Note: Descriptions are shown in the official language in which they were submitted.
WO 94/24240 216 0 2 2 8 PCT/US94/03698
SECONDARY (2,3) ALKYL SULFATE SURFACTANTS IN
STABLE ENZYME-CONTAINING DETERGENT COMPOSITIONS
FIELD OF THE INVENTIOH
The present invention relates to cleaning compositions and
methods which employ secondary (2,3) alkyl sulfate surfactants,
one or more types of detersive enzymes, and an enzyme stabilizer
which provides calcium or magnesium ions.
BACKGROUND OF THE INVENTION
Most conventional detergent compositions contain mixtures of
various detersive surfactants in order to remove a wide variety of
soils and stains from surfaces. For example, various anionic
surfactants, especially the alkyl benzene sulfonates, are useful
for removing particulate soils, and various nonionic surfactants,
such as the alkyl ethoxylates and alkylphenol ethoxylates, are
useful for removing greasy soils.
While a review of the literature would seem to suggest that a
wide selection of surfactants is available to the detergent
manufacturer, the reality is that many such materials are spe-
cialty chemicals which are not suitable for routine use in low
unit cost items such as home laundering compositions. The fact
remains that many home-use laundry detergents still comprise one
or more of the conventional alkyl benzene sulfonate or primary
alkyl sulfate surfactants.
One class of surfactants which has found limited use in
various compositions where emulsification is desired comprises the
secondary alkyl sulfates. The conventional secondary alkyl
sulfates are available as generally pasty, random mixtures of
sulfated linear and/or partially branched alkanes. Such materials
have not come into widespread use in laundry detergents, since
they offer no particular advantages over the alkyl benzene
sulfonates.
It has now been discovered that a particular sub-set of the
class of secondary alkyl sulfates, referred to herein as secondary
(2,3) alkyl sulfates (nSAS~), offers considerable advantages to
the formulator and user of detergent compositions. For example,
the secondary alkyl (2,3J sulfates are more soluble in aqueous
media than their counterpart primary alkyl sulfates of comparable
W O 94/24240 21 6 0 2 ~ 8 PCTAUS94/03698
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chain lengths. Accordingly, they can be formulated as readily-
soluble, high-surfactant (i.e., "high-active~) particles for use
in granular laundry detergents. Moreover, they can be formulated
as stable, homogeneous liquid detergents. In addition, the
solubility of the secondary (2,3) alkyl sulfates allows them to be
formulated in the concentrated form now coming into vogue with
both granular and liquid laundry detergents. Since the secondary
(2,3) alkyl sulfates can be made available in solid, particulate
form, they can be dry-mixed into granular detergent compositions
without the need for passage through spray drying towers.
In addition to the foregoing advantages seen for the
secondary (2,3) alkyl sulfates, it has now been determined that
they are both aerobically and anaerobically degradable, which
assists in their disposal in the environment.
Of course, the manufacturer of fully-formulated detergent
compositions is concerned not only with the safety, ease-of-
handling and performance of the individual components of such
compositions, but also with their compatibility with each other.
For example, various types of detersive enzymes are conventionally
used in laundry detergents to assist in the removal of protein and
lipid stains from fabrics. Enzymes are notorious for their
instability problems, especially when used in contact with deter-
sive surfactants which tend to denature, degrade and deactivate
the enzymes. This is particularly true with lipase enzymes, but
instability is also noted with other important types of enzymes
including proteases, amylases, cellulases and peroxidases. When
formulating granular detergents, it is possible to protect such
enzymes by prilling or other coating techniques which physically
isolate the enzymes from the other ingredients in the composi-
tions. With liquid compositions such techniques are often not
useful, so various stabilizers are added to help provide a
reasonably long shelf life for the resulting compositions.
Whatever technique is used, the search continues for means to
provide more stable enzyme/surfactant systems.
The present invention employs secondary (2,3) alkyl sulfate
surfactants to provide an enhancement of enzyme stability as
compared with conventional anionic sulfated surfactants. It now
appears that the secondary (2,3) alkyl sulfates may be somewhat
~WO 94/24240 216 ~ 2 2 8 PCT~US94/03698
-- 3 --
milder to human tissue than the primary alkyl sulfates. This may
translate into better inherent compatibility with other biological
systems, including detersive enzymes. However, this is not
believed to be the main explanation for the improved stability
(and the resulting improved performance) of the enzyme/secondary
(2,3) alkyl sulfate compositions herein. Rather, it appears that
the presence of cations, especially calcium or magnesium ions, in
detergent compositions substantially enhances the stability of
detersive enzymes. While not intending to be limited by theory,
it may be hypothesized that such cations provide conformational
stability to the overall enzyme structure. Whatever the reason,
abstraction of the cations from the enzyme system, e.g., by
sequestration, precipitation, etc., has a negative impact on
enzyme stability. Accordingly, various sources of calcium ions
(or, less often, magnesium ions) are added to enzyme-containing
detergents (especially liquids, where the stability problem is
usually more acute than in solid products) in order to enhance
stability. By the present invention it has been determined that
the secondary (2,3) allcyl sulfates tend to interact less with such
calcium or magnesium ions than do the conventional primary alkyl
sulfates. As now discovered, the secondary (2,3) alkyl sulfates
appear to have a decreased tendency to abstract such cations from
the enzymes. Whatever the mechanism at the molecular level, the
overall result is that more stable compositions with higher
overall enzymatic cleaning performance can now be secured.
BACKGROUND ART
The problems associated with enzyme instability in detergent
compositions and means to enhance stability are described in
various patents. See, for example: U.S. 4, 537,706, Severson,
August 27, 1985; also U.S. 4,261,868; 4,404,115 and 4,318,818;
Japanese J78028515 published August 15, 1978; Canadian Patents
947,213 and 1,092,036; British 2, 079,305; European 80223, Boskamp,
published June 1, 1983; and German Application 3,330,323.
~ Detergent compositions with various ~secondary" and branched
alkyl sulfates are disclosed in various patents; see: U.S.
2,900,346, Fowkes et al, August 18, 1959; U.S. 3,468,805, Grifo et
al, September 23, 1969; U.S. 3,480,556, DeWitt et al, November 25,
1969 ; U . S . 3,681,424, Bloch et al, August 1, 1972 ; U . S . 4,052,342,
4 ~6~228
Fernley et al, October 4, 1977; U.S. 4,079,020, Mills et al, March 14,
1978; U.S. 4,235,752, Rossall et al, November 25, 1980; U.S.
4,529,541, Wilms et al, July 16, 1985; U.S. 4,614,612, Reilly et al,
September 30, 1986; U.S. 4,880,569, Leng et al, November 14, 1989;
U.S. 5,075,041, Lutz, December 24, 1991; U.K. 818,367, Bataafsche
Petroleum, August 12, 1959; U.K. 1,585,030, Shell, February 18, 1981;
GB 2,179,054A, Leng et al, February 25, 1987 (referring to GB
2,155,031). U.S. Patent 3,234,258, Morris, February 8, 1966, relates
to the sulfation of alpha olefins using HzSO4~ an olefin reactant and
a,low boiling, nonionic, organic crystallization medium.
SUMMARY OF THE INVENTION
The present invention relates to the use of an effective amount
of a secondary (2,3) alkyl sulfate surfactant to provide cleaning
action in a detergent composition which otherwise comprises: (a) an
effective amount of one or more types of enzymes selected from the
group consisting of proteases, amylases, lipases, cellulases,
peroxidases and mixtures thereof; and (b) an effective enzyme-
stabilizing amount of calcium ions, magnesium ions, or mixtures
thereof. The invention also encompasses the use of secondary (2,3)
alkyl sulfate surfactants to provide cleaning action in a fabric
laundering process which employs an aqueous laundry liquor containing
calcium or magnesium ions, or both, and one or more types of detersive
enzymes. In such uses and in the compositions herein, the amount of
calcium or magnesium ions, or both, present is that "enzyme-
stabilizing amount" which is at least sufficient to stabilize the
enzyme from denaturation or degradation which results in any
substantial loss of its cleaning activity. As noted hereinafter,
additional amounts of calcium or magnesium ions, or both, can be
incorporated into the compositions to enhance grease removal
performance. The compatibility of the secondary (2,3) alkyl sulfates
allows for such modifications and improvements to the compositions
herein.
The invention herein provides detergent compositions, especially
fabric laundry compositions, comprising:
(a) at least about 2% by weight of a secondary (2,3) alkyl
sulfate surfactant;
(b) at least about 0.001% by weight of an enzyme preparation
comprising one or a mixture of enzymes selected from the
group consisting of proteases, amylases, lipases,
2 2 8
- 5 -
cellulases, peroxidases and mixtures thereof;
(c) at least about 0.05~ by weight of a water-soluble source
of calcium or magnesium ions, or mixtures thereof;
(d) optional additional enzyme stabilizers; and
(e) optional detersive adjunct materials.
Such compositions can be in the form of liquids, solids, bars, gels,
granules, concentrates, pastes, and the like.
In the present compositions the water-soluble secondary (2,3)
alkyl sulfate detergent preferably has an alkyl chain length in the
range from about 10 to about 18, and mixtures thereof.
The compositions and uses herein are effective with all manner
of detersive enzymes, e.g., members selected from the group consisting
of proteases, amylases, lipases, cellulases, peroxidases and mixtures
thereof.
In one embodiment, the compositions additionally comprise an
enzyme-stabilizing amount of a non-calcium, non-magnesium enzyme
stabilizer, especially a borate or boric acid enzyme stabilizer.
In another embodiment, the compositions herein additionally
comprise an adjunct surfactant, especially non-alkylbenzene sulfonate
surfactants. A preferred class of adjunct surfactants comprises the
polyhydroxy fatty acid amides.
In yet another embodiment, the compositions herein additionally
comprise a detergency builder. For liquid compositions, the builder
is preferably a polycarboxylate builder, especially citrate. For
granular or bar compositions, the detergency builder is preferably a
member selected from the group consisting of zeolite builders, layered
silicate builders, polycarboxylate builders, and mixtures thereof.
However, in bar compositions, the formulator may also use phosphate
builders, since the enzyme/calcium or enzyme/magnesium mixture is
reasonably stable therewith, especially in the absence of alkyl
benzene sulfonate surfactants.
The invention also encompasses a method for cleaning surfaces,
especially soiled fabrics, comprising contacting said surfaces with an
aqueous medium containing an effective amount (typically at least
about 0.01%, preferably at least about 0.05%) of a composition as
disclosed above. Cleaning operations include conventional methods
which employ agitation in automatic washing machines, as well as hand-
washing, both with and without presoaking. The C1o-C20 secondary (2,3)
alkyl sulfates can
9~ -
w o 94/2424~ 21 ~ 0 2 2 8 PCT~US94/~369~ ~
conveniently be employed herein. The C14-C1g compounds are
preferred for laundry cleaning operations.
All percentages, ratios and proportions herein are by weight,
unless otherwise spec;fied. All documents cited are incorporated
herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
PrimarY Inqredients
SecondarY (2.3) AlkYl Sulfate Surfactants - For the conveni-
ence of the formulator, the following identifies and illustrates
the differences between the sulfated surfactants employed herein
and otherwise conventional alkyl sulfate surfactants.
Conventional primary alkyl sulfate surfactants have the
general formula
ROS03-M+
wherein R is typically a linear C1o-C20 hydrocarbyl group and M is
a water-solubilizing cation. Branched-chain primary alkyl sulfate
surfactants (i.e., branched-chain "PAS~) having 10-20 carbon atoms
are also known; see, for example, European Patent Application
439,316, Smith et al, filed 21.01.91.
Conventional secondary alkyl sulfate surfactants are those
materials which have the sulfate moiety distributed randomly along
the hydrocarbyl ~backbone" of the molecule. Such materials may be
depicted by the structure
CH3(cH2)n(cHoso3-M+) (CH2)mCH3
wherein m and n are integers of 2 or greater and the sum of m + n
is typically about 9 to 17, and M is a water-solubilizing cation.
By contrast with the above, the selected secondary (2,3)
alkyl sulfate surfactants used herein comprise structures of
formulas A and B
~A) CH3(CH2)x(CHOSO3-M+) CH3 and
(B) CH3(CH2)y(CH0503~M+) CH2CH3
for the 2-sulfate and 3-sulfate, respectively. Mixtures of the 2-
and 3-sulfate can be used herein. In formulas A and B, x and
(y+1) are, respectively, integers of at least about 6, and can
range from about 7 to about 20, preferably about 10 to about 16.
M is a cation, such as an alkali metal, ammonium, alkanolammonium,
alkaline earth metal, or the like. Sodium is typical for use as M
WO 94/24240 21 6 0 2 2 8 PCT/US94/03698
~__ 7 -
to prepare the water-soluble (2,3) alkyl sulfates, but ethanolam-
monium, diethanolammonium, triethanolammonium, potassium,
ammonium, and the like, can also be used.
By the present invention it has been determined that the
physical/chemical properties of the foregoing types of alkyl
sulfate surfactants are unexpectealy different, one from another,
in several aspects which are important tD formulators of various
types of detergent compositions. For example, the primary alkyl
sulfates can disadvantageously interact with, and even be precipi-
tated by, metal cations such as calcium and magnesium. Thus,
water hardness can negatively affect the primary alkyl sulfates to
a greater extent than the secondary (2,3) alkyl sulfates herein.
Accordingly, the secondary (2,3J alkyl sulfates have now been
found to be preferred for use in the presence of calcium ions and
under conditions of high water hardness, or in the so-called
~under-built~ situation which can occur when nonphosphate builders
are employed.
Importantly, when formulating concentrated liquid detergents
with calcium or magnesium ions to enhance grease cutting or
sudsing performance, and to provide enzyme stability according to
the present invention, it has now been found that the primary
alkyl sulfates can be problematic due to such interactions with
calcium or magnesium cations. Moreover, the solubility of the
primary alkyl sulfates is not as great as the secondary (2,3)
alkyl sulfates. Hence, the formulation of high-active surfactant
particles and high-concentrate liquid detergents has now been
found to be simpler and more effective with the secondary (2,3)
alkyl sulfates than with the primary alkyl sulfates. Thus, in
addition to compatibility with enzymes, the secondary (2,3) alkyl
sulfates are exceptionally easy to formulate as heavy-duty liquid
laundry detergents, especially in combination with short-chain
adjunct surfactants.
~ith regard to the random secondary alkyl sulfates (i.e.,
secondary alkyl sulfates with the sulfate group at positions such
as the 4, 5, 6, 7, etc. secondary carbon atoms), such materials
tend to be tacky solids or, more generally, pastes. Thus, the
random alkyl sulfates do not afford the processing advantages
associated with the solid secondary (2,3) alkyl sulfates when
WO 94Q4240 2 ~ 6 ~ 2 2 8 PCT/US94/03698 ~
formulating detergent granules, bars, or tablets. Moreover, the
secondary (2,3) alkyl sulfates herein provide better sudsing than
the random mixtures. It is preferred that the secondary (2,3)
alkyl sulfates be substantially free (i.e., contain less than
about 20%, more preferably less than about 10X, most preferably
less than about 5X) of such random secondary alkyl sulfates.
One additional advantage of the secondary (2,3) alkyl sulfate
surfactants herein over other positional or ~random~ alkyl sulfate
isomers is in regard to the improved benefits afforded by said
secondary (2,3) alkyl sulfates with respect to soil redeposition
in the context of fabric laundering operations. As is well-known
to users, laundry detergents loosen soils from fabrics being
washed and suspend the soils in the aqueous laundry liquor.
However, as is well-known to detergent formulators, some portion
of the suspended soil can be redeposited back onto the fabrics.
Thus, some redistribution and redeposition of the soil onto all
fabrics in the load being washed can occur. This, of course, is
undesirable and can lead to the phenomenon known as fabric
"greyingn. (As a simple test of the redeposition characteristics
of any given laundry detergent formulation, unsoiled white
"tracer" cloths can be included with the soiled fabrics being
laundered. At the end of the laundering operation the extent that
the white tracers deviate from their initial degree of whiteness
can be measured pho~ometrically or estimated visually by skilled
observers. The more the tracers' whiteness is retained, the less
soil redeposition has occurred.)
It has now been determined that the secondary (2,3) alkyl
sulfates afford substantial advantages in soil redeposition
characteristics over the other positional isomers of secondary
alkyl sulfates in laundry detergents, as measured by the cloth
tracer method noted above. Thus, the select~on of secondary (2,3)
alkyl sulfate surfactants according to the practice of this
invention which preferably are substantially free of other posi-
tional secondary isomers unexpectedly assists in solving the
problem of soil redeposition in a manner not heretofore
recognized.
It is to be noted that the secondary (2,3) alkyl sulfates
used herein are quite different in several important properties
~WO 94/242410 2 1 6 0 2 2 8 PC~/US94J0369~
from the secondary olefin sulfonates (e.g., U.S. Patent 4,064,076,
Klisch et al, 12/20/77); accordingly, the secondary sulfonates are
not the focus of the present invention.
The preparation of the secondary (2,3) alkyl sulfates of the
type useful herein can be carried out by the addition of H2S04 to
olefins. A typical synthesis using ~-olefins and sulfuric acid is
disclosed in U.S. Patent 3,234,258, Morris, or in U.S. Patent
5,075,041, Lutz, granted December 24, 1991. The synthesis,
conducted in solvents which afford the secondary (2,3) alkyl
sulfates on cooling, yields products which, when purified to
remove the unreacted materials, randomly sulfated materials,
unsulfated by-products such as C1o and higher alcohols, secondary
olefin sulfonates, and the like, are typically 90+% pure mixtures
of 2- and 3-sulfated materials (up to 10% sodium sulfate is
typically present) and are white, non-tacky, apparently
crystalline, solids. Some 2,3-disulfates may also be present, but
generally comprise no more than 5% of the mixture of secondary
(2,3) alkyl mono-sulfates. Such materials are available as under
the name "DAN~, e.g., "DAN 200~ from Shell Oil Company.
If increased solubility of the "crystalline~ secondary (2,3)
alkyl sulfate surfactants is desired, the formulator may wish to
employ mixtures of such surfactants having a mixture of alkyl
chain lengths. Thus, a mixture of C12-C1g alkyl chains will
provide an increase -in solubility over a secondary (2,3) alkyl
sulfate wherein the alkyl chain is, say, entirely C16. The
solubility of the secondary (2,3) alkyl sulfates can also be
enhanced by the addition thereto of other surfactants such as the
alkyl ethoxylates or other nonionic surfactants, or by any other
material which decreases the crystallinity of the secondary (2,3)
alkyl sulfates. Such crystallinity-interrupting materials are
typically effective at levels of 20%, or less, of the secondary
~ (2,3) alkyl sulfate.
When formulating liquid compositions, especially clear
liquids, it is preferred that the secondary (2,3) alkyl sulfate
surfactants contain less than about 3X sodium sulfate, preferably
less than about 1% sodium sulfate. In and of itself, sodium
sulfate is an innocuous material. However, it dissolves and adds
to the ionic ~load~ in aqueous media, and this can contribute to
WO 94/~4240 216 0 2 2 8 PCT/US94/03698
- 10 - .
phase separation in the liquid compositions and to gel breaking in
the gel compositions.
Various means can be used to lower the sodium sulfate content
of the secondary (2,3) alkyl sulfates. For example, when the
H2504 addition to the olefin is completed, care can be taken to
remove unreacted H2S04 before the acid form of the secondary (2,3J
alkyl sulfate is neutralized. In another method, the sodium salt
form of the secondary (2,3) alkyl sulfate which contains sodium
sulfate can be rinsed with water at a temperature near or below
the Krafft temperature of the sodium secondary (2,3) alkyl
sulfate. This will remove Na2S04 with only minimal loss of the
desired, purified sodium secondary (2,3) alkyl sulfate. Of
course, both procedures can be used, the first as a
pre-neutralization step and the second as a post-neutralization
step.
The term "Krafft temperature~ as used herein is a term of
art which is well-known to workers in the field of surfactant
sciences. Krafft temperature is described by K. Shinoda in the
text ~Principles of Solution and Solubilityn, translation in
collaboration with Paul Becher, published by Marcel Dekker, Inc.
1978 at pages 160-161. Stated succinctly, the solubility of a
surface active agent in water increases rather slowly with
temperature up to that point, i.e., the Krafft temperature, at
which the solubility evidences an extremely rapid rise. At a
temperature approximately 4-C above the Krafft temperature a
solution of almost any composition becomes a homogeneous phase.
In general, the Krafft temperature of any given type of
surfactant, such as the secondary (2,3) alkyl sulfates herein
which comprise an anionic hydrophilic sulfate group and a
hydrophobic hydrocarbyl group, will vary with the chain length of
the hydrocarbyl group. This is due to the change in water
solubility with the variation in the hydrophobic portion of the
surfactant molecule.
In the practice of the present invention the formulator may
optionally wash the secondary (2,3) alkyl sulfate surfactant which
is contaminated w~th sodium sulfate with water at a temperature
that is no higher than the Krafft temperature, and which is
preferably lower than the Krafft temperature, for the particular
O 94/24240 2 ~ 6 0 2 2 8 PCT/lJS94~(13698
- 11 -
secondary (2,3) alkyl sulfate being washed. This allows the
sodium sulfate to be dissolved and removed with the wash water,
while keeping losses of the secondary (2,3) alkyl sulfate into the
wash water to a minimum.
Under circumstances where the secondary (2,3) alkyl sulfate
surfactant herein comprises a mixture of alkyl chain lengths, it
will be appreciated that the Krafft temperature will not be a
single point but, rather, will be denoted as a "Krafft boundary~.
Such matters are well-known to those skilled in the science of
surfactant/solution measurements. In any event, for such mixtures
of secondary (2,3) alkyl sulfates, it is preferred to conduct the
optional sodium sulfate removal operation at a temperature which
is below the Krafft boundary, and preferably below the Krafft
temperature of the shortest chain-length surfactant present in
such mixtures, since this avoids excessive losses of secondary
(2,3) alkyl sulfate to the wash solution. For example, for C16
secondary sodium alkyl (2,3) sulfate surfactants, it is preferred
to conduct the washing operation at temperatures below about 30-C,
preferably below about 20-C. It will be appreciated that changes
in the cations will change the preferred temperatures for washing
the secondary (2,3) alkyl sulfates, due to changes in the Krafft
temperature.
The washing process can be conducted batchwise by suspending
wet or dry secondary (2,3) alkyl sulfates in sufficient water to
provide 10-50X solids, typically for a mixing time of at least 10
minutes at about 22-C (for a C16 secondary t2,3] alkyl sulfate),
followed by pressure filtration. In a preferred mode, the slurry
will comprise somewhat less than 35% solids, inasmuch as such
slurries are free-flowing and amenable to agitation during the
washing process.
As an additional benefit, the washing process also reduces
- the levels of organic contaminants which comprise the random
secondary alkyl sulfates noted above.
Enz~mes - Enzymes are included in the formulations herein for
a wide variety of fabric laundering purposes, including removal of
protein-based, carbohydrate-based, or triglyceride-based stains,
for example, and for the prevention of refugee dye transfer, and
for fabric restoration. The enzymes to be incorporated include
WO 94/24240 2 1 6 ~ 2 2 8 PCT/US94/03698
.
- 12 -
proteases, amylases, lipases, cellulases, and peroxidases, as well
as mixtures thereof. Other types of enzymes may also be included.
They may be of any suitable origin, such as vegetable, animal,
bacterial, fungal and yeast origin. However, their choice is
governed by several factors such as pH-activity and/or stability
optima, thermostability, stability versus active detergents,
builders and so on. In this respect bacterial or fungal enzymes
are preferred, such as bacterial amylases and proteases, and
fungal cellulases.
Enzymes are normally incorporated at levels sufficient to
provide up to about 5 mg by weight, more typically about 0.01 mg
to about 3 mg, of active enzyme per gram of the composition.
Stated otherwise, the compositions herein will typically comprise
from about 0.001X to about 5X, preferably 0.01%-1%, by weight of a
commercial enzyme preparation. Protease enzymes are usually
present in such commercial preparations at levels sufficient to
provide from 0.005 to 0.1 Anson units (AU) of activity per gram of
composition.
Suitable examples of proteases are the subtilisins which are
obtained from particular strains of B.subtilis and B.licheniforms.
Another suitable protease is obtained from a strain of Bacillus,
having maximum activity throughout the pH range of 8-12, developed
and sold by Novo Industries A/S under the registered trade name
ESPERASE. The preparation of this enzyme and analogous enzymes is
described in British Patent Specification No. 1,243,784 of Novo.
Proteolytic enzymes suitable for removing protein-based stains
that are commercially available include those sold under the
tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark)
and MAXATASE by International Bio-Synthetics, Inc. (The
Netherlands). Other proteases include Protease A (see European
Patent Application 130,756, published January 9, 1985) and
Protease B (see European Patent Application Serial No. 87303761.8,
filed April 28, 1987, and European Patent Application 130,756,
Bott et al, published January 9, 1985).
Amylases include, for example, ~-amylases described in
Brit~.sh Patent Specification No. 1,296,839 (Novo), RAPIDASE,
International Bio-Synthetics, Inc. and It~ WIYL, Novo Industries.
~WO 94/24240 21 6 0 2 2 8 PCT/US94~036g8
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The cellulases usable in the present invention include both
bacterial or fungal cellulase. Preferably, they will have a pH
optimum of between S and 9.5. Suitable cellulases are disclosed
in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984,
which discloses fungal cellulase produced from Humicola insolens
and Humicola strain DSM1800 or a cellulase 212-producing fungus
belonging to the genus Aeromonas, and cellulase extracted from the
hepatopancreas of a marine mollusk (Dolabella Auricula Solander).
Suitable cellulases are also disclosed in GB-A-2.075.028;
GB-A-2.095.275 and DE-OS-2.247.832.
Suitable lipase enzymes for detergent usage include those
produced by microorganisms of the Pseudomonas group, such as
Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent
1,372,034. See also lipases in Japanese Patent Application
53-20487, laid open to public inspection on February 24, 1978.
This lipase is available from Amano Pharmaceutical Co. Ltd.,
Nagoya, Japan, under the trade name Lipase P ~Amano,~ hereinafter
referred to as ~Amano-P.~ Other commercial llpases include
Amano-CES, lipases ex Chromobacter vJscosum, e.g. Chromobacter
viscosum var. Iipo1yticum NRRLB 3673, commercially available from
Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum
lipases from U.S. Biochemica~ Corp., U.S.A. and Disoynth Co., The
Netherlands, and lipases ex Pseudomonas g7adio7i. The LIPOLASE
enzyme derived from Humico7a 7anuginosa and commercially available
from Novo (see also EPO 341,947) is a preferred lipase for use
herein.
Peroxidase enzymes are used in combination with oxygen
sources, e.g., percarbonate, perborate, persulfate, hydrogen
peroxide, etc. They are used for ~solution bleaching,~ i.e. to
prevent transfer of dyes or pigments removed from substrates
during wash operations to other substrates in the wash solution.
Peroxidase enzymes are known in the art, and include, for example,
horseradish peroxidase, ligninase, and haloperoxidase such as
chloro- and bromo-peroxidase. Peroxidase-containing detergent
compositions are disclosed, for example, in PCT International
Application WO 89/099813, published October 19, 1989, by 0. Kirk,
assigned to Novo Industries A/S.
WO 94/24Z40 - 14 - PCT/US94/03698
A wide range of enzyme materials and means for their incorp-
oration into synthetic detergent granules is also disclosed in
U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al ().
Enzymes are further disclosed in U.S. Patent 4,101,457, Place et
al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes,
issued March 26, 1985, both. Enzyme materials useful for liquid
detergent formulations, and their incorporation into such
formulations, are disclosed in U.S. Patent 4,261,868, Hora et al,
issued April 14, 1981. Enzymes for use in detergents can be
stabilized by various techniques. Enzyme stabilization techniques
are disclosed and exemplified in U.S. Patent 4,261,868, issued
April 14, 1981 to Horn, et al, U.S. Patent 3,600,319, issued
August 17, 1971 to Gedge, et al, and European Patent Application
Publication No. O 199 405, Application No. 86200586.5, published
October 29, 1986, Yenegas. Enzyme stabilization systems are also
described, for example, in U.S. Patents 4,261,868, 3,600,319, and
3,519,570.
EnzYme Stabilizers - The enzymes employed herein are
stabilized by the presence of water-soluble sources of calcium
and/or magnesium ions in the finished compositions which provide
such ions to the enzymes. (Calcium ions are generally somewhat
more effective than magnesium ions and are preferred herein if
only one type of cation is being used.) Additional stability can
be provided by the presence of various other art-disclosed
stabilizers, especially borate species: see Severson, U.S.
4,537,706, cited above. Typical detergents, especially liquids,
will comprise from about 1 to about 30, preferably from about 2 to
about 20, more preferably from about 5 to about 15, and most
preferably from about 8 to about 12, millimoles of calcium ion per
liter- of finished composition. This can vary somewhat, depending
on the amount of enzyme present and its response to the calcium or
magnesium ions. The level of calcium or magnesium ions should be
selected so that there is always some minimum level available for
the enzyme, after allowing for complexation with builders, fatty
acids, etc., in the composition. Any water-soluble calcium or
magnesium salt can be used as the source of calcium or magnesium
ions, including, but not limited to, calcium chloride, calcium
sulfate, calcium malate, calcium maleate, calcium hydroxide,
WO 94/242~10 21 6 ~ 2 2 8 PCT/US94/03698
.
- 15 - -
calcium formate, and calcium acetate, and the corresponding
magnesium salts. A small amount of calcium ion, generally from
about 0.05 to about 0.4 millimoles per liter, is often also
present in the composition due to calcium in the enzyme slurry and
formula water. In solid detergent compositions the formulation
may include a sufficient quantity of a water-soluble calcium ion
source to provide such amounts in the laundry liquor. In the
alternative, natural water hardness may suffice.
It is to be understood that the foregoing levels of calcium
and/or magnesium ions are sufficient to provide enzyme stability.
More calcium and/or magnesium ions can be added to the
compositions to provide an additional measure of grease removal
performance. Accordingly, as a general proposition the composi-
tions herein will typically comprise from about 0.05% to about 2%
by weight of a water-soluble source of calcium or magnesium ions,
or both. The amount can vary, of course, with the amount and type
of enzyme employed in the composition.
The compositions herein may also optionally, but preferably,
contain various additional stabilizers, especially borate-type
stabilizers. Typically, such stabilizers will be used at levels
in the compositions from about 0.25% to about 10X, preferably from
about 0.5% to about 5X, more preferably from about 0.75% to about
3%, by weight of boric acid or other borate compound capable of
forming boric acid in the composition (calculated on the basis of
boric ac~d). 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.
Adiunct Inqredients
In addition to enzymes, the compositions herein can option-
ally include one or more other detergent adjunct materials or
other materials for assisting or enhancing cleaning performance,
treatment of the substrate to be cleaned, or to modify the
aesthetics of the detergent composition (e.g., perfumes, color-
ants, dyes, etc.). The following are illustrative examples of
such adjunct materials.
w o 94/24240 2 1 6 0 2 2 8 PCT/11594/03698 ~
Builders - Detergent builders can optionally be included in
the compositions herein to assist in controlling mineral hardness.
Inorganic as well as organic builders can be used. Builders are
typically used in fabric laundering compositions to assist in the
S removal of particulate soils.
The level of builder can vary widely depending upon the end
use of the composition and its desired physical form. When
present, the compositions will typically comprise at least about
lX builder. Liquid formulations typically comprise from about 5X
to about 50%, more typically about 5% to about 30X, by weight, of
detergent builder. Granular formulations typically comprise from
about 10X to about 80Y" more typically from about 15% to about 50%
by weight, of the detergent builder. Lower or higher levels of
builder, however, are not meant to be excluded.
Inorganic detergent builders include, but are not limited to,
the alkali metal, ammonium and alkanolammonium salts of polyphos-
phates (exemplified by the tripolyphosphates, pyrophosphates, and
glassy polymeric meta-phosphates), phosphonates, phytic acid,
silicates, carbonates (including bicarbonates and sesquicarbon-
ates), sulphates, and aluminosilicates. However, non-phosphate
builders are required in some locales. Importantly, the composi-
tions herein function surprisingly well even in the presence of
the so-called ~weak~ builders (as compared with phosphates) such
as citrate, or in the so-called "underbuilt~ situation that may
occur with zeolite or layered silicate builders. Moreover, the
secondary (2,3) alkyl sulfate plus enzyme components perform best
in the presence of weak, nonphosphate builders which allow free
calclum ions to be present. This is especially true for liquid
compos~tions.
Examples of silicate builders are the alkali metal silicates,
particularly those having a SiO2:Na20 ratio in the range 1.6:1 to
3.2:1 and layered silicates, such as the layered sodium silicates
described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P.
Rieck. NaSKS-6 is the trademark for a crystalline layered
silicate marketed by Hoechst (commonly abbreviated herein as
~SKS-6~). Unlike zeolite builders, the Na SKS-6 silicate builder
does not contain aluminum. NaSKS-6 has the delta-Na2SiOs
morphology form of layered silicate. It can be prepared by
WO 94/24240 PCTIUS94rO3698
~ 2160228
- 17 -
methods such as those described in German DE-A-3,417,649 and
DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for
use herein, but other such layered silicates, such as those having
the general formula NaMSixO2x+l YH2O wherein M is sodium or
hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a
number from 0 to 20, preferably 0 can be used herein. Various
other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and
NaSKS-ll, as the alpha, beta and gamma forms. As noted above, the
delta-Na25iOs (NaSKS-6 form) is most preferred for use herein.
Other silicates may also be useful such as for example magnesium
silicate, wh;ch can serve as a crispening agent in granular
formulations, as a stabilizing agent for oxygen bleaches, and as a
component of suds control systems.
Examples of carbonate builders are the alkaline earth and
alkali metal carbonates as disclosed in German Patent Application
No. 2,321,001 published on November 15, 1973.
Aluminosilicate builders are useful in the present invention.
Aluminosilicate builders are of great importance in most currently
marketed heavy duty granular detergent compositions, and can also
be a significant builder ingredient in liquid detergent
formulations. Aluminosilicate builders include those having the
empirical formula:
MZ(zAlo2-ysio2)
wherein M is sodium, potassium, ammonium or substituted ammonium,
z is from about 0.5 to about 2; and y is 1; this material having a
magnesium ion exchange capacity of at least about 50 milligram
equivalents of CaCO3 hardness per gram of anhydrous aluminosili-
cate. Preferred aluminosilicates are zeolite builders which have
the formula:
Naz[(Alo2)z (Sio2)y]-xH2o
wherein z and y are integers of at least 6, the molar ratio of z
to y is in the range from 1.0 to about 0.5, and x is an integer
from about lS to about 264.
Useful aluminosilicate ion exchange materials are commer-
3 cially available. These aluminosilicates can be crystalline or
amorphous in structure and can be naturally-occurring aluminosili-
cates or synthetically derived. A method for producing alumino-
silicate ion exchange materials is disclosed in U.S. Patent
WO 94l2424~ 21 6 0 ~ 2 8 pcT/uss4m36ss ~
3,985,669, Krummel, et al, issued October 12, 1976. Preferred
synthetic crystalline aluminosilicate ion exchange materials
useful herein are available under the designations Zeolite A,
Zeolite P (BJ, and ~eolite X. In an especially preferred embodi-
ment, the crystalline aluminosilicate ion exchange material has
the formula:
Nal2[(A102)12(5iO2)l2] ~XH20
wherein x is from about 20 to about 30, especially about 27. This
material is known as ~eolite A. Preferably, the aluminosilicate
has a particle size of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the
present invention include, but are not restricted to, a wide
variety of polycarboxylate compounds. As used herein, ~polycar-
boxylate" refers to compounds having a plurality of carboxylate
groups, preferably at least 3 carboxylates. Polycarboxylate
builder can generally be added to the composition in acid form,
but can also be added in the form of a neutralized salt. When
utilized in salt form, alkali metals, such as sodium, potassium,
and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of
categories of useful materials. One important category of poly-
carboxylate builders encompasses the ether polycarboxylates,
including oxydisuccinate, as disclosed in Berg, U.S. Patent
3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent
3,635,830, issued January 18, 1972. See also ~TMS/TDS~ builders
of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
Suitable ether polycarboxylates also include cyclic compounds,
particularly alicyclic compounds, such as those described in U.S.
Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
~ther useful detergency builders include the ether hydroxy-
polycarboxylates, copolymers of maleic anhydride with ethylene or
vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisul-
phonic acid, and carboxymethyloxysuccinic acid, the various alkali
metal, ammonium and substituted ammonium salts of polyacetic acids
such as ethylenediamine tetraacetic acid and nitrilotriacetic
acid, as well as polycarboxylates such as mellitic acid, succinic
~WO 94/24240 2 ~ 6 0 2 2 8 PCT/US94/03698
- 19 -
acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricar-
boxylic acid, carboxymethyloxysuccinic acid, and soluble salts
thereof.
Citrate builders, e.g., citric acid and soluble salts thereof
(particularly sodium salt), are polycarboxylate builders of
particular importance for heavy duty liquid detergent formulations
due to their availabil~ty from renewable resources and their
biodegradability. Citrates can also be used in granular composi-
tions, especially in combination with zeolite and/or layered
silicate builders. Oxydisuccinates are also especially useful in
such compositions and combinations.
Also suitable in the detergent compositions of the present
invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the
related compounds disclosed in U.S. Patent 4,566,984, Bush, issued
January 28, 1986. Useful succinic acid builders include the
Cs-C20 alkyl and alkenyl succinic acids and salts thereof. A
particularly preferred compound of this type is dodecenylsuccinic
acid. Specific examples of succinate builders include: laurylsuc-
cinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate
(preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccin-
ates are the preferred builders of this group, and are described
in European Patent Application 86200690.5/0,200,263, published
November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent
4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S.
Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl
U.S. Patent 3,723,322.
Fatty acids, e.g., C12-C1g monocarboxylic acids, can also be
incorporated into the compositions alone, or in combination with
the aforesaid builders, especially citrate and/or the succinate
builders, to provide additional builder activity. Such use of
fatty acids will generally result in a diminution of sudsing,
which should be taken into account by the formulator.
In situations where phosphorus-based builders can be used,
and especially in the formulation of bars used for hand-laundering
operations, the various alkali metal phosphates such as the
well-known sodium tripolyphosphates, sodium pyrophosphate and
sodium orthophosphate can be used. Phosphonate builders such as
WO 94/24240 21~ 0 2 2 8 PCT/US94/03698 ~
- 20 -
ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates
(see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021;
3,400,148 and 3,422,137) can also be used.
Bleachinq ComPounds - Bleaching A~ents and Bleach Activators
- The detergent compositions herein may optionally contain
bleaching agents or bleaching compositions containing a bleaching
agent and one or more bleach activators. When present, bleaching
agents will typically be at levels of from about lX to about 30%,
more typically from about 5% to about 20%, of the detergent
composition, especially for fabric laundering. If present, the
amount of bleach activators will typically be from about 0.1X to
about 60%, more typically from about 0.5X to about 40% of the
bleaching composition comprising the bleaching agent-plus-bleach
activator.
The bleaching agents used herein can be any of the bleaching
agents useful for detergent compositions in textile cleaning, hard
surface cleaning, or other cleaning purposes that are now known or
become known. These include oxygen bleaches as well as other
bleaching agents. Perborate bleaches, e.g., sodium perborate
(e.g., mono- or tetra-hydrate) can be used herein.
One category of bleaching agent that can be used without
restriction encompasses percarboxylic acid bleaching agents and
salts thereof. Suitable examples of this class of agents include
magnesium monoperoxyphthalate hexahydrate, the magnesium salt of
meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid
and diperoxydodecanedioic acid. Such bleaching agents are dis-
closed in U.S. Patent 4,483,781, Hartman, issued November 20,
1984, U.S. Patent Application 740,446, Burns et al, filed June 3,
1985, European Patent Application 0,133,354, Banks et al, pub-
lished February 20, 1985, and U.S. Patent 4,412,934, Chung et al,
issued November 1, 1983. Highly preferred bleaching agents also
include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S.
Patent 4,634,551, issued January 6, 1987 to Burns et al.
Peroxygen bleaching agents can also be used. Suitable
peroxygen bleaching compounds include sodium carbonate peroxy-
hydrate and equivalent ~percarbonate" bleaches, sodium pyrophos-
phate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
2 2 8 PCT/US94/03698
- 21 -
Persulfate bleach (e.g., OXONE, manufactured commercially by
DuPont) can also be used.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the percarbon-
ates, etc., are preferably combined with bleach activators, which
lead to the in situ production in aqueous solution (i.e., during
the washing process) of the peroxy acid corresponding to the
bleach activator. Various nonlimiting examples of activators are
disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao
et al, and U.S. Patent 4,412,934. The nonanoyloxybenzene
sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activat-
ors are typical, and mixtures thereof can also be used. See also
U.S. 4,634,551 for other typical bleaches and activators useful
herein.
Bleaching agents other than oxygen bleaching agents are also
known in the art and can be utilized herein. One type of non-
oxygen bleaching agent of particular interest includes photo-
activated bleaching agents such as the sulfonated zinc and/or
aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July
5, 1977 to Holcombe et al. If used, detergent compositions will
typically contain from about 0.025% to about 1.25%, by weight, of
such bleaches, especially sulfonated zinc phthalocyanine.
PolYmeric Soil Release Aqent - Any polymeric soil release
agent known to those skilled in the art can optionally be employed
in the compositions and processes of this invention. Polymeric
soil release agents are characterized by having both hydrophilic
segments, to hydrophilize the surface of hydrophobic fibers, such
as polyester and nylon, and hydrophobic segments, to deposit upon
hydrophobic fibers and remain adhered thereto through completion
of washing and rinsing cycles and, thus, serve as an anchor for
the hydrophilic segments. This can enable stains occurring
subsequent to treatment with the soil release agent to be more
easily cleaned in later washing procedures.
The polymeric soil release agents useful herein especially
include those soil release agents having: (a) one or more
non10nic hydrophile components consisting essentially of (i)
polyoxyethylene segments with a degree of polymerization of at
least 2, or (ii) oxypropylene or polyoxypropylene segments with a
WO 94/24240 21~ 0 2 2 8 PCT/US94103698 ~
- 22 -
degree of polymerization of from 2 to 10, wherein said hydrophile
segment does not encompass any oxypropylene unit unless it is
bonded to adjacent moieties at each end by ether linkages, or
(iii) a mixture of oxyalkylene units comprising oxyethylene and
from I to about 30 oxypropylene units wherein said mixture con-
tains a sufficient amount of oxyethylene units such that the
hydrophile component has hydrophilicity great enough to increase
the hydrophilicity of conventional polyester synthetic fiber
surfaces upon deposit of the soil release agent on such surface,
said hydrophile segments preferably comprising at least about 25X
oxyethylene units and more preferably, especially for such compon-
ents having about 20 to 30 oxypropylene units, at least about 50X
oxyethylene units; or (b) one or more hydrophobe components
comprising (i) C3 oxyalkylene terephthalate segments, wherein, if
said hydrophobe components also comprise oxyethylene terephthal-
ate, the ratio of oxyethylene terephthalate:C3 oxyalkylene tere-
phthalate units is about 2:1 or lower, (ii) C4-C6 alkylene or oxy
C4-C6 alkylene segments, or mixtures therein, (iii) poly (vinyl
ester) segments, preferably poly(vinyl acetate), having a degree
of polymerization of at least 2, or (iv) Cl-C4 alkyl ether or C4
hydroxyalkyl ether substituents, or mixtures therein, wherein said
substituents are present in the form of Cl-C4 alkyl ether or C4
hydroxyalkyl ether cellulose derivatives, or mixtures therein, and
such cellulose derivatives are amphiphilic, whereby they have a
sufficient level of Cl-C4 alkyl ether and/or C4 hydroxyalkyl ether
units to deposit upon conventional polyester synthetic fiber
surfaces and retain a sufficient level of hydroxyls, once adhered
to such conventional synthetic fiber surface, to increase fiber
surface hydrophilicity, or a combination of (a) and (b).
-Typically, the polyoxyethylene segments of (a)(i) will have a
degree of polymerization of from 2 to about 200, although higher
levels can be used, preferably from 3 to about 150, more prefer-
ably from 6 to about 100. Suitable oxy C4-C6 alkylene hydrophobe
segments include, but are not limited to, end-caps of polymeric
soil release agents such as M03S(CH2)nOCH2CH20-, where M is sodium
and n is an integer from 4-6, as disclosed in U.S. Patent
4,721,580, issued January 26, 1988 to Gosselink.
~0 94/24240 21 6 0 2 2 8 PCT/US94/03698
- 23 -
Polymeric soil release agents useful in the present invention
also include cellulosic derivatives such as hydroxyether cellu-
losic polymers, copolymeric blocks of ethylene terephthalate or
propylene terephthalate with polyethylene oxide or polypropylene
oxide terephthalate, and the like. Such agents are commercially
available and include hydroxyethers of cellulose such as METHOCEL
(Dow). Cellulosic soil release agents for use herein also include
those selected from the group consisting of Cl-C4 alkyl and C4
hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December
28, 1976 to Nicol, et al.
Soil release agents characterized by poly(vinyl ester)
hydrophobe segments include graft copolymers of poly(vinyl ester),
e.g., C1-C6 vinyl esters, preferably poly(vinyl acetate) grafted
onto polyalkylene oxide backbones, such as polyethylene oxide
backbones. See European Patent Application 0 219 048, published
April 22, 1987 by Kud, et al. Commercially available soil release
agents of this kind include the SOKALAN type of material, e.g.,
SOKALAN HP-22, available from BASF (West Germany).
One type of preferred soil release agent is a copolymer
having random blocks of ethylene terephthalate and polyethylene
oxide (PEO) terephthalate. 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 May 25, 1976
and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
Another preferred polymeric soil release agent is a 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
from a polyoxyethylene glycol of average molecular weight
300-5,000. Examples of this polymer include the commercially
available material ZELCON 5126 (from Dupont) and MILEASE T (from
ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to
Gosselink.
Another preferred polymeric soil release agent is a
sulfonated product of a substantially linear ester oligomer
comprised of an oligomeric ester backbone of terephthaloyl and
oxyalkyleneoxy repeat units and terminal moieties covalently
attached to the backbone. These soil release agents are described
WO 94/24240 21~ 0 2 2 8 PCTrUS94/03698 ~
- 24 -
fully in U.S. Patent 4,968,451, issued November 6, 1990 to J. J.
Scheibel and E. P. Gosselink.
Other suitable polymeric soil release agents include the
terephthalate polyesters of U.S. Patent 4,711,730, issued December
8, 1987 to Gosselink et al, the anionic end-capped oligomeric
esters of U.S. Patent 4,721,580, issued January 26, 1988 to
Gosselink, and the block polyester oligomeric compounds of U.S.
Patent 4,702,857, issued October 27, 1987 to Gosselink.
Preferred polymeric soil release agents also include the soil
release agents of U.S. Patent 4,877,896, issued October 31, 1989
to Maldonado et al, which discloses anionic, especially sulfo-
aroyl, end-capped terephthalate esters.
If utilized, soil release agents will generally comprise from
about 0.01% to about 10.0~., by weight, of the detergent composi-
tions herein, typically from about 0.lX to about 5X, preferably
from about 0.2% to about 3.0X.
Chelatinq Aqents - The detergent compositions herein may also
optionally contain one or more iron and/or manganese chelating
agents. Such chelating agents can be selected from the group
consisting of amino carboxylates, amino phosphonates,
polyfunctionally-substituted aromatic chelating agents and
mixtures therein, all as hereinafter defined. Without intending
to be bound by theory, it is believed that the benefit of these
materials is due in part to their exceptional ability to remove
iron and manganese ions from washing solutions by formation of
soluble chelates.
Amino carboxylates useful as optional chelating agents
include ethylenediaminetetraacetates, N-hydroxyethylethylenedi-
aminetriacetates, nitrilotriacetates, ethylenediamine tetrapropri-
onates, triethylenetetraaminehexaacetates, diethylenetriamine-
pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and
substituted ammonium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as chelating
agents in the compositions of the invention when at least low
levels of total phosphorus are permitted in detergent
compositions, and include ethylenediaminetetrakis (methylenephos-
phonates), nitrilotris (methylenephosphonates) and diethylenetri-
aminepentakis (methylenephosphonates) as DEQUEST. Preferably,
W O 94/24240 ~ 2 ~ 8 PCTnUS9~3~8
- 25 -
these amino phosphonates do not contain alkyl or alkenyl groups
with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are
also useful in the compositions herein. See U.S. Patent
3,812,044, issued May 21, 1974, to Connor et al. Preferred
compounds of this type in acid form are dihydroxydisulfobenzenes
such as 1,2-dihydroxy - 3, 5-disulfobenzene.
A preferred biodegradable chelator for use herein is ethyl-
enediamine disuccinate (nEDDS~), as described in U.S. Patent
0 4,704,233, November 3, 1987, to Hartman and Perkins.
If utilized, these chelating agents will generally comprise
from about 0.1% to about 10X by weight of the detergent composi-
tions herein. More preferably, if utilized, the chelating agents
will comprise from about 0.1% to about 3.0X by weight of such
compositions.
Clav Soil Removal/Anti-rede~osition Aqents - The compositions
of the present invention can also optionally contain water-soluble
ethoxylated amines having clay soil removal and anti-redeposition
propert~es. Granular detergent compositions which contain these
compounds typically contain from about 0.01% to about 10.0% by
weight of the water-soluble ethoxylated amines; liquid detergent
compositions typically contain about 0.01% to about g%.
The most preferred soil release and anti-redeposition agent
is ethoxylated tetraethylenepentamine. Exemplary ethoxylated
amines are further described in U.S. Patent 4,597,898, VanderMeer,
issued July 1, 1986. Another group of preferred clay soil
removal/antiredeposition agents are the cationic compounds dis-
closed in European Patent Application 111,965, Oh and 60sselink,
published June 27, 1984. Other clay soil removal/antiredeposition
agent~ which can be used include the ethoxylated amine polymers
disclosed in European Patent Application 111,984, Gosselink,
published June 27, 1984; the zwitterionic polymers disclosed in
European Patent Application 112,592, Gosselink, published July 4,
1984; and the amine oxides disclosed in U.S. Patent 4,548,744,
Connor, issued October 22, 1985. Other clay soil removal and/or
anti redeposition agents known in the art can also be utilized in
WO 94/24240 2 1 6 0 ~ 2 8 PCT/US94/03698 ~
the compositions herein. Another type of preferred antiredeposi-
tion agent includes the carboxy methyl cellulose (CMC) materials.
These materials are well known in the art.
PolYmeric Dis~ersing Agents - Polymeric dispersing agents can
advantageously be utilized at levels from about 0.1% to about 7X,
by weight, in the compositions herein, especially in the presence
of zeolite and/or layered silicate builders. Suitable polymeric
dispersing agents include polymeric polycarboxylates and poly-
ethylene glycols, although others known in the art can also be
used. It is believed, though it is not intended to be limited by
theory, that polymeric dispersing agents enhance overall detergent
builder performance, when used in combination with other builders
(including lower molecular weight polycarboxylates) by crystal
growth inhibition, particulate soil release peptization, and
anti-redeposition
Polymeric polycarboxylate materials can be prepared by
polymerizing or copolymerizing suitable unsaturated monomers,
preferably in their acid form. Unsaturated monomeric acids that
can be polymerized to form suitable polymeric polycarboxylates
include acrylic acid, maleic acid (or maleic anhydride), fumaric
acid, itaconic acid, aconitic acid, mesaconic acid, citraconic
acid and methylenemalonic acid. The presence in the polymeric
polycarboxylates herein of monomeric segments, containing no
carboxylate radicals such as vinylmethyl ether, styrene, ethylene,
etc. is suitable provided that such segments do not constitute
more than about 40% by weight.
Particularly suitable polymeric polycarboxylates can be
derived from acrylic acid. Such acrylic acid-based polymers which
are useful herein are the water-soluble salts of polymerized
acrylic acid. The average molecular weight of such polymers in
the acid form preferably ranges from about 2,000 to 10,000, more
preferably from about 4,000 to 7,000 and most preferably from
about 4,000 to 5,000. Water-soluble salts of such acrylic acid
polymers can include, for example, the alkali metal, ammonium and
substituted ammonium salts. Soluble polymers of this type are
known materials. Use of polyacrylates of this type in detergent
compositions has been disclosed, for example, in Diehl, U.S.
Patent 3,308,067, issued March 7, 1967.
~VO 94/24240 2 1 6 Q 2 2 8 PC'r/US94~03698
- 27 -
Acrylic/maleic-based copolymers may also be used as a pre-
ferred component of the dispersing~anti-redeposition agent. Such
materials include the water-soluble salts of copolymers of acrylic
acid and maleic acid. The average molecular weight of such
copolymers in the acid form preferably ranges from about 2,000 to
100,000, more preferably from about 5,000 to 75,000, most prefer-
ably from about 7,000 to 65,000. The ratio of acrylate to maleate
segments in such copolymers will generally range from about 30:1
to about 1:1, more preferably from about 10:1 to 2:1. Water-
soluble salts of such acrylic acid/maleic acid copolymers can
include, for example, the alkali metal, ammonium and substituted
ammonium salts. Soluble acrylate/maleate copolymers of this type
are known materials which are described in European Patent Appli-
cation No. 66915, published December 15, 1982.
Another polymeric material which can be included is poly-
ethylene glycol (PEG). PEG can exhibit dispersing agent perform-
ance as well as act as a clay soil removal/antiredeposition agent.
Typical molecular weight ranges for these purposes range from
about 500 to about 100,000, preferably from about 1,000 to about
50,000, more preferably from about 1,500 to about 10,000.
Polyaspartate and polyglutamate dispersing agents may also be
used, especially in conjunction with zeolite builders.
Briqhtener - Any optical brighteners or other brightening or
whitening agents known in the art can be incorporated at levels
typically from about 0.05% to about 1.2X, by weight, into the
detergent compositions herein. Commercial optical brighteners
which may be useful in the present invention can be classified
~nto subgroups which include, but are not necessarily limited to,
derivatiYes of stilbene, pyrazoline, coumarin, carboxylic acid,
methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and
6-membered-ring heterocycles, and other miscellaneous agents.
Examples of such brighteners are disclosed in "The Production and
Application of Fluorescent Brightening Agentsn, M. Zahradnik,
Published by John Wiley h Sons, New York (1982).
Specific examples of optical brighteners which are useful in
the present compositions are those identified in U.S. Patent
4,790,856, issued to Wixon on December 13, 1988. These brighten-
ers include the PHORWHITE series of brighteners from Verona.
WO 94124240 21~ ~ 2 2 8 PCT/US94/03698 ~
- 28 -
Other brighteners disclosed in this reference include: Tinopal
UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy;
Arctic White CC and Artic White CWD, available from Hilton-Davis,
located in Italy; the 2-(4-styryl-phenyl)-2H- naphtholt1,2-d]-
triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stil- benes; 4,4'-bis-
(styryl)bisphenyls; and the aminocoumarins. Specific examples of
these brighteners include 4-methyl-7-diethyl- amino coumarin;
1,2-bis(-benzimidazol-2-yl)ethylene; 1,3-diphenylphrazolines;
2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naphth-[1,2-d]oxazole;
and 2-(stilbene-4-yl)-2H-naphtho- t1,2-d]triazole. See also U.S.
Patent 3,646,015, issued February 29, 1972 to Hamilton.
Suds SuDDressors - Compounds for reducing or suppressing the
formation of suds can be incorporated into the compositions of the
present invention. Suds suppression can be of particular import-
ance under conditions such as those found in European-style front
loading laundry washing machines, or in the concentrated deter-
gency process of U.S. Patents 4,489,455 and 4,489,574, or when the
detergent compositions herein optionally include a relatively high
sudsing adjunct surfactant.
A wide variety of materials may be used as suds suppressors,
and suds suppressors are well known to those skilled in the art.
See, for example, Kirk Othmer Encyclopedia of Chemical Technology,
Third Edition, Volume 7, pages 430-447 (John Wiley h Sons, Inc.,
1979). One category of suds suppressor of particular interest
encompasses monocarboxylic fatty acids and soluble salts therein.
See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St.
John. The monocarboxylic fatty acids and salts thereof used as
suds suppressor typically have hydrocarbyl chains of 10 to about
24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts
include the alkali metal salts such as sodium, potassium, and
lithium salts, and ammonium and alkanolammonium salts.
The detergent compositions herein may also contain non-
surfactant suds suppressors. These include, for example: high
molecular weight hydrocarbons such as paraffin, fatty acid esters
(e.g., fatty acid triglycerides), fatty acid esters of monovalent
alcohols, aliphatic C18-C40 ketones (e.g. stearone), etc. Other
suds inhibitors include N-alkylated amino triazines such as tri-
to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines
~VO 94124240 ~ ~ 6 ~ ~ 2 8 PCT/US94/03698
- 29 -
formed as products of cyanuric chloride with two or three moles of
a primary or secondary amine containing 1 to 24 carbon atoms,
propylene oxide, and monostearyl phosphates such as monostearyl
alcohol phosphate ester and monostearyl di-alkali metal (e.g. K,
Na, and Li) phosphates and phosphate esters. The hydrocarbons
such as paraffin and haloparaffin can be utilized in liquid form.
The liquid hydrocarbons will be liquid at room temperature and
atmospheric pressure, and will have a pour point in the range of
about -40-C and about 5-C, and a minimum boiling point not less
than about llO-C (atmospheric pressure). It is also known to
utilize waxy hydrocarbons, preferrably having a melting point
below about 100-C. The hydrocarbons constitute a preferred
category of suds suppressor for detergent compositions.
Hydrocarbon suds suppressors are described, for example, in U.S.
Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The
hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and
heterocyclic saturated or unsaturated hydrocarbons having from
about 12 to about 70 carbon atoms. The term "paraffin,~ as used
in this suds suppressor discussion, is intended to include
mixtures of true paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds suppressors
comprises silicone suds suppressors. This category includes the
use of polyorganosiloxane oils, such as polydimethylsiloxane,
dispersions or emulsions of polyorganosiloxane oils or resins, and
combinations of polyorganosiloxane with silica particles wherein
the polyorganosiloxane is chemisorbed of fused onto the silica.
Silicone suds suppressors are well known in the art and are, for
example, disclosed in U.S. Patent 4,265,779, issued May S, 1981 to
Gandolfo et al and European Patent Application No. 89307851.9,
published February 7, 1990, by Starch, M. S.
Other silicone suds suppressors are disclosed in U.S. Patent
3,455,839 which relates to compositions and processes for
defoaming aqueous solutions by incorporating therein small amounts
of polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described, for
instance, in German Patent Application DOS 2,124,526. Silicone
defoamers and suds controlling agents in granular detergent
compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et
WO 94124240 21~ 0 2 2 8 PCT/US94/03698 ~
- 30 -
al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24,
1987.
An exemplary silicone based suds suppressor for use herein is
a suds suppressing amount of a suds controlling agent consisting
essentially of:
(i) polydimethylsiloxane fluid having a viscosity of from
about 20 cs. to about 1500 cs. at 25-C;
(ii) from about 5 to about 50 parts per 100 parts by weight
of (i) of siloxane resin composed of (CH3)3 Si~1/2 units
of SiO2 units in a ratio of from (CH3)3 Si~1/2 units and
to SiO2 units of from about 0.6:1 to about 1.2:1; and
(iii) from about 1 to about 20 parts per 100 parts by weight
of (i) of a solid silica gel;
In the preferred silicone suds~suppressor used herein, the
solvent for a continuous phase is made up of certain polyethylene
glycols or polyethylene-polypropylene glycol copolymers or
mixtures thereof (preferred), and not polypropylene glycol. The
~ primary silicone suds suppressor is branched/crosslinked and not
linear.
To illustrate this point further, typical liquid laundry
detergent compositions with controlled suds will optionally
comprise from about 0.001 to about 1, preferably from about 0.01
to about 0.7, most preferably from abut 0.05 to about 0.5, weight
% of said silicone suds suppressor, which comprises (1) a
nonaqueous emulsion of a primary antifoam agent which is a mixture
of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone
resin-producing silicone compound, (c) a finely divided filler
material, and (d) a catalyst to promote the reaction of mixture
components (a), (b) and (c), to form silanolates; (2) at least one
nonionic silicone surfactant; and (3) polyethylene glycol or a
copolymer of polyethylene-polypropylene glycol having a solubility
in water at room temperature of more than about 2 weight X; and
without polypropylene glycol. Similar amounts can be used in
granular compositions, gels, etc. See also U.S. Patents
4,978,471, Starch, issued December 18, 1990, and 4,983,316,
Starch, issued January 8, 1991, and U.S. Patents 4,639,489 and
4,749.740, Aizawa et al at column 1, line 46 through column 4,
line 35.
~W0 94/24240 ~ 1 6 ~ 2 2 8 PCT/US94~03698
- 31 -
The sillcone suds suppressor herein preferably comprises
polyethylene glycol and a copolymer of polyethylene glycol/poly-
propylene glycol, all having an average molecular weight of less
than about 1,000, preferably between about 100 and 800. The
polyethylene glycol and polyethylene/polypropylene copolymers
herein have a solubility in water at room temperature of more than
about 2 weight %, preferably more than about 5 weight %.
The preferred solvent herein is polyethylene glycol having an
average molecular weight of less than about 1,000, more preferably
between about 100 and 800, most preferably between 200 and 400,
and a copolymer of polyethylene glycol/polypropylene glycol,
preferably PPG 200/PEG 300. Preferred is a weight ratio of
between about 1:1 and 1:10, most preferably between 1:3 and 1:6,
of polyethylene glycol:copolymer of polyethylene~polypropylene
glycol.
The preferred silicone suds suppressors used herein do not
contain polypropylene glycol, particularly of 4,000 molecular
weight. They also preferably do not contain block copolymers of
ethylene oxide and propylene oxide, like PLURONIC L101.
Other suds suppressors useful herein comprise the secondary
alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols
wlth silicone oils, such as the silicones disclosed in U.S.
4,798,679, 4,075,118 and EP 150,872. The secondary alcohols
include the C6-C16 alkyl alcohols having a C1-C16 chain. A
preferred alcohol is 2-butyl octanol, which is available from
Condea under the trademark ISOFOL 12. Mixtures of secondary
alcohols are available under the trademark ISALCHEM 123 from
Enichem. Mixed suds suppressors typically comprise mixtures of
alcohol + silicone at a weight ratio of 1:5 to 5:1.
~or any detergent compositions to be used in automatic
laundry washing machines, suds should not form to the extent that
they overflow the washing machine. Suds suppressors, when
utilized, are preferably present in a ~suds suppressing amount.~
By ~suds suppressing amount~ is meant that the formulator of the
composition can select an amount of this suds controlling agent
that will sufficiently control the suds to result in a low-sudsing
laundry detergent for use in automatic laundry washing machines.
WO 94/24240 2 ~ 6 ~ 2 2 8 PCT/US94/03698 ~
- 32 -
The compositions herein will generally comprise from ~X to
about 5% of suds suppressor. When utilized as suds suppressors,
monocarboxylic fatty acids, and salts therein, will be present
typically in amounts up to about 5X, by weight, of the detergent
composition. Preferably, from about 0.5X to about 3% of fatty
monocarboxylate suds suppressor is utilized. Silicone suds
suppressors are typically utilized in amounts up to about 2.0X, by
weight, of the detergent composition, although higher amounts may
be used. This upper limit is practical in nature, due primarly to
concern with keeping costs minimized and effectiveness of lower
amounts for effectively controlling sudsing. Preferably from
about 0.01% to about 1% of silicone suds suppressor is used, more
preferably from about 0.25X to about 0.5%. As used herein, these
weight percentage values include any silica that may be ~Itilized
in combination w~th polyorganosiloxane, as well as any adjunct
materials that may be utilized. Monostearyl phosphate suds
suppressors are generally utilized in amounts ranging from about
0.1% to about 2X, by weight, of the composition. Hydrocarbon suds
suppressors are typically utilized in amounts ranging from about
0.01% to about 5.0%, although higher levels can be used. The
alcohol suds suppressors are typically used at 0.2%-3% by weight
of the finished compositions
In addition to the foregoing ingredients, the compositions
herein can also be used with a variety of other adjunct ingredi-
ents which provide still other benefits in various compositions
within the scope of this invention. The following illustrates a
variety of such adjunct ingredients, but is not intended to be
limiting therein.
Fabric Softeners - Various through-the-wash fabric softeners,
especially the impalpable smectite clays of U.S. Patent 4,062,647,
Storm and Nirschl, issued December 13, 1977, as well as other
softener clays known in the art, can optionally be used typically
at levels of from about 0.5% to about 10% by weight in the present
compositions to provide fabric softener benefits concurrently with
fabric cleaning. Clay softeners can be used in combination with
amine and cationic softeners, as disclosed, for example, in U.S.
Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent
4,291,071, Harris et al, issued September 22, 1981.
~WO 94/24240 - 2 ~ 6 0 2 2 8 PCTIUS94/03698
- 33 -
Adiunct Surfactants - The compositions herein can optionally
contain various anionic, nonionic, zwitterionic, etc. surfactants.
If used, such adjunct surfactants are ~ypically present at levels
of from about 5% to about 35% of the compositions. However, it is
to be understood that the incorporation of adjunct anionic
surfactants is entirely optional herein, inasmuch as the cleaning
performance of the secondary (2,3) alkyl sulfates is excellent and
these materials can be used to entirely replace such surfactants
as the alkyl benzene sulfonates in fully-formulated detergent
compositions.
Nonlimiting examples of optional surfactants useful herein
include the conventional C11-C1g alkyl benzene sulfonates and
primary and random alkyl sulfates (having due regard for the
enzyme stability issues noted above), the C1o-C1g alkyl alkoxy
sulfates (especially EO 1-5 ethoxy sulfates), C10-cl8 alkyl alkoxy
carboxylates (especially the EO 1-5 ethoxycarboxylates), the
C10-cl8 alkyl polyglycosides and their corresponding sulfated
polyglycosides, C12-C1g alpha-sulfonated fatty acid esters,
C12-C1g alkyl and alkyl phenol alkoxylates (especially ethoxylates
and mixed ethoxy/propoxy), C12-C1g betaines and sulfobetaines
(nsultaines~), C10-cl8 amine oxides, and the like. Other conven-
tional useful surfactants are listed in standard texts.
One particular class of adjunct nonionic surfactants
especially useful herein comprises the polyhydroxy fatty acid
amides of the formula:
0, Rl
(I) R2 - C - N - Z
wherein: Rl is H, C1-Cg hydrocarbyl, 2-hydroxyethyl, 2-hydroxy-
propyl, or a mixture thereof, preferably C1-C4 alkyl, more prefer-
ably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and
R2 is a Cs-C32 hydrocarbyl moiety, preferably straight chain
C7-C1g alkyl or alkenyl, more preferably straight chain Cg-C17
alkyl or alkenyl, most preferably straight chain C11-C1g alkyl or
alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl
moiety having a linear hydrocarbyl chain with at least 2 (in the
case of glyceraldehyde) or at least 3 hydroxyls (in the case of
other reducing sugars) directly connected to the chain, or an
alkoxylated derivative (preferably ethoxylated or propoxylated)
WO 94/24240 ~16 0 2 2 8 PCT/US94/03698 ~
- 34 -
thereof. Z preferably will be derived from a reducing sugar in a
reductive amination reaction; more preferably Z is a glycityl
moiety. Suitable reducing sugars include glucose, fructose,
maltose, lactose, galactose, mannose, and xylose, as well as
glyceraldehyde. As raw materials, high dextrose corn syrup, high
fructose corn syrup, and high maltose corn syrup can be utilized
as well as the individual sugars listed above. These corn syrups
may yield a mix of sugar components for Z. It should be
understood that it is by no means intended to exclude other
suitable raw materials. Z preferably will be selected from the
group consisting of -CH2-(CHOH)n-CH20H, -CH(CH20H)-(CHOH)n 1-
CH20H, -CH2-(CHOH)2(CHOR')(CHOH)-CH2OH, where n is an integer from
1 to 5, inclusive, and R' is H or a cyclic mono- or poly-
saccharide, and alkoxylated derivatives thereof. Most preferred
are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH20H.
In Formula (I), R1 can be, for example, N-methyl, N-ethyl,
N-propyl, N-isopropyl, N-butyl, N-isobutyl, N-2-hydroxy ethyl, or
N-2-hydroxy propyl. For highest sudsing, Rl is preferably methyl
or hydroxyalkyl. If low sudsing is desired, R1 is preferably
C2-Cg alkyl, especially n-propyl, iso-propyl, n-butyl, iso-butyl,
pentyl, hexyi and 2-ethyl hexyl.
R2-C0-N< can be, for example, cocamide, stearamide, oleamide,
lauramide, myristamide, capricamide, palmitamide, tallowamide,
etc.
While polyhydroxy fatty acid amides can be made by the
process of Schwartz, U.S. 2,703,798, contamination with cyclized
by-products and other colored materials can be problematic. As an
overall proposition, the preparative methods described in
W0-9,206,154 and W0-9,206,984 will afford high quality polyhydroxy
fatty- acid amides. The methods comprise reacting N-alkylamino
polyols with, preferably, fatty acid methyl esters in a solvent
using an alkoxide catalyst at temperatures of about 85-C to
provide high yields (90-98%) of polyhydroxy fatty acid amides
having desirable low levels (typically, less than about 1.0X) of
sub-optimally degradable cyclized by-products and also with
improved color and improved color stabil~ty, e.g., Gardner Colors
below about 4, preferably between 0 and 2. (With compounds such
as butyl, iso-butyl and n-hexyl, the methanol introduced via the
~VO 94124240 21~ 0 2 2 8 PCT/US94/03698
..
- 35 -
catalyst or generated during the reaction provides sufficient
fluidization that the use of additional reaction solvent may be
optional.) If desired, any unreacted N-alkylamino polyol
remaining in the product can be acylated with an acid anhydride,
e.g., acetic anhydride, maleic anhydride, or the like, to minimize
the overall level of such residual amines in the product. Resi-
dual sources of classical fatty acids, which can suppress suds,
can be depleted by reaction with, for example, triethanolamine.
By ~cyclized by-products~ herein is meant the undesirable
reaction by-products of the primary reaction wherein it appears
that the multiple hydroxyl groups in the polyhydroxy fatty acid
amides can form ring structures which are, in the main, not
readily biodegradable. It will be appreciated by those skilled in
the chemical arts that the preparation of the polyhydroxy fatty
acid amides herein using the di- and higher saccharides such as
maltose will result in the formation of polyhydroxy fatty acid
amides wherein linear substituent Z (which contains multiple
hydroxy substituents) is naturally "capped~ by a polyhydroxy ring
structure. Such mater~als are not cyclized by-products, as
defined herein.
The foregoing polyhydroxy fatty acid amides can also be
sulfated, e.g., by reaction with 503/pyridine, and the resulting
sulfated material used as an adjunct anionic surfactant herein.
Moreover, there has now been found to be a substantial and
remarkable improvement in cold water solubility as a result of the
blending and agglomeration of a mixture of the secondary (2,3)
alkyl sulfates (SAS) herein with polyhydroxy fatty acid amide
surfactants (PFAS), alkyl ethoxylate surfactants (AE) and primary
alkyl sulfate surfactants (AS) to prov~de mixed SAS/PFAS/AE/AS
parti-cles. While not intending to be limited by theory, it
appears that this increase in solubility may be due to the
destruction of the crystallinity of the SAS. Whatever the reason,
the improved solubility is of substantial benefit under cold water
conditions (e.g., at temperatures in the range of 5-C to about
30-C) where the rate of solubility of detergent granules in an
aqueous washing liquor can be problematic. Of course, the
improved solubility achieved herein is also of substantial benefit
w o 94/24240 216 0 2 2 8 PcT/usg4/n3698 ~
when preparing the modern compact or dense detergent granules
where solubility can be problematic.
Other Inqredients - A wide variety of other ingredients
useful in detergent compositions can be included in the composi-
tions herein, including other active ingredients, carriers,
hydrotropes, processing aids, dyes or pigments, solvents for
liquid formulations, etc. If high sudsing is desired, suds
boosters such as the C1o-C16 alkanolamides can be incorporated
into the compositions, typically at 1%-10% levels. The C1o-C14
monoethanol and diethanol amides illustrate a typical class of
such suds boosters. Use of such suds boosters with high sudsing
adjunct surfactants such as the amine oxides, betaines and
sultaines noted above is also advantageous. If desired, soluble
magnesium salts such as MgCl2, MgS04, and the like, can be added
at levels of, typically, 0.1%-2%, to provide additional suds~ng.
Various detersive ingredients employed in the present compo-
sitions optionally can be further stabilized by absorbing said
~ngredients onto a porous hydrophobic substrate, then coating said
substrate with a hydrophobic coating. Preferably, the detersive
ingredient is admixed with a surfactant before being absorbed into
the porous substrate. In use, the detersive ingredient is
released from the substrate into the aqueous washing liquor, where
it performs its intended detersive function.
To illustrate this technique in more detail, a porous hydro-
phobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a
proteolytic enzyme solution containing 3%-5% of C13 15 ethoxylated
alcohol EO(7) nonionic surfactant. Typically, the enzyme/surfact-
ant solution is 2.5 X the weight of silica. The resulting powder
is dispersed with stirring in silicone oil (various silicone oil
viscosities in the range of 500-12,500 can be used). The result-
ing silicone oil dispersion is emulsified or otherwise added to
the final detergent matrix. By this means, ingredients such as
the aforementioned enzymes, bleaches, bleach activators, bleach
catalysts, photoactivators, dyes, fluorescers, fabric conditioners
and hydrolyzable surfactants can be "protected~ for use in deter-
gents, including liquid laundry detergent compositions.
Liquid detergent compositions can contain water and other
solvents as carriers. Low molecular weight primary or secondary
~v 216 Q 2 2 ~ PCTIUS94103698
- 37 -
alcohols exemplified by methanol, ethanol, propanol, and isopro-
panol are suitable. Monohydric alcohols are preferred for solu-
bilizing surfactant, but polyols such as those containing from 2
to about 6 carbon atoms and from 2 to about 6 hydroxy groups
(e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-
propanediol) can also be used. The compositions may contain from
5% to 90%, typically 10~ to 50X of such carriers.
The detergent compositions herein will preferably be formu-
lated such that, during use in aqueous cleaning operations, the
wash water will have a pH of between about 6.5 and about 11,
preferably between about 7.5 and about 10.5. Liquid dishwashing
product formulations preferably have a pH between about 6.8 and
about 9Ø Laundry products are typically at pH 9-11. Techniques
for controlling pH at recommended usage levels include the use of
buffers, alkalis, acids, etc., and are well known to those skilled
in the art.
The following are typical, nonlimiting examples which illus-
trate the detergent compositions and uses of the secondary (2,3)
alkyl sulfates according to this invention. Preferred composi-
tions for most purposes contain no phosphates.
The liquid laundry detergent of Example I is prepared by
dissolving or dispersing the indicated ingredients in an aqueous
carrier and adjusting the pH in the range of 9.0-10.5.
- EXAMPLE I
A liqu~d laundry detergent composition herein comprises the
following.
Inqredient % (wt.)
Secondary (2,3) alkyl sulfate* 15.0
C14 N-methyl glucamide 5.0
Sodium citrate 3.0
C10 alcohol ethoxylate (3) 13.0
Monoethanolamine 2.5
MAXATASE (enzyme) 0.5
LIPOLASE (enzyme) 0.5
CaCl2 0 9
Water/propylene glycol/ethanol (100:1:1) Balance
*C12-C16 average chain length; Na salt form; less than 1% Na2S04.
WO 941:24240 216 0 2 2 8 PCT/US94/03698 ~
- 38 -
In general terms, particulate detergents herein comprising
the secondary (2,3) alkyl sulfate surfactants can be prepared
using a variety of well-known processes. For example, particles
can be formed by agglomeration, wherein solids (including the
5secondary (2,3) alkyl sulfates) are forced/hurled together by
physical mixing and held together by a binder. Suitable apparatus
for agglomeration includes dry powder mixers, fluid beds and
turbilizers, available from manufacturers such as Lodige, Eric,
Bepex and Aeromatic.
10In another mode, particles can be formed by extrusion. In
this method, solids such as the secondary (2,3) alkyl sulfates are
forced together by pumping a damp powder at relatively high
pressures and high energy inputs through small holes in a die
plate. This process results in rod like particles which can be
15divided into any desired particle size. Apparatus includes axial
or radial extruders such as those available from Fuji, Bepex and
Teledyne/Readco.
In yet another mode, particles can be formed by prilling. In
this method, a liquid mixture containing the desired ingredients
20(i.e., one of them being secondary (2,3) alkyl sulfate particles)
is pumped under high pressure and sprayed into cool air. As the
liquid droplets cool they become more solid and thus the particles
are formed. The solidification can occur due to the phase change
of a molten binder to a solid or through hydration of free mois-
25ture into crystalline bound moisture by some hydratable material
in the original liquid mixture.
In still another mode, particles can be formed by compaction.
This method is similar to tablet formation processes, wherein
solids (i.e., secondary t2,3] alkyl sulfate particles) are forced
30together by compressing the powder feed into a die/mold on rollers
or flat sheets.
In another mode, particles can be formed by melt/solidifica-
tion. In this method, particles are formed by melting the second-
ary (2,3) alkyl sulfate with any desired additional ingredient and
35allowing the melt to cool, e.g., in a mold or as droplets.
Binders can optionally be used in the foregoing methods to
enhance particle integrity and strength. Water, alone, is an
operative binder with secondary (2,3) alkyl sulfates, since it
~'0 94/24240 21 6 0 2 2 8 PCT/US94/03698
- 39 ~
will dissolve some of the secondary (2,3) alkyl sulfate to provide
a binding function. Other binders include, for example, starches,
~ polyacrylates, carboxymethylcellulose and the like. Binders are
well-known in the particle making literature. If used, binders
are typically employed at levels of 0.1%-5% by weight of the
finished particles.
If desired, fillers such as hydratable and nonhydratable
salts, crystalline and glassy solids, various detersive ingredi-
ents such as zeolites and the like, can be incorporated in the
particles. If used, such fillers typically comprise up to about
20% by weight of the particles.
Particles prepared in the foregoing manner can be subse-
quently dried or cooled to adjust their strength, physical proper-
ties and final moisture content, according to the desires of the
formulator.
The preferred overall making process for particulate products
herein involves three distinct Steps: (1) agglomeration of the
ingredients to form the base formula, followed by; (2) admixing
various ingredients with the agglomerates formed in Step (1)
(e.g., percarbonate bleach, bleach activators, and the like); and
optionally, but preferably, (3) spraying materials such as perfume
onto the final mix.
The base formula is agglomerated as opposed to spray dried in
order to prevent degradation of some of the heat sensitive
surfactants. The resulting product is a hlgh density (ranging
from 600 g/liter - 800 g/liter) free flowing detergent mix that
can be used in place of current spray dried laundry detergents.
With regard to the base Agglomeration (Step 1, above), this
procedure is comprised of four Steps:
-(A) preparing a surfactant paste using mixers such as the
Readco Standard Sigma Mixer, T-Series;
(B) agglomerating powder components with the surfactant
paste using mixers such as the Eirich Mixer, R-Series;
(C) drying the agglomerates, such as in a batch-type
Aeromatic fluidized bed or a continuous type static or
vibrating fluidized bed (NIRO, Bepex or Carrier
Companies); and
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(D) coating the agglomerates using a mixer such as an Eirich
Mixer, R-Series.
The following describes the Agglomeration Step in more
detail.
SteD A - PreParation of Surfactant Paste - The objective is
to combine the surfactants and liquids in the compositions into a
common mix in order to aid in surfactant solubilization and
agglomeration. In this Step, the surfactants and other liquid
components in the composition are mixed together in a Sigma Mixer
at 140-F (60-C) at about 40 rpm to about 75 rpm for a period of
from 15 minutes to about 30 minutes to provide a paste having the
general consistency of 20,000-40,000 centipoise. Once thoroughly
mixed, the paste is stored at 140-F (60-C) until agglomeration
Step (B) is ready to be conducted. The ingredients used in this
Step include surfactants, acrylate/maleic polymer (m.w. 70,000)
and polyethylene glycol ~PEG~ 4000-8000.
SteD ~ - Aqqlomeration of Powders with Surfactant Paste - The
purpose of this Step is to transform the base formula ingredients
into flowable detergent particles having a medium particle size
range of from about 300 microns to about 600 microns. In this
Step, the powders (including materials such as zeolite, citrate,
citric acid builder, layered silicate builder (as SKS-6), sodlum
carbonate, ethylenediaminedisuccinate, magnesium sulfate and
optical brightener) are charged into the Eirich Mixer (R-Series)
and mixed briefly (ca. 5 seconds - 10 seconds) at about 1500 rpm
to about 3000 rpm in order to mix the various dry powders fully.
The surfactant paste from Step A is then charged into the mixer
and the mixing is continued at about 1500 rpm to about 3000 rpm
for a period from about 1 minute to about 10 minutes, preferably
1-3 minutes, at ambient temperature. The mixing is stopped when
coarse agglomerates (average particle size 800-1600 microns) are
formed.
SteD C - The purpose of this Step is to reduce the agglomer-
ates' stickiness by removing/drying moisture and to aid in
particle size reduction to the target particle size (in the median
size range from about 300 to about 600 microns, as measured by
sieve analys~s). In this Step, the wet agglomerates are charged
into a fluidized bed at an air stream temperature of from about
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41-C to about 60-C and dried to a final moisture content of the
particles from about 4% to about 10X.
SteD D - Coat Aqqlomerates and Add Free-Flow Aids - The
objective in this Step is to achieve the final target particle
size range of from about 300 microns to about 600 microns, and to
admix materials which coat the agglomerates, reduce the
caking/lumping tendency of the particles and help maintain
acceptable flowability. In this Step, the dried agglomerates from
Step C are charged into the Eirich Mixer (R-Series) and mixed at a
rate of about 1500 rpm to about 3000 rpm while adding 2-6X Zeolite
A (median particle size 2-5~m) during the mixing. The mixing is
continued until the desired median particle size of from about
1200 to about 400 microns is achieved (typically from about 5
seconds to about 45 seconds). At this point, from about 0.1X to
about 1.5X by weight of precipitated silica (average particle size
1-3 microns) is added as a flow aid and the mixing is stopped.
The following illustrates a laundry detergent composition
prepared in the foregoing manner.
EXAMPLE II
Aqqlomerate
X (wt.) in X (wt.) in
final Droduct aqqlomerate
C14 15 alkyl sulfate, Na 5.8 6.8
C16 secondary (2,3) alkyl sulfate, Na17.3 20.4
C12-C13 ethoxylated alcohol (E03) 4.7 5.5
C12_14 N-methylglucamide 4.7 5.5
Acrylate/maleate copolymer 6.2 7.3
Polyethylene glycol 1.4 1.7
Aluminosilicate (zeolite) 8.8 10.3
Sodium citrate 1.9 2.2
Citric acid/SKS-61 11.5 13.5
Sodium carbonate 12.2 14.4
EDDS2 0.4 0.5
Mg sulfate 0.4 0.5
Optical brightener 0.1 0.1
Moisture 7.6 8.9
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Silica3 0.4 0.5
Balance (unreacted and Na2S~4) 1.6 1.9
Agglomerate total 85.0 100.0
Drv Mix
Percarbonate, Na (400-600 microns~ 7.8
NoBS4 5.9
Silicone/PEG antifoam 0.3
Lipolase 0.3
Savinase 0.3
SPrav-on
Perfume 0.4
Finished product total 100.0
lCo-part~cle of citric acid and layered silicate (2.0 ratio)
2Ethylened~amine.disuccinate
3Hydrophobic precipitated silica (trade name SIPERNAT D-ll)
4Sod~um nonanoyloxybenzene sulfonate
EXAMPLE III
A concentrated, heavy duty, low-sudsing liquid laundry
detergent is as follows.
Inqredient % (wt.)
Secondary (2,3) alkyl sulfate, Na 17.0
C14 N-butyl glucamide 7.0
Sodium citrate 3.0
Calcium formate 1.5
Clo alcohol ethoxylate (E03) 6.0
Boric acid o.l
Silicone* 0.7
MAXATASE (enzyme) 0.5
LIPOLASE (enzyme) 0.5
Monoethanolamine to pH 8.5
Water/propylene glycol/ethanol (100:1:1) Balance
*Antifoam
EXAMPLE IV
A laundry bar suitable for hand-washing soiled fabrics is
prepared by standard extrusion processes and comprises the
following:
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Ingredient % (wt.)
C16 secondary (2,3) alkyl sulfate, Na 30
C12 13 alkyl benzene sulfonate 7
C1z 14 N-methylglucamide 5
Sodium tripolyphosphate 7
Sodium pyrophosphate 7
Sodium carbonate 25
Zeolite A (0.1-10~) 5
Coconut monoethanolamide 2
Carboxymethylcellulose 0.2
Polyacrylate (m.w. 1400) 0.2
Brightener, perfume 0.2
Protease 0-3
CaS04
MgS04
Water 4
F~ller* --- Balance ---
*Can be selected from convenient materials such as CaC03, talc,
clay, s~licates, and the like.
EXAMPLE V
Gel compositions are as follows.
To 0.8 grams of magnesium sulfate, 0.8 grams of Ca formate
and 6.7 grams of cocoamido propyl betaine (30% active, Albright-
Wilson, United Kingdom) dissolved in 25 grams of water, 8 grams of
C91-8T Dobanol (lOOX active, Shell, USA), 1.00 grams of boric acid
and 20 grams of urea (99X active, Fisher Scientific, USA) are
added and mixed at 71-74-C. Once a homogeneous mixture is
obtained, 8 grams of 97.6% active coconut N-methyl glucamide and
28 grams of sodium C16 secondary (2,3) alkyl sulfate are added and
agitation is continued. (Ingredients such as detersive enzymes
can be added when the temperature of the liquid reaches about
35-40-C.) The final liquid product forms a gel on cooling.
In an alternate mode, a gel is provided wlthout urea. To a
solution formed by dissolving 0.002 grams of blue dye in 42 grams
of water at 62-C, 0.25 grams of MgS04, 0.25 grams of CaClz, O.SO
grams of perfume and 35% of 50X coconutalkyl C1z-C14 N-methyl
glucamide paste are added with agitation. Once all the materials
are dissolved, 21 grams of an 80% sodium C1z 14 secondary (2,3)
-
WO 94124240 21 6 0 2 2 8 PCT/US94tO3698 ~
alkyl sulfate paste is added. The solution is stirred for an
additional 30 minutes at 77-C. At about 40-C, O.S grams of a
commercial detersive protease composition is added and stirring is
continued. Once stirring is stopped, the viscous liquid quickly
solidifies into a gel after cooling.
EXAMPLE VI
A granular detergent herein comprises the following.
Inqred~ent % (wt.)
Secondary (2,3) alkyl sulfate* 10.0
Zeolite A (1-10 micrometer) 26.0
C12 14 primary alkyl sulfate, Na salt 5.0
Sodium citrate 5.0
Sodium carbonate 20.0
Optical brightener - 0.1
Detersive enzyme** 1.0
Sodium sulfate 15.0
MgS04 1.0
CaS04 1.0
Water and minors Balance
*C14-C1g average chain length; Na salt.
**1:1 m~xture LIPOLASE/ESPERASE.
EXAMPLE YII
The compositions of Example I and II are modified by
including 0.5% of a commercial amylase preparation (TERMAMYLJ
thereln.
Fx4MPLE VIII
Addltional examples of particulate laundry detergents with
mixed surfactants especially suitable for use in front-loading
washing machines such as those commonly used in Europe are as
follows.
A B C
Surfactants % (wt.l % (wt.) % (wt.)
C16 secondary (2,3) alkyl sulfate, Na6.92 9.00 7.60
C16/18 primary alkyl sulfate 2.05 3.00 1.30
C12-C15 alkyl ethoxy (1-3) sulfate 0.17 0.40 0.10
C14-C1s alkyl ethoxylate (E07) 4.02 5.00 1.30
C16-C1g AE11 alkyl ethoxylate (E011) 1.10 1.40 1.10
C16-C1g AE25 alkyl ethoxylate (E025) 0.85 -- 0.66
~JO 94124240 21 fi 0 2 2 ~ PCTlUS94~03698
- 45 -
Dimethylmonoeth~XY C12-14
alkylammonium chloride -- -- 1.40
Builders
Citrate 5.20 10.005.00
Zeolite 4A 20.50 37.2017.90
Carbonate (Na) 15.00 5.5012.10
Amorphous silicate 2.0 3.00 2.003.10
SOKALAN cps1 4.00 4.903.20
Carboxymethylcellulose 0.31 0.390.20
Bleach
Perborate monohydrate 8.77 -- 5.80
Perborate tetrahydrate 11. 64 -- 7.40
C03/S04 coated percarbonate -- 12.0 --
TAED2 5.00 -- 3.40
Zinc phthalocyanine 20 ppm -- 20 ppm
DEQUEST 2060 (Monsanto) 0.36 0.600.38
MgS04 0.40 0.400.40
LIPOLASE (100,000LU/g) 0.36 0.250.15
Savinase (4.0 KNPU) 1.40 1.601.40
Cellulase (1000CEVU/g) 0.13 0.130.26
Soil release polymer3 0.20 0.200.15
Anionic optical brightener 0.19 -- 0.15
Polyvinyl pyrrolidone -- 0.15 --
Bentonite clay -- -- 12.50
Polyethyleneglycol4 -- -- 0.30
61ycerol -- -- 0.62
Perfume 0.43 0.430.43
Silicone + dispersant (antifoam)0.49 0.600.49
Moisture, minors ---- Balance ----
1Copolymer acrylic/maleic acid; mol. wt. range 70,000; Na salt.
2Tetraacetylethylenediamine.
3Anionic polyester reaction product of sulfobenzoic acid,
terephthalic acid, propane-1,2-diol, ethylene glycol,
sulfoisophthalic acid per Maldonado, ibid.
4M.W. 4,000,000 range.
While the foregoing examples illustrate the practice of this
invention, they are not irtended to be limiting thereof. Weight
ratios of Ca or Mg cations:secondary (2,3) alkyl sulfates are
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preferably near about stoichiometric, and are conveniently in the
range of about 1:16 to about 1:30, but higher and lower ratios may
be used. ~t will be appreciated that higher ratios may negatively
impact the formulatability of liquids and gels, but may be
acceptable in some instances. Lower ratios, in the range of
1:300, still provide benefits in overall product formulations.
While the foregoing examples illustrate the practice of this
invention using the secondary (2,3) alkyl sulfate surfactants and
other, mainly anionic, adjunct surfactants, such compositions can
also optionally contain various adjunct cationic surfactants and
mixtures of cationic and nonionic adjunct surfactants. Useful
cationics include the C1o-C1g alkyl trimethylammonium halides, the
C10-cl8 alkyl dimethyl (C1-C6) hydroxyalkylammonium halides,
C10-cl8 choline esters, and the like. If used, such cationic
surfactants can typically comprise from 1% to 15% by weight of the
compositions herein.
