Note: Descriptions are shown in the official language in which they were submitted.
WO 94/24239 21 6 0 2 2 7 PCT/US94tO3697
CALCIUM-CONTAINING DETERGENT COMPOSITIONS IN STABLE LIQUID,
GEL OR OTHER FORMS WlTH SECONDARY (2,3) ALKYL SULFATE SURFACTANTS
FIELD OF THE INVENTION
The present invention relates to cleaning compositions and
methods which employ secondary (2,3) alkyl sulfate surfactants and
a source of calcium ions to enhance the removal of greasy, oily
stains and soils from substrates.
lo BACKGROUND OF THE INYENTION
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
S for removing particulate soils, and various nonionic surfactants,
such as the alkyl ethoxylates and alkylphenol ethoxylates, are
useful for removing greasy soils.
~hile a review of the literature would seem to suggest that a
wide selection of anionic surfactants is available to the
detergent manufacturer, the reality is that many such materials
are specialty 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.
~t has now been discovered that a particular sub-set of the
35 class of secondary alkyl sulfates, referred to herein as secondary
(2,3) alkyl sulfates (~SAS~), offers considerable advant ?es to
the formulator and user of detergent compositions. For example,
the secondary alkyl (2,3) sulfates are more soluble in aqueous
media than their counterpart primary alkyl sulfates of comparable
W O 94/24239 21 6 0 2 2 7 PCTAUS94/03697
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chain lengths. Accordingly, 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. They are milder to skin in, for
example, hand dishwashing operations. Moreover, the secondary
(2,3) alkyl sulfates as used herein appear to exhibit good
compatibility with detersive enzymes. Thus, in addition to
compatibility with enzymes, the secondary (2,3) alkyl sulfates are
exceptionally easy to formulate as heavy-duty liquid laundry
detergents.
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, it has been discovered that the presence of calcium
ions in a properly formulated detergent composition can assist in
the removal of greasy/oily stains and soils. This is particularly
true for hand dishwashing compositions. However, calcium can
cause instability problems when used with detersive surfactants,
which tend to precipitate or phase separate in liquid compositions
in the presence of calcium ions. This is problematic under
circumstances where liquid compositions are being formulated, and
is intolerable where homogeneous clear and/or colorless liquids or
gels are desired.
By the present invention it has been determined that the
secondary (2,3) alkyl sulfates tend to negatively interact less
with calcium ions than do the conventional primary alkyl sulfates.
The overall result is that more stable compositions, especially
liquids and gels, with higher overall grease/oil cleaning
performance can now be secured.
BACKGROUND ART
The problems associated with the formulation of stable liquid
detergent compositions and means to enhance stability are
WO 94/24239 21 6 0 2 2 7 PCT/US94/03697
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described in various patents. See, for example: U.S. 3,998,750,
Payne, as well as U.S. 4,435,317, Gerritsen, and U.S. 4,671,894,
Lamb.
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, De~itt et al, November 25,
1969; U.S. 3,681,424, Bloch et al, August 1, 1972; U.S. 4,052,342,
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, ~ilms 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
H2S04, an olefin reactant and a low boiling, nonionic, organic
crystallization medium.
SUMMARY OF TH~ INVENTIOH
The present invention relates to the use of a secondary (2,3)
alkyl sulfate surfactant in a stable, homogeneous liquid or gel
detergent compositions, or in bar or granular compositions,
containing a source of calcium ions which enhances cleaning
performance, especially against greasy and oily soils and stains.
The invention herein provides preferably liquid and gel, but
also granular and bar, detergent compositions, comprising:
(a) at least about lX, preferably at least about 2%,
typically from about 3% to about 30% by weight of a
secondary (2,3) alkyl sulfate surfactant;
(b) at least about 0.05% by weight of calcium ions;
(c) optionally, a detersive-active amount of a detersive
adjunct material, or mixtures thereof;
(d) optionally, at least about 0.1% by weight of magnesium
ions; and
(e) optionally, a fluid carrier.
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Weight ratios of calcium cations:anionic surfactant herein
are typically near about stoichiometric, and are conveniently in
the range from about 1:16 to about 1:30. Higher ratios are
useful, but may negatively impact the formulatability of liquid
and gel products. Lower ratios, say, in the range of 1:300, still
provide benefits in overall product performance.
In one embodiment that is particularly useful for dishwashing
and fabric laundering, the compositions contain one or more
detersive adjunct materials (c) which are detersive surfactants
comprising a member selected from the group consisting of amine
oxide surfactants, polyhydroxy fatty acid amide surfactants,
sulfated polyhydroxy fatty acid amide surfactants, betaine
surfactants, sultaine surfactants, alkyl ethoxy carboxylate
surfactants, alkyl ethoxy sulfate surfactants, alkyl ethoxylate
surfactants, alkyl polyglycoside surfactants, and mixtures
thereof.
In another embodiment, the invention comprises compositions
wherein said detersive adjunct material (c) is a polycarboxylate
builder, especially a citrate or oxydisuccinate builder. Such
compositions are especially useful as laundry detergents.
Low-sudsing compositions which additionally comprise a
suds-control agent are also provided herein. High-sudsing compo-
sitions which are substantially free of primary C14 and higher
fatty acids are also provided. In yet another embodiment, clear
liquid or gel compositions and/or colorless compositions are
provided. The C1 -C20 secondary (2,3) alkyl sulfates can conveni-
ently be employed herein. The C14-C1g compounds are preferred for
laundry cleaning operations. The C12-C16 compounds are preferred
for dishwashing compositions.
The invention herein also encompasses a method for cleaning
soiled surfaces, especially dishes but including 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 the compositions of this
invention, under conditions of agitation. Such cleaning can be
carried out in an automatic cleaning apparatus, or by hand, both
with and without a presoak.
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All percentages, ratios and proportions herein are by weight,
unless otherwise specified. 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
R0503-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 ~PASn) 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(CH0503-M+) (CH2)mCH3
wherein m and n are integers of 2 or greater and the sum of m + n
is typically about 9 to 15, 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(CHOS03~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
to prepare the water-soluble (2,3) alkyl sulfates, but ethanolam-
monium, diethanolammonium, triethanolammonium, potassium,
ammonium, and the like, can also be used.
wO 94/24239 21 6 0 2 2 7 pcTrus94lo3697
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By the present invention it has been determined that the
physical/chemical properties of the foregoing types of alkyl
sulfate surfactants are unexpectedly different, one from another,
in several aspects which are important to 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 (2,3) 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 so-called
~under-built" situations which can occur with nonphosphate
builders.
Importantly, when formulating concentrated liquid detergents
with calcium or magnesium ions to enhance grease cutting or
sudsing performance 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 liquid and gel
detergents has now been found to be simpler and more effective
with the secondary (2,3) alkyl sulfates than with the primary
alkyl sulfates.
With 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 pastes, and thus do not afford the
processing advantages associated with the secondary (2,3) alkyl
sulfates when formulating detergent bars, granules or tablets.
Moreover, sudsing of the random alkyl sulfates is also less than
with the secondary (2,3) alkyl sulfates herein. This is an
important consideration for hand dishwashing, where users expect
high, persistent sudsing. It is preferred that the secondary
(2,3) alkyl sulfates be substantially free (i.e., contain less
than about 20X, more preferably less than about 10%, most
preferably less than about 5%) of such random secondary alkyl
sulfates.
WO 94/24239 - 216 0 2 ~ 7 I'CT/US94/03697
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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 photometrically 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 selection of secondary (2,3)
alkyl sulfate surfactants according to the practice of this
invention which preferably are substantially free of other
positional secondary isomers unexpectedly assist 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
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
WO 94124239 21 6 0 2 2 7 PCT/US94/03697
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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
S 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 (some sodium sulfate may be
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 n crystalline n 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-C18 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.
~hen formulating liquid and gel compositions, especially
clear liquids, it is preferred that the secondary (2,3) alkyl
sulfate surfactants contain less than about 3% 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 phase separation in 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
H2SO4 addition to the olefin is completed, care can be taken to
remove unreacted H2SO4 before the acid form of the secondary (2,3)
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WO 94124239 PCTIUS94/03697
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g
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 (2,3J alkyl sul-
fate. 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
10 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
15 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.
20 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
25 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 with sodium sulfate with water at a temperature
30 that is no higher than the Krafft temperature, and which is
preferably lower than the Krafft temperature, for the particular
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
35 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
WO 94/24239 216 0 2 2 7 PCT/US94/03697
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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
S 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 ZO-C. It will be appreciated that changes in the
cation 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 10-50% solids, typically for a mixing time of at least 10
minutes at about 22-C (for a C16 secondary [2,3] 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.
Calcium lon Source - The present compositions will contain at
least about 0.05% by weight of a water-soluble source of calcium
ions, further details of which, along with a nonlimiting listing
of suitable and convenient calcium ion sources, are listed herein-
after under ~Enzyme Stabilizers~.
Detersive Adiunct Materials
EnzYmes - Detersive enzymes can optionally be included in the
detergent formulations herein for a wide variety of fabric laun-
dering purposes, including removal of protein-based, carbohydrate-
based, or triglyceride-based stains, for example, for the
prevention of refugee dye transfer, and for fabric restoration.
The enzymes to be incorporated include proteases, amylases,
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WO 94t24239 - PCT/US94/03697
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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, thermostabil-
ity, 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 S 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 0.001% to about 5%, preferably 0.1%-1%, by weight of a
commercial enzyme preparation. Protease enzymes are usually
present in such commercial preparations at levels sufficient to
provide from O.OOS 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
British Patent Specification No. 1,296,839 (Novo), RAPIDASE,
International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.
The cellulases usable in the present invention include both
- bacterial or fungal cellulase. Preferably, they will have a pH
WO 94124239 216 0 2 2 7 PCT/US94103697
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
S 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 enzymçs 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, n hereinafter
referred to as ~Amano-P.~ Other commercial lipases include
Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter
viscosum var. 7ipo1yticum NRRLB 3673, commercially available from
Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum
lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The
Netherlands, and lipases ex Pseudomonas g7adio7i. The LIPOLASE
enzyme derived from ~umicola 1anuginosa 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 ~0 89/099813, published October 19, 1989, by 0. Kirk,
assigned to Novo Industries A/S.
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 S, 1971 to McCarty et al ().
21602~7
WO 94/24239 - PCT/US94/03697
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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, Venegas. Enzyme stabilization systems are also
described, for example, in U.S. Patents 4,261,868, 3,600,319, and
3,519,570.
Enzvme Stabilizers - The enzymes optionally employed herein
are stabilized by the presence of water-soluble sources of calcium
ions in the finished compositions which provide calcium ions to
the enzymes. 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 ions. The level of
calcium ion 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 salt can be used as the source of
calcium ion, including, but not limited to, calcium chloride,
calcium sulfate, calcium malate, calcium hydroxide, calcium
formate, and calcium acetate. 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
2160227
WO 94124239 PcTruss4to3697
- 14 -
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
ions are sufficient to provide enzyme stability. In the present
invention, sufficient calcium ions are added to the compositions
to provide the desired additional measure of grease removal
performance provided by this invention. Accordingly, the
compositions herein will typically comprise from about 0.05X to
about 2% by weight of a water-soluble source of calcium ions,
which is more than sufficient to stabilize any enzymes which may
optionally be present and which provides additional cleaning.
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 5%, 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 acid). Boric acid is preferred, although other compounds
such as boric oxide, borax and other alkali metal borates (e.g.,
sodium ortho-, meta- and pyroborate, and sodium pentaborate) are
suitable. Substituted boric acids (e.g., phenylboronic acid,
butane boronic acid, and p-bromo phenylboronic acid) can also be
used in place of boric acid.
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,
colorants, dyes, etc.). The following are illustrative examples
of such other adjunct materials.
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
removal of particulate soils.
The level of builder can vary widely depending upon the end
use of the composition and its desired physical form. For "light
21 6022 7
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duty" liquids such as those used for dishwashing, typically no
builder is present. When present, the compositions will typically
comprise at least about 1% builder. Liquid formulations typically
comprise from about 5X to about 50%, more typically about 5% to
about 30%, by weight, of detergent builder. Lower or higher
levels of builder, however, are not meant to be excluded. Gel
compositions can tolerate only low levels of water-soluble
builders, generally no more than about 5%-10%. Granular and bar
compositions can contain from 10X-60X by weight of builder.
If a solid or bar product is desired, the insoluble zeolite
builders and/or silicate builders can be employed therein. Useful
aluminosilicate ion exchange materials are commercially available.
These aluminosilicates can be crystalline or amorphous in
structure and can be naturally-occurring aluminosilicates or
synthetically derived. A method for producing aluminosilicate ion
exchange materials is disclosed in U.S. Patent 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 (B), and Zeolite X.
In an especially preferred embodiment, the crystalline
aluminosilicate ion exchange material has the formula:
Nal2~(A102)l2(siO2)l2] XH20
wherein x is from about 20 to about 30, especially about 27. This
material is known as Zeolite A. Preferably, the aluminosilicate
has a particle size of about 0.1-10 microns in diameter.
Useful layered silicate builders are disclosed in U.S.
4,664,839. 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
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 NaMSix02x+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
WO 94124239 216 ~ 2 2 7 PCT/US94/03697
NaSKS-11, as the alpha, beta and gamma forms. As noted above, the
delta-Na2SiOs (NaSKS-6 form) is most preferred for use herein.
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,
~polycarboxylate~ 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. ~hen 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
polycarboxylate 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 S, 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.
Other 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
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 laundry detergent
formulations due to their availability from renewable resources
and their biodegradability. Citrates can also be used in granular
compositions, especially in combination with zeolite and/or
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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-Clg 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 compositions 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
ethane-l-hydroxy-l,l-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 ComDounds - Bleachinq Aqents 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. ~hen present, bleaching
agents will typically be at levels of from about lX to about 307.,
more typically from about 5% to about 20%, of the detergent
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composition, especially for fabric laundering. If present, the
amount of bleach activators will typically be from about 0.1% to
about 60X, more typically from about 0.5% 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.
Persulfate bleach (e.g., OXONE, manufactured commercially by
- 30 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
WO 94/24239 216 0 2 2 7 PCT/US94/03697
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19
sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activa-
tors 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 0.025X to about 1.25%, by weight, of
sulfonated zinc phthalocyanine.
Polvmeric Soil Release Aqent - Any polymeric soil release
agent known to those skilled in the art can optionally be employed
in the laundry compositions and laundry cleaning 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
nonionic 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
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 1 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,
WO 94/24239 216 0 2 2 7 PCT/VS94103697
- 20 -
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 50%
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.
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.
WO 94/24239 ; 216 0 2 2 7 PCT/US94/03697
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- 21 -
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 (PE0) 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
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.
WO 94124239 21 6 0 2 2 7 PCTrUS94/03697
- 22 -
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 0.1% to about 5%, preferably
from about 0.2% to about 3.0%.
ClaY Soil Removal/Anti-redew sition Aqents - The laundry
compositions of the present invention can also optionally contain
water-soluble ethoxylated amines having clay soil removal and
anti-redeposition properties. 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 5%.
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 Gosselink,
published June 27, 1984. Other clay soil removal/antiredeposition
agents 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
antiredeposition agents known in the art can also be utilized in
the compositions herein. Another type of preferred anti-
redeposition agent includes the carboxy methyl cellulose (CMC)
materials. These materials are well known in the art.
Chelatinq Aqents - Laundry compositions, especially with
bleaches, may also contain various chelants, typically at levels
of 0.1%-3% by weight. Chelants such as the amino phosphonates
(DEQUEST) can be used. A preferred biodegradable chelant is
ethylenediamine disuccinate (EDDS); see U.S. Patent 4,704,233,
WO 94/24239 216 0 2 2 7 PCT/US94/03697
- 23 -
November 3, 1987, to Hartman and Perkins. Other such chelants are
well-known in the trade and patent literature.
Pol~meric DisDersinq Aqents - Polymeric dispersing agents can
advantageously be utilized at levels from about 0.1% to about 7%,
by weight, in the laundry compositions herein, especially in the
presence of zeolite and/or layered silicate builders. Suitable
polymeric dispersing agents include polymeric polycarboxylates and
polyethylene 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.
lS 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 40X 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. ~ater-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.
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Acrylic/maleic-based copolymers may also be used as a
preferred 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
preferably 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.
~ater-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 Application 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 1.2%, by weight, into the
laundry detergent compositions herein. Commercial optical bright-
eners which may be useful in the present invention can be classi-
fied into subgroups which include, but are not necessarily limited
to, derivatives 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 Agents n ~ M. Zahradnik.
Published by John Wiley ~ 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.
w O 94/24239 21 6 ~ 2 2 7 PcTrus94lo3697
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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- naphthol[1,2-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- [1,2-d]triazole. See also U.S.
Patent 3,646,015, issued February 29, 1972 to Hamilton.
Suds SuDPressors - 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
importance under conditions such as those found in European-style
front loading laundry washing machines, or in the concentrated
detergency 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- & 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 C1g-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
WO 94/24239 216 0 2 2 7 PCTrUS94/03697
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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 S-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 lOO C. The hydrocarbons constitute a preferred
category of suds suppressor for detergent compositions. Hydrocar-
bon suds suppressors are described, for example, in U.S. Patent
4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocar-
bons, thus, include aliphatic, alicyclic, aromatic, and hetero-
cyclic 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 5, 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 94/24239 216 0 2 2 7 PCTrUS94/03697
- 27 -
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 SiOl/2 units
of SiO2 units in a ratio of from (CH3)3 SiOl/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 %; 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.
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The silicone 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 X, 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
with 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 1Z3 from
Enichem. Mixed suds suppressors typically comprise mixtures of
alcohol + silicone at a weight ratio of 1:5 to 5:1.
For 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.
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The compositions herein will generally comprise from 0% to
about 5% of suds suppressor. ~hen utilized as suds suppressors,
monocarboxylic fatty acids, and salts therein, will be present
typically in amounts up to about 5%, by weight, of the detergent
composition. Preferably, from about 0.5% to about 3% of fatty
monocarboxylate suds suppressor is utilized. Silicone suds
suppressors are typically utilized in amounts up to about 2.0%, 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 0.25% to about 0.5%. As used herein, these
weight percentage values include any silica that may be utilized
in combination with 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 2%, 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 surfactant
compositions herein can also be used with a variety of other
adjunct ingredients 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.
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Ad.iunct Surfactants - The compositions herein can optionally
contain various anionic, nonionic, zwitterionic, etc. surfactants.
If used, such adjunct surfactants are typically present at levels
of from about 1% 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. However, such adjunct surfactants, e.g., the
betaines, sultaines and amine oxides, may be especially useful
when high sudsing is desired, i.e., especially in hand dishwashing
operations.
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 C10-cl8 alkyl alkoxy
sulfates (especially EO 1-5 ethoxy sulfates), the 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
(~sultaines~), 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:
O Rl
(I) R2 - C - N - Z
wherein: R1 is H, C1-Cg hydrocarbyl, Z-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-Clg 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
2160227
WO 94/24239 PCT/US94/03697
- 31 -
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)
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 l-
CH20H, -CH2-(CHOH)2(CHOR')(CHOH)-CH20H, 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), Rl 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, Rl is preferably
C2-Cg alkyl, especially n-propyl, iso-propyl, n-butyl, iso-butyl,
pentyl, hexyl and 2-ethyl hexyl.
R2-C0-N< can be, for example, cocamide, stearamide, oleamide,
lauramide, myristamide, capricamide, palmitamide, tallowamide,
etc.
~hile 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
~0-9,206,154 and ~0-9,206,984 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 l.C%) of
sub-optimally degradable cyclized by-products and also with
2160~27
WO 94/24239 PCT/US94/03697
improved color and improved color stability, e.g., Gardner Colors
below about 4, preferably between 0 and 2. (~ith compounds such
as butyl, iso-butyl and n-hexyl, the methanol introduced via the
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 materials are not cyclized by-products, as
defined herein.
The foregoing polyhydroxy fatty acid amides can also be
sulfated, e.g., by reaction with S03/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 provide mixed SAS/PFAS/AF/AS
particles. ~hile 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. ~hatever 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
WO 94/24239 21 6 0 2 2 7 PCT/US94/03697
-
- 33 -
aqueous washing liquor can be problematic. Of course, the
improved solubility achieved herein is also of substantial benefit
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 C10-cl6 alkanolamides can be incorporated
into the compositions, typically at lX-lOX 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, 0.1X-2X, to provide additional sudsing.
Various detersive ingredients employed in the present compo-
sitions optionally can be further stabilized by absorbing said
ingredients 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 3X-5X of C13 15 ethoxylated
alcohol EO(7) nonionic surfactant. Typically, the enzyme/surfact-
- 30 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.
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Liquid detergent compositions can contain water and other
solvents as carriers. Low molecular weight primary or secondary
alcohols exemplified by methanol, ethanol, propanol, and
isopropanol are suitable. Monohydric alcohols are preferred for
solubilizing 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 50% of such carriers.
The detergent compositions herein will preferably be
formulated such that during use in aqueous laundering 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 product
formulations preferably have a pH between about 7.5 and about 9.5,
more preferably between about 7.5 and about 9Ø 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
illustrate the detergent compositions and uses of the secondary
(2,3) alkyl sulfates according to this invention. For most
purposes, the preferred compositions are free of phosphate
builders.
The liquid dishwashing detergents of Examples I-II are
prepared by dissolving or dispersing the indicated ingredients in
an aqueous carrier and adjusting the pH in the range of 6-8.
EXAMPLE I
A dishwashing composition with high grease removal properties
is as follows.
Inqredient % (wt.
C12 N-methyl glucamide 9.0
C12 ethoxy (1) sulfate 5.0
C14 secondary (2,3) alkyl sulfate (Na)* 6.5
C12 ethoxy (2) carboxylate 4.5
C12 alcohol ethoxylate (4) 3.0
C12 amine oxide 3.0
Sodium cumene sulfonate 2.0
Ethanol 4 0
WO 94/24239 216 0 2 2 7 PCT/US94/03697
-
- 35 -
Mg++ (as M9Cl2) 0.2
Ca++ (as CaCl2) 0 4
~ater Balance
*Purified to contain less than 1% Na2S04.
EXAMPLE II (A and B)
A B
Inqredient % (wt.) X (wt.)
C14 secondary (2,3) alkyl sulfate* 12 8
C12 13 alkyl ether (3 avg.) sulfate 16 12
C12 13 alkyl dimethyl amine oxide 2 2
C12 13 monoethanolamide 3 --
C12 N-methylglucamide -- 8
C11 EO(9)** 5
Ca++ (as CaCl2) 0.6 0.1
Mg++ (as MgCl2) -- 0.4
Sodium cumene sulfonate 2 --
Sodium xylene sulfonate -- 2
~ater, perfume, dye, minors, enzyme*** --- Balance ---
*C12-14 or C16 alkyl may be used; as Na salt
**As NEODOL 1E9
***Optional
Compositions of the foregoing type exhibit good grease
removal performance on dishware, with high sudsing, but with good
mildness to the user's hands.
The user of modern detergent compositions has appreciated the
advantages of having such compositions available in a wide variety
of forms, not only for convenience, but also for performance and
aesthetic reasons. Accordingly, formulators of such compositions
have made substantial efforts to provide detergent compositions as
bars, flakes, spray-dried granules, and liquids. Most recently, a
substantial proportion of consumers have begun using detergents
which are available in gel form. In some Latin American
countries, such as Venezuela, gel detergents are available in tub
containers, and are especially popular and preferred for home
dishwashing operations. following local habits and practices, the
gel is applied directly to a sponge or other wiping implement, and
applied with water to the eating or cooking utensil being
WO 94/24239 21 6 0 2 2 7 PCT/US94/03697
- 36 -
cleansed. Accordingly, formulators have turned increasing atten-
tion to the problems associated with the formulation of high
quality, stable and economical gel detergent compositions.
The formulation of gels is a complex phenomenon involving the
association of solute molecules in an aqueous medium. ~hile a
precise definition of the gel state is difficult, most aqueous
gels can be considered as having most of the properties of a solid
or semi-solid, while still containing as high as 99% water. Gels
of the type used in gel detergents provided herein are typically
in the form of gelatinized or gelled compositions which can have
viscosities as high as 5,000,000 centipoise, and typically range
from about 500,000 to about 4,000,000 centipoise.
A wide variety of means have been used to form gels, and
standard formularies reveal that various commercial gums are used
for this purpose in various consumer products. See, for example,
M. G. deNavarre ~The Chemistry and Manufacture of Cosmetics~ Vol.
III 2nd ed. 1975 Continental Press, Orlando, Florida USA.
Materials such as urea and urea derivatives can also be used to
form gels.
In a mode which is designed to enhance the grease removal
performance of the instant compositions, calcium ions, or, more
preferably, a mixture of calcium and magnesium ions, are incorpor-
ated into the gel. Levels of calcium or mixed calcium/magnesium
ions up to about 2X, typically from about 0.4% to about 1.5%,
provide superior grease removal in a hand dishwashing operation.
Ratios of Ca:Mg of from about 5:1 to about 1:5, are preferably
used. In one mode, the gel is prepared using a calcium salt and
the magnesium form of an adjunct surfactant such as an alkyl
ethoxy sulfate surfactant. Alternatively, water-soluble calcium
and magnesium salts such as the halides, sulfates, hydroxides, and
the like, can be used.
The incorporation of calcium and magnesium cations in the
gels of this invention enhances cleaning performance, especially
with regard to greasy soils of the type typically encountered in
dishwashing operations. Unfortunately, the presence of ionic
ingredients does tend to decrease gel viscosity. For lower
viscosity gels herein (500,000-1,500,000 cps) the addition of
common magnesium salts such as magnesium chloride, magnesium
WO 94/24239 21 6 0 2 2 7 PCT/l~S94/03697
-
- 37 -
sulfate, magnesium formate, magnesium citrate, and the like can
also be used to selectively control final product viscosity. For
gels of higher viscosity (above about 2,000,000 cps) such
- magnesium salts disrupt the desired physical properties and such
common magnesium salts are preferably not used above about 0.3%
levels. In order to overcome this problem and to allow the
formulator to incorporate magnesium cations at levels of about
0.5X and greater, generally up to about 2%, typically 0.5%-1.5X,
in the finished gels, it is preferred to add at least some of the
magnesium in the form of the magnesium salt of the anionic
surfactant. Stated otherwise, all of the magnesium cations can be
added as the magnesium form of the surfactant, or part can come
from the magnesium surfactant and part from other magnesium salts,
as noted above. The magnesium form of the alkyl alkoxy sulfate
surfactant can be generated in situ by combining Mg(OH)2 with the
acid form of the surfactant during the mixing step herein. In an
alternate mode, the use of other surfactants such as the C16
dimethyl amine oxides and/or C12 14 betaine surfactants will
assist in the performance of magnesium-containing gels.
EXAMPLE III
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-
~ilson, 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 (99% active, Fisher Scientific, USA) are
added and mixed at 71-74-C. Once a homogeneous mixture is
obtained, 8 grams of 97.6X active coconut N-methyl glucamide and
28 grams of sodium C16 secondary (2,3) alkyl sulfate are added and
agitation is continued. (lngredients 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 without 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 CaCl2, O.SO
grams of perfume and 35% of 50% coconutalkyl C12-C14 N-methyl
glucamide paste are added with agitation. Once all the materials
are dissolved, 21 grams of an 80% sodium C12 14 secondary (2,3)
W O 94/24239 2 ~ 6 0 ~ 2 7 PCTrUS94/03697
- 38 -
alkyl sulfate paste is added. The solution is stirred for an
additional 30 minutes at 77-C. At about 40-C, 0.5 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.
~hile the preferred compositions herein are in the form of
stable, homogeneous liquids and gels, other forms such as bars,
granules and the like are also provided.
EXAMPLE IV
A laundry bar suitable for hand-washing soiled fabrics is
prepared by standard extrusion processes and comprises the
following:
Ingredient % (wt.)
C16 secondary (2,3) alkyl sulfate, Na 30
C12 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) O. 2
Brightener, perfume 0. 2
Protease 0. 3
Ca S04
Mg SO4
~ater 4
Filler* --- Balance ---
*Can be selected from convenient materials such as CaC03, talc,
clay, silicates, and the like.
In general terms, particulate detergent compositions compris-
ing 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
secondary (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
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- 39 -
turbilizers, available from manufacturers such as Lodige, Eric,
Bepex and Aeromatic.
In 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
divided 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
(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-
ture 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 [2,3] alkyl sulfate particles) are forced
together 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
allowing 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. ~ater, alone, is an
operative binder with secondary (2,3) alkyl sulfates, since it
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.
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- 40 -
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 high 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.
~ith 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 (NIR0, Bepex or Carrier
Companies); and
(D) coating the agglomerates using a mixer such as an Eirich
Mixer, R-Series.
The following describes the Agglomeration Step in more
detail.
SteP A - PreDaration 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
WO 94/24239 216 0 2 2 7 PCTIUS94/03697
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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 B - 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), sodium
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
particle range from about 300 to about 600 microns, as measured by
sieve analysis). In this Step, the wet agglomerates are charged
into a fluidized bed at an air stream temperature of from about
41-C to about 60-C and dried to a final moisture content of the
particles from about 4% to about 10%.
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
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acceptable flowability. In this Step, the dried agglomerates from
Step t are charged into the Eirich Mixer (R-Series) and mixed at a
rate of about 1500 rpm to about 3000 rpm while adding 2-6% 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 0.1% to
about 1.5% 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.
EXAMPEE V
Aqqlomerate
X (wt.) in X (wt.) in
final Product 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 (4000) 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 o 5
Mg sulfate 0.2 0.2
Ca sulfate O. 2 0.3
Optical brightener 0.1 0.1
Moisture 7. 6 8.9
Silica3 0.4 0.5
Balance (unreacted and Na2SO4) 1.6 1.9
Agglomerate total 85.0 100.0
DrY Mix
Percarbonate, Na (400-600 microns) 7.8
NoBS4 5.9
Silicone/PEG antifoam 0.3
Lipolase 0.3
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Savinase 0.3
SDrav-on
Perfume 0.4
Finished product total100.0
1Co-particle of citric acid and layered silicate (2.0 ratio)
- 2Ethylenediamine disuccinate
3Hydrophobic precipitated silica (trade name SIPERNAT D-11)
4Sodium nonanoyloxybenzene sulfonate
The following are additional, nonlimiting examples of liquid
compositions according to this invention.
EXAMPLE VI
Inqredient % (wt.)
C12 N-methyl glucamide 9.0
C12 ethoxy (lJ sulfate 6.0
DAN 214 SAS (Shell) 6.0
2-methyl undecanoic acid 4.5
C12 ethoxy (3) carboxylate4.5
C11 alcohol ethoxylate (9)4.0
C12 14 amine oxide 2.0
Sodium cumene sulfonate 2.0
Ethanol 4.0
Mg++ (as MgCl2) 0.1
Ca++ (as Ca formate) 0.4
KCL 0.5
~ater Balance
EXAMPLE YII
The C12 ethoxy(1)sulfate in Example VI is replaced by an
equivalent amount of DAN 216 SAS (Shell).
~hile 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.
