlorine bleach compatibility.
In addition, the compositions contain potassium and
sodium ions, in a molar ratio of potassium to sodium of
from about 1.4 to about 5.0, preferably from about 1.5
10 to about 2.5, and at a level sufficient to neutralize
the anionic species and provide the desired product pH.
Solvent System
The solvent system fox the compositions is com-
prised of propylene glycol and water.
The propylene glycol ~1,2-propane diol is particu-
larly preferred) represents from about 5~ to about 20%,
preferably from about 8% to about 18%, by weight of the
composition.
The compositions also contain from about 15% to
20 about 45~, preferably from about 20% to about 40%, by
weight of water.
In addition, the propylene glycol and water
represent from about 30% to about 55~, preferably about
35% 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 sulfon-
ate and ethoxylated nonionic surfactantsj together,
30 represent from about lS% to about 40%, preferably from
r about 20% to about 35%, by weight of the composition.
The weight ratio of the sulfonate surfactant to the
ethoxylated nonionic surfactant should also be from
about 1 to about 10, preferably from about 1.5 to about
35 5.
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1 31 5635
-- ~o --
The succinate and citrate builders together
represent from about 10~ to about 25%, preferably from
about 13g to about 20%, by weight of the composition.
In addi~ion, the above builders and surfactants
represent a total of from about 30% to about 55%,
preferably from about 40% to about 50%, by weight of the
composition.
Finally, all of the above components are selected
to provide an isotropic liquid detergent at 68F ~20DC),
10 and preferably at 90F (32.2C) and at 55F (12.8C).
The components are also selected to provide an initial
pH of from about 6.0 to about 10.0, preferably from
about 7.0 to about 9.0, at a concentration of 10% by
weight in water at 68F (20C).
Optional Components
The liquid detergents herein can contain other
surfactants and builders, and other components known for
use in detergent compositions, including enzymes, enzyme
stabilizing agents, polyacids, soil removal agents,
20 antiredeposition agents, suds regulants, hydrotropes,
opacifiers, antioxidants, bactericides, dyes~ perfumes,
and brighteners, such as Athose described in the U.S.
Patent 4,285,841, Barrat et al, issued August 25, 1981!
and in U.S. Patent 4,507,219, Hughes, issued March 26,
25 1985 Such
optional components generally represent less than about
15%, preferably from about 2~ to about 10%, by weight of
the composition.
Particularly preferred compositions herein contain
30 rom about 0.1% to about 10~, preferably from about 0.5%
to about 8~, more preferably from about 1% to about 6%,
by weight of relatively water-insoluble particles
comprising an alkyl amine-anionic surfactant ion-pair
complex as a fabric care agent.
The complex can be represented by the following
formula:
.~
1 3 1 563~
1 1
R2- N H A
5 wherein R1 and R2 can independently be C16 to C20 alkyl
or alkenyl groups. Preferred amines used to form these
complexes are water-insoluble and include hydrogenated
or unhydrogenated ditallow amine. A represents an
anionic surfactant selected from the group consisting of
10 alkyl sulfonates, aryl sulfonates, alkylaryl sulfonates,
and paraffin sulfonates. Preferred anionic surfactants
are C1 to C20 linear alkylbenzene sulfonates and Cl2 to
Cl~ paraffin sulfonates. Mixtuxes of these ion pairs
can also be used.
lS It has been found that in order for these ion-pair
complex particles to impart their fabric care benefits
they must have an average particle diameter of from
about 10 to about 300 microns, preferably from about 10
to about 250 microns, more preferably from about 10 to
20 about 200 microns, and most preferably from about 10
microns to ahout 150 microns. The term "average
particle diametern represents the mean particle size
diameter of the actual particles of a given material.
The mean is calculated on a weight percent basis. The
25 mean is determined by conventional analytical techniques
such as, for example, laser light diffraction or
microscopic determination utilizing a scanning electron
microscope. Preferably, greater than 50% by weight,
more preferably greater than 60% by weight, and most
30 preferably greater than 70~ by weight, of the particles
have actual dimaters which fall within the range of from
about lO to about 300 microns, preferably from about 10
to about 250 microns, more preferably from about 10 to
about 200 microns, and most preferably from about 10
35 microns to about 150 microns.
Starting alkyl amines are of the formula:
.~ . . ' `
,: - .
1 31 5635
- 12 -
Rl~
/ N ~ H
R~
5 wherein Rl and R2 are Cl6 to C20 y
groups, preferably Cl6 to C18 alkyl or alkenyl, and most
preferably C16 to C1~ alkyl. Suitable non-limiting
examples of starting amines include hydrogenated
di~allow amine, unhydrogenated ditallow amine,
10 dipalmityl amine, distearyl amine, diarachidyl amine,
palmityl stearyl amine, palmityl arachidyl amine and
stearyl arachidyl amineO Most preferred are the
hydrogenated and unhydrogenated forms of ditallow amine.
The anionic surfactants ~A) useful in the ion-pair
15 complex of present invention are the Cl to C20 alkyl
sulfonates, aryl sulfonates, C1 to C20 alkylaryl
sulfonates and C12 to C1~ paraffin sulfonates. These
classes of anionic surfactants have been fully described
above.
Particularly preferred are the linear Cl to C20
alkylaryl sulfonates and more particularly preferred are
the linear C~-C13 alkylbenzene sulfonates. Most
preferred are the linear C6 to C13 alkyl benzene
sulfonates.
Non-limiting examples of ion-pair complexes
suitabl~ for use in the present invention include:
ditallow amine Ihydrogenated or unhydrogenated)
complexed with a linear C1 C20 alkyl benzene sulfonate
~LAS),
30 dipalmityl amine complexed with a C1-C20 LAS,
distearyl amine complexed with a C1-C20 LAS,
diarachidyl amin4 complexed with a C~-C20 LAS,
palmityl stearyl amine complexed with a C1 C20 LAS,
parlmityl arachidyl amine complexed with a ~l-C20 LAS,
35 stearyl arachidyl amine complexed with a Cl-C20 LAS,
- ~:
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:
1 31 5635
ditallow amine (hydrogenated or unhydrogenated)
complexed with a Cl-C20 alkyl sulfonate (AS),
dipalmityl amine complexed with a C1-C20 AS,
distearyl amine complexed with a Cl-C20 AS,
5 diarachidyl amine complexed with a Cl-C20 AS~
palmityl stearyl amine complexed with a C1-C20 AS,
palmityl arachidyl amine complexed with a Cl-C20 AS,
stearyl arachidyl amine complexed with a Cl-C20 AS,
ditallow amine (hydrogenated or unhydrogenated)
10 complexed with a C12 C1~ paraffin sulfonate (PS),
dipalmityl amine complexed with a C12-C18 PS,
distearyl amine complexed with a C12-C18 P5,
diarachidyl amine complexed with a C12-C18 PS,
palmityl stearyl amine complexed with a C12-C18 PS,
15 palmityl arachidyl amine complexed with a C12-C18 PS,
stearyl ara~hidyl amine complexed with a C12-C18 PS, and
mixtures of these ion-pair complexes.
More preferred are complexes formed from the
combination of ditallow amine (hydrogenated or
20 unhydrogenated) complexed with Cl-C20 LAS, C1-C20 AS~ or
C12-C18 PS. Even more preferred are those complexes
formed from ditallow amine ~hydrogenated or
unhydrogenated) ccmplexed with a C1-C20 LAS. Most
preferred are complexes formed from ditallow amine
25 (hydrogenated or unhydrogenated) complexed with C6-C13
LAS.
The amine-surfactant complexes herein are prepared
separately from the balance of the composition, and are
preferably then added to the detergent ingredients in
30 such a way as to insure that the complexes are
homogeneously dispersed therein. The amine and
surfactant components are combined in a molar ratio of
alkyl amine to surfactant ranging from about 1:10 to
about 10:1, preferably from about 1:1 to about 9:1.
35 This can be accomplished by any of a variety of means,
including but not limited to, preparing a melt of the
~ .
~, . . . . . . .
~'
1 31 563C)
- 14 -
anionic surfactant and the amine and then dispersing the
molten complex into the balance of the detersive
ingredients, with constant agitation.
Alternatively, the above molten complex can be
5 allowed to cool, preferably while stirring the molten
mixture.
Other methods of forming ~he ion-pair complex
include dissolving the components in an organic solvent,
or by heating the amine to a liquid state and then
10 adding this molten amine component to a heated acidified
aqueous solution of the anionic surfactant, and then
extracting the ion-pair complex by using a solvent, such
as chloroform.
The complexing of the amine and the anionic
15 surfactant res-ults in an entity (ion-pair) which is
chemically distinct from either of the two starting
materials.
The desired particle sizes can be achieved by, for
example, mechanically grinding the resulting ion-pair
20 complex in blenders (e.g., an OsterR blender) or in
large scale mills (e.g~, a Wiley R Mill) to the desired
particle size range.
Such factors as the type of amine employed and the
ratio of the amine-surfactant components can affect the
25 physical properties of the resulting complex. Complexes
which are gelatinous at room temperature can be
mechanically ground to achieve the desired particle size
after flash freezing by using, for example, liquid
nitrogen.
The complexes are further characterized by their
melting points, which generally lie in the range of from
about 10C to about 75C. A particularly preferred
complex, which comprises a hydrogenated ditallow amine
complexed with a linear C6 to C13 alkyl benzene
35 sulfonate surfactant in a 1:1 molar ratio has a melting
point of a~OUt 20C.
i,. ..
'
131563';
- 15 -
It has been found that these fabric care agents,
unlike those of the prior art, can be incorporated into
the detergent compositions of the present invention with
little, if any, detrimental effect on cleaning. These
detergent compositions provide fabric care benefits
across a variety of laundering conditions, that is,
machine or hand washing and machine drying, and also
machine or hand washing and line drying. Additionally~
these same fabric care agents can be used with a variety
10 of surfactant systems.
Preferaby, the compositions of the present
invention contain a stabilizing agent to maintain the
fabric care agent uniformly dispersed in the liquid
detergent. Otherwise, density differences between the
15 insoluble particles and the liquid base detergent can
cause eventual particle settling or creaming.
The choice of the stabilizing agent for the present
compositions depends upon factors such as the type and
level of solvent ingredients in the composition.
Suitable suspending agents include various clay
materials, such as montmorillonite clay, quaternized
montmorillonite clays ~e.g. Bentone 14, available from
NL Industries), polysaccharide gums (e.g. xanthan gum
available from Kelco Division of Merck & CoO, Inc.), any
25 of several long-chain acyl derivative materials or
mixtures of such materials, diethanolamide of a
long-chain fatty acid (e.g., PEG 3 lauramide), block
polymers of ethylene oxide and propylene oxide (such as
Pluronic F88 offered by BASF Wyandotte), sodium
30 chloride, ammonium xylene ~ulfonate, sodium sulfate, and
polyvinyl alcohol. Other suspending agents found useful
are alkanol amides of fatty acids, having from about 16
to about 22 carbon atoms, preferably from abou~ 16 to
about 18 carbon atoms. Preferred alkanol amides are
35 stearic monoethanolamide, stearic diethanolamide,
-i stearic monoisopropanolamide and stearic
~.,
1 3 1 5~3S
- 16
monoethanolamide stearate. Other long-chain acyl
derivatives i~cl~de long-chain esters of long-chain
alkanol amides ~e.g., stearamide DEA distearate,
stearamide MEA stearate).
s The most preferred suspending agent for use in the
present invention is the quaternized montmorillonite
clay.
This suspending agent is preferably present at a
level of from about 0.1% to about 10.0~, preferably from
10 about 0.5% to about 1.5~, by weight of the detergent
composition.
The compositions herein can also contain polymeric
soil release agents, including cellulosic derivatives
such as hydroxyether cellulosic polymers, copolymeric
15 blocks of ethylene terephthalate and polyethylene oxide
or polypropylene oxide terephthalate, and cationic guar
gums, and the like.
The cellulosic derivatives that are functional as
soil release agents are commercially available and
20 include hydroxyethers of cellulose such as MethocelR
(Dow) and cationic cellulose ether derivatives such as
Polymer JR-124R, JR-400R, and JR-30MR (Union Carbide).
See also U.S. Patent 3,928,213 to Temple et al.l issued
December 23, 1975.
Other effective soil release agents are cationic
guar gums such as Jaguar PlauR (Stein Hall) and Gendrive
458 (General Mills).
Preferred cellulosic soil release agents for use
herein are selected from the group consisting of methyl
30 cellulose; hydroxypropyl methylcellulose; hydroxybutyl
methylcellulose; or a mixture thereof, said cellulosic
polymer having a viscosity in aqueous solution at 20C
of 15 to 75,000 centipoise.
A more preferred soil release agent is a copolymer
35 having random blocks of ethylene terephthalate and
r~ polyethylene oxide (PEO) terephthalate. More
-` 1 31 5635
specifically, these polymers are comprised of repeating
units of ethylene terephthalate and PEO terephthalate in
a mole ration of ethylene terephthalate units ~o PEO
terephthalate units of from about 25:75 to about 35:65,
said PEO terephthalate units containing polyethylene
oxide having molecular weights of from about 300 to
about 2000. The molecular weight of this polymeric soil
release agent is in the range of from about 25,000 to
about 55,000. See U.S. Patent 3,959,230 to Hays, issued
lO May 25, 1976, which is incorporated by reference. See
also U.S. Patent 3,893,929 to Basadur issued July 8,
1975 which discloses similar
copolymers. Surprisingly, it has been found that these
pol~meric soil release agents balance the distribution
15 of the fabric care agent of the present invention
against a broad range of synthetic fabrics such as
polyesters, nylons, polycottons and acrylics. This more
uniform distribution of the fabric care agent can result
in improved fabric care qualities. .
Another preferred polymeric soil release agent is a
crystalizable polyester with repeat units of ethylene
terephthalate units containing 10-15% by weight of
ethylene terephthalate units together with 90-80% by
weight of polyoxyethylene terephthalate units, derived
25 from a polyoxyethylene glycol of average molecular
weight 300-5,000, and the mole ratio of ethylene
terephthalate units to polyoxyethylene terephthala~e
units in the crystalliæable polymeric compound is
between 2:1 and 6:1. Examples of this polymer include
30 and commercially available material ZelconR 5126 (from
Dupont) and Milease (from ICIj.
Particularly preferred polymers herein and methods
of their preparation are more fully described in
European Patent ~pplication 185,417, Gosselink,
35 published June 25, 1986 .
. .
~ '
1 3 1 5~3~
- 18 -
If utilized, these soil release agents will
generally comprise from about 0.05% to about 5.0~ by
weight of the detergent compositions herein, more
preferably from about 0.2% to about 3.0% by weight of
such compositions.
While the above compositions con~aining the
ion-pair complex can contain other detergent
surfactants, they preferably contain less than about 5%,
preferably less than about 3~, most preferably less than
lO about 1%, by weight of anionic sulfate and ethoxy
sulfate surfactants, for example, those of the formula
RO~C2H4O~mSO3M, where R is a C10-Cl6 alkyl or
hydroxyalkyl group, m is 0 or averayes up to about 4,
and M is a compatible cation. Most preferably, the
15 compositions are substantially free of such sulfate
surfactants, which inhi~it deposition of the above
fabric care active.
The compositions herein can contain up to about 2~
by weight of ethanol as an additional solubilizing
20 agent. However, the compositions do not require ethanol
for phase stability, and preferably contain little or no
ethanol (e.g., less than about 1% by weight) for
compatibility with the above fabric care active, which
can be solubilized by ethanol. They preferably are
25 substantially free of ethanol.
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
The following composition is prepared by adding the
components to a mixing tank in the order listed with
continuous mixing.
1 31 5G3~)
-- 19 --
Wt.% in
% Actual Wt. Wt.~ Finished
Components Assayl Added (lb) Added Product
Water100.00 115.83 5.26 24.11
1,2~Propanediol100.00 318.78 14.49 14.49
Sodium hydroxide50.00 106.48 4.84 2.42
Potassium hydroxide 45.00 262.4611.93 5.802
C12_13 alcohol poly- 2
ethoxylate (6.5)* 100.00 147.40 6.70 8.70
10 Sodium diethylene-
triamine penta-
acetate41.00 15.56 0.71 0.29
C12 alkenyl succinic
anhydride100.00 246.62 11.21 11.21
15 Calcium formate10.00 22.00 1.00 0.10
Sodium formate30.00 36.67 1.67 0.50
C11 4 linear aikyl~
benzene sulfonic
acid 96.00 3g4.17 17.92 17.20
20 Citric acid50.00 153.12 6.96 3.48
Monoethanolamine100.00 20.46 0 93 1.932
Brightener3.90,114.47 5.20 0.20
TEPA 15-18 80.0039.88 1.81 1.45
(Base prQduct
25total) (1993~88) (90.63)
Potassium hydroxide45.0021.10 0.96
(Total molar
K :Na ) (1.7)
Soil release
30polymer*** 100.0021.34 0.97 0.97
Protease enzyme - 12.76 0.58
(2.5 AU/g)
Amylase enzyme - 6.60 0.30
(155 AMU/m~)
35 Bentone 14 clay100.0015.84 0.72 0.72
DTA/LAS complex 100.00 116.82 5.31 5.31
1 31 563'~
- 20 -
Dye 1.00 6060 0.30 0.01
Perfume 100.00 5.06 0.23 0.23
(Finished product total~ (2~00.00) (100.00~
lBalance to 100% is water unless otherwise noted.
From more than one source.
3Balance also includes 19.23~ monoethanolamine and
38-46% C12-13 alcohol polyethoxylate (6.5)*.
*Alcohol and monoethoxylated alcohol removed.
**T~traethylene pentaimine ethoxylated with 15-18
moles (avg.) of ethylene oxide at each hydrogen site on
each nitrogen.
***Poly(terephthalate propyleneglycol ester~
ethoxylated with about 30 moles of ethylene oxide.
The composition has a pH of about 14 and a
temperature of about 37.8C when the C12 alkenyl
succinic anhydride is added. (The anhydride is used
because it is easier to handle and provides lighter
colored product than the corresponding acid.) The
20 temperature is allowed to rise up to about 71.1C with
moderate agitation. The high temperature, high pH and
substantial water availability are designed to drive ths
hydrolysis and neutralization of the anhydride to
completion. This is accomplished prior--to the addition
25 of the monoethanolamine to avoid reaction between the
monoethanolamine and the anhydride and the formation of
the corresponding amide, which is not effective as a
builder. The composition is then cooled to about 26.7C
by the time the Bentone 14 clay is added.
The DTA/LAS ion-pair complex is made by mixing
hydrogenated ditallow amine (available from Sherex
Chemical Corp., Dublin, OH as Adogen R240, which has
been topped to reduce the monotallow amine content from
about 5~ to less than about 1~ by weight, e.g., 0.9~, to
35 improve particle integrity and physical stability~ with
Cl1 4 linear alkylbenzene sulfonic acid, in a weight
''
:
-" 1 31 5635
- 21 -
ratio of 90:10DTA:LAS, at 71.1-76.7C to form a smooth
syrupy liquid. The complex, at a temperature of
65.6-76.7C, is slowly added ~o the 26.7C composition
under high shear mixing conditions. This causes the
5 complex to disperse into fine droplets that fxeeze as
particles having an average size of about 40-50 microns,
and a median size of about 20 microns, as measured using
a Malvern 2600 particle size analyzer. Moreover, about
69~ of the particles have a size between 9 and 160
10 microns.
The base product is a stable isotropic liquid at
20C and has an initial pH of about 8.2 at a
concentration of 10~ by weight in water at 20C. The
finished product is a stable homogeneous dispersion at
15 20C and has an initial pH of about ~.6 at a
concentration of 10~ by weight in water at 20C.
Other compositions of the present invention are
obtained when the above molar ratio of potassium to
sodium is adjusted to about 2.85; when the levels of C12
20 alkenyl succinic anhydride and citric acid are adjusted
to 14% and 2%, respectively; and when the levels of
C12 13 alchol polyethoxylate and 1,2-propanediol are
adjusted to 5% and 18.5%, respectively.
Other compositions of the present invention are
25 obtained when the above DTAtLAS ion-pair complex is
replaced, in whole or in part, with an equivalent amount
of ditallow amine (hydrogenated or unhydrogenated)
complexed with C6, C8, C10 or C13 linear alkylbenzene
sulfonic acid.
B
.
