Note: Descriptions are shown in the official language in which they were submitted.
WO 94/24238 216 01~ 8 PCT/US94/03728
. _
DEll~RGENT COMPOSITIONS
FIELD OF THE IHVEN~ION
Layered silicate builders are used in combination with
secondary (2,3) alkyl sulfate surfactants in laundry detergent
compositions. The compositions minimize the deposition of inor-
ganic matter onto fabrics, which helps to maintain the soft ~hand~
0 of fabrics laundered therewith.
BACKGROUHD OF THE INVEN~IOH
Detergent formulators are faced ~ith a variety of diffi-
culties when preparing laundry detergent composltions. In
general, such compositions must be safe with respect to the user
and with respect to the fabrics being laundered. On the other
hand, such compositions must be sufficiently robust that they will
remove a wide variety of tenacious soils and st-ins from fabrics
under usage conditions which range from cold water washing tem-
peratures up to boil washes.
Phosphate builders were once highly important to detergent
formulators, since they safely and economically enhance the
cleaning performance of synthetic detersive surfactants. However,
phosphate builders are not now in use in many regions of the
world, and detergent formulators have turned to nonphosphorus
2s builder materials, including various polycarboxylate builders.
However, polycarboxylate builders are not as effective as phos-
phates and must often be used in combination with other ingredi-
ents to enhance detergency performance.
Since the mid-1970's, zeolites have become the builders of
choice, especially for the formulation of heavy-duty granular
laundry detergents. Unfortunately, minuscule amounts of the
zeolites can deposit onto fabric surfaces each time fabrics are
laundered with zeolite-built detergents. As the fabrics undergo
multiple washes, the zeolite build-up (also sometimes referred to
as ~ash~ or ~inorganics~) can reach sufficient levels that the
original soft feel, or ~hand~, of the fabrics is substantially
diminished.
By the present invention it has been determined that the
proper selection of surfactants, i.e., the secondary (2,3) alky~
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WO 94/24238 ` `~ ` - PCT/US94/03728 - 2 -
sulfates (~SAS~), used in combination with layered silicate
builders, provides detergent compositions which minimize much of
the aforesaid undesirable build-up of inorganic deposits onto
fabrics. The secondary (2,3) alkyl sulfates are mild to skin.
Moreover, the secondary alkyl (2,3) sulfates are more soluble in
aqueous media than their counterpart primary alkyl sulfates of
comparible chain lengths. Accordingly, they can be formulated as
readily-soluble, high-surfactant (i.e., ~high-active~) concen-
trated granular laundry detergents. Since the secondary (2,3)
alkyl sulfates can be made available in solid, particulate form,
they can be dry-mixed into granular detergent compositions without
the need for passage through spray drying towers. In addition to
the foregoing advantages seen for the secondary (2,3) alkyl
sulfates when used in the manner disclosed herein, it has now been
determined that they are both aerobically and anaerobically
degradable, which assists in their disposal in the environment.
Preferred detergent compositions which comprise biodegradable or
otherwise ecologically acceptable ingredients can thus be
provided.
BACKGROUND ART
Layered silicates for use in detergents and water softeners
are described in Japanese laid-open patent applications, Applica-
tion Numbers 63-334933, 63-334934, 62-313599 and 60-74595, and in
U.S. 4,664,849, ~ans-Peter Rieck, granted May 12, 1987. 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, 1959i U.S. 3,468,805, Grifo et al, September Z3,
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, Hovember 25, 1980; U.S. 4,529,541,
~ilms et al, July 16, 1985i 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, 1959i 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 H2SO4, an olefin
WO 94124238 216 ~1~ 8 PCT/US94/03728
- 3 --
reactant and a low boiling, nonionic, organic crystallization
medium.
SUMMARY OF THE INVENTION
The present invention relates to detergent compositions
especially adapted to laundering fabrics with -minimized build-up
of inorganic residues, especially zeolite builder residues, on
said fibrics, characterized by:
i) a builder system which comprises a layered silicate
builder and optional adjunct builders; and
ii) a detersive surfactant system which comprises secondary
(2,3) alkyl sulfates and optional adjunct surfactants.
In the preferred compositions herein, the minimum amount of
layered silicate builder in the finished product is at least 4%,
by weight, and preferably ranges from about 10% to about 50% by
weight of the compositions.
Limited amounts of zeolites can optionally be used as adjunct
builders in the present compositions. For compositions which
contain 10% or more, by weight, of peroxygen bleaching compounds,
the amount of zeolite builder should be no more than 22%, prefer-
ably no more than 16%, by weight of said compositions. For
compositions which comprise less than 10% by weight of peroxygen
bleaching compounds, or no peroxygen bleaching compounds, the
amount of zeolite builder should be no more than 30%, preferably
no more than 22%, by weight of said compositions.
The compositions can also comprise polycarboxylate adjunct
builders, especially citrate, and thus include mixtures of such
carboxylate builders plus the layered silicate, optionally with
zeolites. If used, the polycarboxylate builders will typically
comprise from about 5% to about 20% by weight of the compositions.
Mixtures of layered silicate/citrate and layered silicate/cit-
rate/zeolite builders within the compositional ranges noted above
are preferred builders herein.
In addition to the secondary (2,3) alkyl sulfate surfactant~
the compositions can optionally comprise nonionic adjunct
surfactants as well as optional anionic adjunct surfactants such
as members selected from the group consisting of alkylbenzene
sulfonates, alkylether sulfates, alpha-sulfonated fatty acid
esters, branched-chain and linear primary alkyl sulfates, and
21~0108
WO 94/24238 PCT/US94/03728
- 4 -
mixtures thereof. However, the secondary (2,3) alkyl sulfate
should comprise no less than 50% by weight of the mixed anionic
surfactant systems used herein. Typical laundry detergent compo-
sitions will comprise from about 5X to about 50%, preferably 10%
to about 30X, by weight of the secondary (2,3) alkyl sulfate
surfactants.
The compositions herein can also optionally contain various
adjunct cationic surfactants, and mixtures of such cationic and
nonionic adjunct surfactants. Useful cationics include the
C10-C18 alkyl trimethylammonium halides, the C1o-C18 alkyl
dimethyl (C1-C6) hydroxyalkylammonium halides, C1o-C1g choline
esters, and the like. If used, such cationic surfactants can
comprise from 1% to 15% by weight of the compositions herein.
The compositions herein can additionally comprise a dispers-
ing agent, which further assists in the diminution of inorganic
residues on fabrics. Preferred compositions comprise said layered
silicate builder, said secondary (2,3) alkyl sulfate surfactant,
from OX to 22% by weight of zeolite adjunct builder and a dispers-
ing agent, especially polyaspartate, at levels of dispersing agent
preferably in the range from about 0.1% to about 7% by weight.
The compositions herein can additionally comprise one or more
auxiliary cleaning or fabric conditioning agents selected from the
group consisting of enzymes, soil release agents, bleach and
bleach activators, clay fabric softeners, optical brighteners, and
mixtures thereof. Such agents typically comprise from about 0.1%
to about 45X by weight of the compositions.
A highly preferred granular detergent composition herein
comprises nonphosphate ingredients, characterized in that at least
60% of the ingredients therein comprise a mixture of:
i) an anionic surfactant, typically 10%-30% by weight,
which is a secondary (2,3) alkyl sulfate;
ii) optionally, a nonionic surfactant which is a polyhydroxy
fatty acid amide, an alkyl polyglycoside, or mixtures
thereof, typically 5%-30% by weight;
iii) optionally, an anionic surfactant which is a member
selected from the group consisting of linear primary
alkyl sulfates, alkyl ether sulfates, or mixtures
thereof;
WO 94/24238 216 0 10 8 PCT/US94/03728
. _
- 5 -
iv) at least 4%, preferably from about 4% to about 35% by
weight, of a layered silicate builderi
v) optionally, a polycarboxylate builder;
vi) optionally, a zeolite builder which comprises no more
than 22% by weight, preferably no more than 16% by
weight, of the total composition;
vii-) optionally, but preferably, a polyaspartate dispersing
agent;
viii) percarbonate bleach;
ix) optionally, a nonphosphorus chelant selected from the
group consisting of ethylenediamine-N,N'-disuccinate,
ethylenediamine-N,N'-diglutarate and 2,hydroxypropylene-
diamine-N,N'-disuccinate; and
x) optionally, but preferably, one or more enzymes;
wherein the balance of the composition comprises conventional,
nonphosphorus detergent ingredients, nonphosphorus fillers and the
like. Preferably, such compositions comprise less than 15% alkyl
benzene sulfonate surfactants.
The invention also encompasses a method for cleaning fabrics
while minimizing zeolite builder residues on said fabrics,
characterized in that it comprises contacting said fabrics,
preferably with agitation, with an aqueous bath which contains at
least about 100 ppm (typically 100 ppm-5000 ppm) of a laundry
detergent which comprises a secondary (2,3) alkyl sulfate
surfactant, and a layered silicate builder, said detergent
composition containing no more than 22% by weight of zeolite
builder. The C1o-C20 secondary (2,3) alkyl sulfates can conveni-
ently be employed herein. ~he C14-C1g compounds are preferred for
laundry cleaning operations.
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
Primarv Inqredients
SecondarY (2.3) Alkvl 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.
216010g
WO 94/24238 PCT/US94/03728
- 6
Conventional primary alkyl sulfate surfactants have the
general formula
ROS03-M+
wherein R is typically a linear C1o-C20 hydrocarbyl group and M is
a water-solubilizing cation. Branched-chain primary alkyl sulfate
surfactants (i.e., branched-chain ~PAS~) having 10-20 carbon atoms
are also known; see, for example, European Patent Application
43~,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
C~13(CH2)n(CHOS03-M+J (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(cHoso3-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+l) are, respectively, integers of at least about 6, and can
range from about 7 to about 20, preferably about lO 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.
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
WO 94/24238 216 010 ~ PCT/US94/03728
`_ 7
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 the so-called
~under-built~ situation which can occur when nonphosphate builders
are employed.
Importantly, when formulating detergents with calcium or
magnesium ions to enhance grease cutting or sudsing performance
and to provide enzyme stability, it has now been found that the
primary alkyl sulfates can be problematic due to such interactions
with calcium or magnesium cations. Moreover, the solubility of
the primary alkyl sulfates is not as great as the secondary (2,3)
alkyl sulfates. Hence, the formulation of high-active surfactant
particles has now been found to be simpler and more effective with
the secondary (2,3) alkyl sulfates than with the primary alkyl
sulfates. Thus, in addition to compatibility with enzymes, the
secondary (2,3J alkyl sulfates are exceptionally easy to formulate
as heavy-duty laundry detergents.
~ith regard to the random secondary alkyl sulfates (i.e.,
secondary alkyl sulfates with the sulfate group at positions such
as the 4, 5, 6, 7, etc. secondary carbon atoms), such materials
tend to be tacky solids or, more generally, pastes. Thus, the
random alkyl sulfates do not afford the processing advantages
associated with the solid secondary (2,3) alkyl sulfates when
formulating detergent granules, bars, or tablets. Moreover, the
secondary ~2,3) alkyl sulfates herein provide better sudsing than
the random mixtures. It is preferred that the secondary (2,3)
alkyl sulfates be substantially free (i.e., contain less than
about 20%, more preferably less than about 10%, most preferably
less than about 5%) of such random secondary alkyl sulfates.
One additional advantage of the secondary (2,3) alkyl sulfate
surfactants herein over other positional or ~random~ alkyl sulfate
isomers is in regard to the improved benefits afforded by said
secondary (2,3) alkyl sulfates with respect to soil redeposition
in the context of fabric laundering operations. As is well-known
to users, laundry detergents loosen soils from fabrics being
washed and suspend the soils in the aqueous laundry liquor.
However, as is well-known to detergent formulators, some portion
of the suspended soil can be redeposited back onto the fabrics.
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WO 94/24238 PCT/US94/03728
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
"greying~. (As a simple test of the redepositlon 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 posi-
tional secondary isomers unexpectedly assists in solving the
problem of soil redeposition in a manner not heretofore
recognized. ~hile not intending to be limited by theory, it can
be speculated that this soil redeposition phenomenon may also
partially account for the desirable decrease in zeolite deposition
onto fabric surfaces in the manner of this invention.
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)i 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 Q-olefins and sulfuric acid is
disclosed in U.S. Patent 3,234,258, Morris, or in U.S. Patent
5,075,041, Lutz, granted December 24, 1991. The synthesis,
conducted in solvents which afford the secondary (2,3) alkyl
sulfates on cooling, yields products which, when purified to
remove the unreacted -materials, randomly sulfated materials,
unsulfated by-products such as C1o and higher alcohols, secondary
WO 94/24238 216 ~1~ 8 PCT/US94/03728
g
olefin sulfonates, and the like, are typically 90+X pure mixtures
of 2- and 3-sulfated materials (up to 10% sodium sulfate is
typically present) and are white, non-tacky, apparently
crystalline, solids. Some 2,3-disulfates may also be present, but
generally comprise no more than 5% of the mixture of secondary
(2,3) alkyl mono-sulfates. Such materials are available as under
the name ~DAN~, e.g., ~DAN 200~ from Shell Oil Company.
If increased solubil~ty of the ~crystailine~ secondary (2,3)
alkyl sulfate surfactants is desired, the formulator may wish to
10 employ mixtures of such surfactants having a mixture of alkyl
chain lengths. Thus, a mixture of C12-C1g alkyl chains will
provide an increase in solubility over a secondary (2,3) alkyl
sulfate wherein the alkyl chain is, say, entirely C16. The
solubility of the secondary (2,3J alkyl sulfates can also be
15 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 (2,3J
alkyl sulfates. Such crystallinity-interrupting materials are
typically effective at levels of 20X, or less, of the secondary
20 (2,3) alkyl sulfate.
LaYered Silicate Builders
The layered silicate builders used herein include various
alkali metal silicates, particularly those having a SiO2:Na20
ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as
25 the layered sodium silicates described in U.S. Patent 4,664,839,
issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for
a crystalline layered silicate marketed by Hoechst (commonly
abbreviated herein as ~SKS-6~). Unlike zeolite builders, the Na
SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the
30 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 NaMsixo2x+l YH20 wherein
35 M is sodium or hydrogen, x is a number from 1.9 to 4, preferably
2, and y is a number from O to 20, preferably O can be used
herein. Various other layered silicates from Hoech.t include
NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
216010~
WO 94/24238 - PCT/US94/03728
- 10 -
As noted above, the delta-Na2SiOs (NaSKS-6 form) is most preferred
for use herein. Other silicates may also be useful such as for
example magnesium silicate, which can serve as a crispening agent
in granular formulations, as a stabilizing agent for oxygen
bleaches, and as a component of suds control systems.
Adiunct Inqredients
Builders - Additional 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 composi-
tions to assist in the removal of particulate soils.
The level of adjunct builder can vary widely depending upon
the end use of the composition and its desired physical form.
~hen present, the compositions will typically comprise at least
about 1% adjunct builder. Granular formulations typically com-
prise from about 10X to about 80X, more typically from about 15X
- to about 50X by weight, of the detergent builder. Lower or higher
levels of builder, however, are not meant to be excluded, so long
as the relative total amounts of the layered silicate builder and
the zeolite adjunct builder set forth hereinabove are followed.
Aluminosilicate builders, i.e., zeolites, are useful adjunct
builders in the present invention. Aluminosilicate builders are
of great importance in most currently marketed heavy duty granular
detergent compositions, and can also be a significant builder
ingredient in liquid detergent formulations. Aluminosilicate
builders include those having the empirical formula:
HZ(zAlo2 YSiO2)
wherein M is sodium, potassium, ammonium or substituted ammonium,
z is from about 0.5 to about 2; and y is 1; this material having a
magnesium ion exchange capacity of at least about 50 milligram
equivalents of CaC03 hardness per gram of anhydrous aluminosili-
cate. Preferred aluminosilicates are zeolite builders which have
the formula:
Naz[(Alo2)z (Sio2)y]-xH2o
wherein z and y are integers of at least 6, the molar ratio of z
to y is in the range from 1.0 to about 0.5, and x is an integer
from about 15 to about 264.
WO 94/24238 2 16 0 i 0 8 PCT/US94/03728
~-- 1 1 -- ,
Useful aluminosilicate ion exchange materials are commer-
cially available. These aluminosilicates can be crystalline or
amorphous in structure and can be naturally-occurring aluminosili-
cates or synthetically derived. A method for producing alumino-
5 silicate 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 embodi-
ment, the crystalline aluminosilicate ion exchange material has
the formula:
Na12[(AlO2)12(sio2)l2] xH2o
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.
Organic detergent builders suitable for the purposes of the
present invention include, but are not restricted to, a wide
variety of polycarboxylate compounds. As used herein, ~polycar-
boxylate~ refers to compounds having a plurality of carboxylate
groups, preferably at least 3 carboxylates. Polycarboxylate
builder can generally be added to the composition in acid form,
but can also be added in the form of a neutralized salt. ~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 poly-
carboxylate builders encompasses the ether polycarboxylates,
including oxydisuccinate, as disclosed in Berg, U.S. Patent
3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent
3,635,830, issued January 18, 1972. See also ~TMS/TDS~ builders
of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
Suitable ether polycarboxylates also include cyclic compounds,
particularly alicyclic compounds, such as those described in U.S.
Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
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
WO 94,2423~!15 010 8 PCT/US94/03728
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 detergent formulations
due to their availability from rer.~!ahle resources and their
biodegradability. Citrates can also be used in granular composi-
tions, especially in combination with zeolite and/or layered
silicate builders. Oxydisuccinates are also especially useful in
such compositions and combinations.
Also suitable in the detergent compositions of the present
invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the
related compounds disclosed in U.S. Patent 4,566,984, Bush, issued
~anuary 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-C18 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.
WO 94/24238 21~ ~1 0 8 PCT/US94/03728
_ 13
Examples of carbonate builders are the alkaline earth and
alkali metal carbonates as disclosed in German Patent Application
No. 2,321,001 published on Hovember 15, 1973.
Phosphate builders may be used in regions of the world where
S they are acceptable, but are not preferred herein.
EnzYmes - Detersive enzymes may optionally, but preferably,
be included in the detergent formulations herein for a wide
variety of fabric laundering 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, lipases, cellulases, and peroxidases, as well
as mixtures thereof. Other types of enzymes may also be included.
They may be of any suitable origin, such as vegetable, animal,
bacterial, fungal and yeast origin. However, their choice is
governed by several factors such as pH-activity and/or stability
optima, thermostability, stability versus active detergents,
builders and so on. In this respect bacterial or fungal enzymes
are preferred, such as bacterial amylases and proteases, and
fungal cellulases.
Enzymes are normally incorporated at levels sufficient to
provide up to about 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 0.01%-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 s~itable for removing protein-based stains
that are commercially available include those sold under the
WO 94124238 216 010 8 PCT/US94/03728
- 14 -
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, Hovo Industries.
The cellulases usable in the present invention include both
bacterial or fungal cellulase. Preferably, they will have a pH
optimum of between 5 and 9.5. Suitable cellulases are disclosed
in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984,
which discloses fungal cellulase produced from Humicola insolens
and Humicola strain DSM1800 or a cellulase 212-producing fungus
belonging to the genus Aeromonas, and cellulase extracted from the
hepatopancreas of a marine mollusk (Dolabella Auricula Solander).
Suitable cellulases are also disclosed in GB-A-2.075.028;
GB-A-2.095.275 and DE-OS-2.247.832.
Suitable lipase enzymes for detergent usage include those
produced by microorganisms of the Pseudomonas group, such as
Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent
1,372,034. See also lipases in Japanese Patent Application
53-20487, laid open to public inspection on February 24, 1978.
This lipase is available from Amano Pharmaceutical Co. Ltd.,
Nagoya, Japan, under the trade name Lipase P ~Amano,~ hereinafter
referred to as ~Amano-P.~ Other commercial 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 g7adio1i. The LIPOLASE
enzyme derived from Humico1a 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
WO 94/24238 216 010 8 PCTrUS94/03728
- 15 -
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 5, 1971 to McCarty et al ().
Enzymes are further disclosed in U.S. Patent 4,101,457, Place et
al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes,
issued March 26, 1985, both. Enzyme materials useful for liquid
detergent formulations, and their incorporation into such
formulations, are disclosed in U.S. Patent 4,261,868, Hora et al,
issued April 14, 1981. Enzymes for use in detergents can be
stabilized by various techniques. Enzyme stabilization techniques
are disclosed and exemplified in U.S. Patent 4,261,868, i ssued
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.
EnzYme Stabilizers - The enzymes employed herein are
stabilized by the presence of water-soluble sources of calcium
and/or magnesium ions in the finished compositions which provide
such ions to the enzymes. (Calcium ions are generally somewhat
more effective than magnesium ions and are preferred herein if
only one type of cation is being used.) Additional stability can
be provided by the presence of various other art-disclosed stabil-
izers, especially borate species: see Severson, U.S. 4,537,706,
cited above. Typical detergents, especially liquids, will com-
prise 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
2160108
WO 94/24238 ' PCT/US94/03728
finished composition. This can vary somewhat, depending on the
amount of enzyme present and its response to the calcium or
magnesium ions. The level of calcium or magnesium ions should be
selected so that there is always some minimum level available for
the enzyme, after allowing for~complexation with builders, fatty
acids, etc., in the composition. Any water-soluble calcium or
magnesium salt can be used as the source of calcium or magnesium
ions, including, but not limited to, calcium chloride, calcium
sulfate, calcium malate, calcium maleate, calcium hydroxide,
calcium formate, and calcium acetate, and the corresponding
magnesium salts. A small amount of calcium ion, generally from
about 0.05 to about 0.4 millimoles per liter, is often also
present in the composition due to calcium in the enzyme slurry and
formula water. In solid detergent compositions the formulation
may include a sufficient quantity of a water-soluble calcium ion
source to provide such amounts in the laundry liquor. In the
alternative, natural water hardness may suffice.
It is to be understood that the foregoing levels of calcium
and/or magnesium ions are sufficient to provide enzyme stability.
More calcium and/or magnesium ions can be added to the composi-
tions to provide an additional measure of grease removal perform-
ance. Accordingly, as a general proposition the compositions
herein will typically comprise from about 0.1% to about 2X by
weight of a water-soluble source of calcium or magnesium ions, or
both. The amount can vary, of course, with the amount and type of
enzyme employed in the composition.
The compositions herein may also optionally, but preferably,
contain various additional stabilizers, especially borate-type
stabilizers. Typically, such stabilizers will be used at levels
in the compositions from about 0.25% to about 10%, 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
3s 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,
WO 94/24238 21 G 010 8 PCT/US94/0372$
~_ 17
butane boronic acid, and p-bromo phenylboronic acid) can also be
used in place of boric acid.
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 1% to about 30%,
more typically from about 5% to about 20%, of the detergent
composition, especially for fabric laundering. If present, the
amount of bleach activators will typically be from about 0.1% to
about 60%, 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 wlthout
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, 8urns 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
pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodiu~
peroxide. Persulfate bleach (e.g., OXONE, manufactured
commercially by DuPont) can also be used.
WO 94/24238 216 010 8 PCTrUS94/03728
- 18 -
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 sulfon-
ate (NOBS) and tetraacetyl ethylene diamine (TAED) activators 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, 19~ to Holcombe et al. If used, detergent compositions will
typically contain from about 0.025% to about 1.25%, by weight, of
such bleaches, especially sulfonated zinc phthalocyanine.
PolYmeric Soil Release Aaent - Any polymeric soil release
agent known to those skilled in the art can optionally be employed
in the compositions and processes of this invention. Polymeric
soil release agents are characterized by having both hydrophilic
segments, to hydrophilize the surface of hyd.ophobic fibers, such
as polyester and nylon, and hyd~ophobic segments, to deposit upon
hyd~ophobic 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
216~10~
WO 94/24238 PCT/US94/03728
- 19 -
(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,
said hjdrophile segments preferably comprising at least about 25%
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.
3s Polymeric soil release agents useful in the present invention
also include cellulosic derivatives such as hydroxyether cellu-
losic polymers, copoly~eric blocks of ethylene terephthalate or
propylene terephthalate with polyethylene oxide or polypropylene
216~108
WO 94124238 PCT/US94/03728
,.
- 20 -
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 C1-C4 alkyl and C4
hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December
28, 1976 to Nicol, et al.
Soil release agents characterized by poly(vinyl ester)
hydrophobe segments include graft copolymers of poly(vinyl ester),
e.g., C1-C6 vinyl esters, preferably poly(vinyl acetate) grafted
onto polyalkylene oxide backbones, such as polyethylene oxide
backbones. See European Patent Application 0 219 048, published
April 22, 1987 by Kud, et al. Commercially available soil release
agents of this kind include the SOKALAN type of material, e.g.,
SOKALAN HP-22, available from BASF (~est Germany).
One type of preferred soil release agent is a copolymer
having random blocks of ethylene terephthalate and polyethylene
oxide (PEO) terephthalate. The molecular weight of this polymeric
soil release agent is in the range of from about 25,000 to about
55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976
and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
Another preferred polymeric soil release agent is a polyester
with repeat units of ethylene terephthalate units containing
10-15% by weight of ethylene terephthalate units together with
90-80% by weight of polyoxyethylene terephthalate units, derived
from a polyoxyethylene glycol of average molecular weight
300-5,000. Examples of this polymer include the commercially
available material ZELCON 5126 (from Dupont) and MILEASE T (from
ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to
Gosselink.
Another preferred polymeric soil release agent is a sulfon-
ated 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.
WO 94/24238 216 010 8 PCT~US94/03728
- 21 -
Other suitable polymeric soil release agents include the
terephthalate polyesters of U.S. Patent 4,711,730, issued December
8, 1987 to Gosselink et al, the anionic end-capped oligomeric
esters of U.S. Patent 4,721,580, issued January 26, 1988 to
Gosselink, and the block polyester oligomeric compounds of U.S.
- Patent 4,702,857, issued October 27, 1987 to Gosselink.
Preferred polymeric soil release agents also include the soil
release agents of U.S. Patent 4,877,896, issued October 31, 1989
to Maldonado et al, which discloses anionic, especially sulfo-
aroyl, end-capped terephthalate esters.
If utilized, soil release agents will generally comprise from
about 0.01X 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 3.0X.
Chelatinq Aqents - The detergent compositions herein may also
optionally contain one or more iron and/or manganese chelating
agents. Such chelating agents can be selected from the group
consisting of amino carboxylates, amino phosphonates,
polyfunctionally-substituted aromatic chelating agents and
mixtures therein, all as hereinafter defined. Without intending
to be bound by theory, it is believed that the benefit of these
materials is due in part to their exceptional ability to remove
iron and manganese ions from washing solutions by formation of
soluble chelates.
Amino carboxylates useful as optional chelating agents
include ethylenediaminetetraacetates, N-hydroxyethylethylenedi-
aminetriacetates, nitrilotriacetates, ethylenediamine tetrapropri-
onates, triethylenetetraaminehexaacetates, diethylenetriamine-
pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and
substituted ammonium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as chelating
agents in the compositions of the invention when at least low
levels of total phosphorus are permitted in detergent composi-
tions, and include ethylenediaminetetrakis (methylenephosphon-
ates), nitrilotris (methylenephosphonates) and diethylenetriamine-
pentakis (methylenephosphonates). Preferably, these amino phos-
phonates do not contain alkyl or alkenyl groups with more than
about 6 carbon atoms.
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WO 94/24238 `- - PCT/US94/03728
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Polyfunctionally-substituted aromatic chelating agents are
also useful in the compositions herein. See U.S. Patent
3,812,044, issued May 21, 1974, to Connor et al. Preferred
compounds of this type in acid form are dihydroxydisulfobenzenes
such as 1,2-dihydroxy -3,5-disulfobenzene.
A very highly preferred biodegradable chelator for use herein
is ethylenediamine disuccinate (~EDDS~), as described in U.S.
Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
If utilized, these chelating agents will generally comprise
from about 0.1% to about 10X by weight of the detergent composi-
tions herein. More preferably, if utilized, the chelating agents
will comprise from about 0.1% to about 3.0X by weight of such
compositions.
ClaY Soil Removal/Anti-redeDosition Aqents - The compositions
of the present invention can also optionally contain water-soluble
ethoxylated amines having clay soil removal and anti-redeposition
properties. 6ranular 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.
WO 94124238 ~16 01~ 8 PCTrUS94/03728
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PolYmeric DisDersinq Aqents - Polymeric dispersing agents can
advantageously be utilized at levels from about O.lX to about 7%,
by weight, in the compositions herein, especially in the presence
of zeolite and/or layered silicate builders. Suitable polymeric
dispersing agents include polymeric polycarboxylates and poly-
ethylene glycols, although others known in the art can also be
used. It is believed, though it is not intended to be limited by
theory, that polymeric dispersing agents enhance overall detergent
builder performance, when used in combination with other builders
(including lower molecular weight polycarboxylates) by crystal
growth inhibition, particulate soil release peptization, and
anti-redeposition.
Polymeric polycarboxylate materials can be prepared by
polymerizing or copolymerizing suitable unsaturated monomers,
preferably in their acid form. Unsaturated monomeric acids that
can be polymerized to form suitable polymeric polycarboxylates
include acrylic acid, maleic acid (or maleic anhydride), fumaric
acid, itaconic acid, aconitic acid, mesaconic acid, citraconic
acid and methylenemalonic acid. The presence in the polymeric
polycarboxylates herein of monomeric segments, containing no
carboxylate radicals such as vinylmethyl ether, styrene, ethylene,
etc. is suitable provided that such segments do not constitute
more than about 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.
Acrylic/maleic-based copolymers may also be used as a pre-
ferred component of the dispersing/anti-redeposition agent. Such
materials include the water-soluble salts of copolymers of acrylic
WO 94/24238 216 010 8 PCT/US94/03728
- 24 -
acid and maleic acid. The average molecular weight of such
copolymers in the acid form preferably ranges from about 2,000 to
100,000, more preferably from about 5,000 to 75,000, most prefer-
ably from about 7,000 to 65,000. The ratio of acrylate to maleate
segments in such copolymers will generally range from about 30:1
to about 1:1, more preferably from about 10:1 to 2~ 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 Appli-
cation No. 66915, published December 15, 1982.
Another polymeric material which can be included is poly-
ethylene glycol (PEGJ. 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 are
especially preferred for use herein, especially in conjunction
with zeolite adjunct 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
detergent compositions herein. Commercial optical brighteners
which may be useful in the present invention can be classified
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 Agentsn, M. Zahradnik,
Published by John ~iley & 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 ~ixon on December 13, 1988. These
brighteners include the PHOR~HITE series of brighteners from
Verona. Other brighteners disclosed in this reference include:
WO 94/24238 216 01~ ~ PCT/US94/03728
- 25 -
Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-
Geigy; Arctic ~hite CC and Artic ~hite C~D, available from Hilton-
Davis, located in Italy; the 2-(4-styryl-phenyl)-2H- naphthol[l, 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 ~amilton.
Suds SuDDressors - Compounds for reducing or suppressing the
formation of suds can be incorporated into the compositions of the
present invention. Suds suppression can be of particular import-
ance under conditions such as those found in European-style front
loading laundry washing machines, or in the concentrated deter-
gency process of U.S. Patents 4,489,455 and 4,489,574, or when the
detergent compositions herein optionally include a relatively high
sudsing adjunct surfactant.
A wide variety of materials may be used as suds suppressors,
and suds suppressors are well known to those skilled in the art.
See, for example, Kirk Othmer Encyclopedia of Chemical Technology,
Third Edition, Volume 7, pages 430-447 (John ~iley ~ 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 ~ayne 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 Clg-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
fonmed as products of cyanuric chloride with two or three moles of
WO 94/24238 216 01~ ~ PCTrUS94/03728
- 26 -
a primary or secondary amine containing 1 to 24 carbon atoms,
propylene oxide, and monostearyl phosphates such as monostearyl
alcohol phosphate ester and monostearyl di-alkali metal (e.g. K,
Na, and Li) phosphates and phosphate esters. The hydrocarbons
such as paraffin and haloparaffin can be utilized in liquid form.
The liquid hydrocarbons will be liquid at room temperature and
atmospheric pressure, and will have a pour point in the range of
about -40-C and about 5-C, and a minimum boiling point not less
than about llO-C (atmospheric pressure). It is also known to
utilize waxy hydrocarbons, preferrably having a melting point
below about lOO-C. ~he hydrocarbons constitute a preferred
category of suds suppressor for detergent compositions.
Hydrocarbon suds suppressors are described, for example, in U.S.
Patent 4,265,779, issued May S, 1981 to Gandolfo et al. The
hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and
heterocyclic saturated or unsaturated hydrocarbons having from
about 12 to about 70 carbon atoms. The term ~paraffin,~ as used
in this suds suppressor discussion, is intended to include
mixtures of true paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds suppressors
comprises silicone suds suppressors. This category includes the
use of polyorganosiloxane oils, such as polydimethylsiloxane,
dispersions or emulsions of polyorganosiloxane oils or resins, and
combinations of polyorganosiloxane with silica particles wherein
the polyorganosiloxane is chemisorbed of fused onto the silica.
Silicone suds suppressors are well known in the art and are, for
example, disclosed in U.S. Patent 4,265,779, issued May 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
i nstance, in German Patent Application W S 2,124,526. Si1icone
defoamers and suds controlling agents in granular detergent
compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et
WO 94/24238 216 010 8 PCT/IIS94/03728
._
- 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
S 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 Si1/2 units
of SiO2 units in a ratio of from (CH3)3 Si1/2 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
15 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 %i 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.
21~0108
WO 94/24238 PCT/US94/03728
- 28 -
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 %, 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 discl-osed in U.S.
4,798,679, 4,075,118 and EP 150,872. The secondary alcohols
include the C6-C16 alkyl alcohols having a C1-C16 chain. A
preferred alcohol is 2-butyl octanol, which is available from
Condea under the trademark ISOFOL 12. Mixtures of secondary
alcohols are available under the trademark ISALCHEM 123 from
Enichem. Mixed suds suppressors typically comprise mixtures of
alcohol + silicone at a weight ratio of 1:5 to 5:1.
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.
WO 94/24238 216 0 t 0 8 PCTAJS94/03728
- 29 -
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 3X 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 0.01X 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
0.1X 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 compositions
herein can also be used with a variety of other adjunct ingredi-
ents which provide still other benefits in various compositions
within the scope of this invention. The following illustrates a
variety of such adjunct ingredients, but is not intended to be
limiting therein.
Fabric Softeners - Various through-the-wash fabric softeners,
especially the impalpable smectite clays of U.S. Patent 4,062,647,
Storm and Nirschl, issued December 13, 1977, as well as other
softener clays known in the art, can optionally be used typically
at levels of from about 0.5% to about 10% by weight in the present
compositions to provide fabric softener benefits concurrently with
fabric cleaning. Clay softeners can be used in combination with
amine and cationic softeners, as disclosed, for example, in U.S.
Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent
4,291,071, Harris et al, issued September 22, 1981.
WO 94/24238 216 01 0 8 PCT/US94/03728
- 30 -
Adiunct Surfactants - The compositions herein can optionally
contain various anionic,-;`nonionic, cationic, zwitterionic, etc.
surfactants. If used, such adjunct surfactants can be present at
levels of from about 5X to about 35% of the compositions.
However, it is to be understood that the incorporation of adjunct
anionic surfactants is entirely optional herein, inasmuch as the
cleaning performance of the secondary (2,3) alkyl sulfates is
excellent and these materials can be used to entirely replace such
surfactants as the alkyl benzene sulfonates in fully-formulated
detergent compositions.
Nonlimiting examples of optional surfactants useful herein
include the conventional C11-C1g alkyl benzene sulfonates and
primary and random alkyl sulfates, the C10-C18 alkyl alkoxy
sulfates (especially EO 1-5 ethoxy sulfates), C10-cl8 alkyl alkoxy
carboxylates (especially the EO 1-5 ethoxycarboxylates), the
C10-cl8 alkyl polyglycosides and their corresponding sulfated
polyglycosides, C12-C1g alpha-sulfonated fatty acid esters,
C12-C1g alkyl and alkyl phenol alkoxylates (especially ethoxylates
and mixed ethoxy/propoxy), C12-C1g betaines and sulfobetaines
(~sultaines~), C1o-C1g 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 R1
(I) R2 - ~ - N - Z
wherein: Rl is H, C1-Cg hydrocarbyl, 2-hydroxyethyl, 2-hydroxy-
propyl, or a mixture thereof, preferably C1-C4 alkyl, more prefer-
ably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and
R2 is a Cs-C32 hydrocarbyl moiety, preferably straight chain
C7-C1g alkyl or alkenyl, more preferably straight chain Cg-C17
alkyl or alkenyl, most preferably straight chain C11-C1g alkyl or
alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl
moiety having a linear hydrocarbyl chain with at least 2 (in the
case of glyceraldehyde) or at least 3 hydroxyls (in the case of
other reducing sugars) directly connected to the chain, or an
alkoxylated derivative- (preferably ethoxylated or propoxylated)
thereof. Z preferably will be derived from a reducing sugar in a
WO 94/24238 ~16 010 ~ PCT/US94/03728
- 31 -
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-(CHOHJn-CH2OH, -CH(CH20H)-(CHOH)n l-
CH2OH, -CH2-(CHOH)2(CHOR')(CHOH)-CH2OH, where n is an integer from
1 to 5, inclusive, and R' is H or a cyclic mono- or poly-
saccharide, and alkoxylated derivatives thereof. Most preferred
are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2OH.
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-CO-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
WO-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 (90-98X) of polyhydroxy fatty acid amides
having desirable low levels (typically, less than about 1.0%) of
sub-optimally degradable cyclized by-products and also with
improved color and improved color stability, e.g., Gardner Colors
below about 4, preferably between 0 and 2. (With compounds such
as butyl, iso-butyl and n-hexyl, the methanol introduced via the
catalyst or generated during the reaction provides sufficient
W O 94/24238 216 010 8 PCTrUS94/03728
- 32 -
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 anhydridé, or the like, to minimize
s the overall level of such residual-amines in the product. Resi-
dual sources of classical fatt~ icids, 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 ~ (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 is a substantial and remarkable improvement
in cold water solubility as a result of the blending and agglomer-
ation 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/AE/AS particles. ~hile not intend-
ing 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 tempera-
tures in the range of 5-C to about 30-C) where the rate of
solubility of detergent granules in an aqueous washing liquor can
be problematic. Of course, the improved solubility achieved
herein is also of substantial benefit when preparing the modern
compact or dense detergent granules where solubility can be
problematic.
WO 94/24238 216 (~ ~ O ~ PCT/US94/03728
- 33 -
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 Clo-cl6 alkanolamides can be incorporated
intc the compositions, typically at 1%-10% levels. The Clo-Cl4
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 MgC12, MgS04, and the like, can be added
at levels of, typically, 0.1%-2%, 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.
~o illustrate this technique in more detail, a porous hydro-
phobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a
proteolytic enzyme solution containing 3X-5% of C13 15 ethoxylated
alcohol EO(7) nonionic surfactant. Typically, the enzyme/surfact-
ant solution is 2.5 X the weight of silica. The resulting powder
is dispersed with stirring in silicone oil (various silicone oil
viscosities in the range of 500-12,500 can be used). The result-
ing silicone oil dispersion is emulsified or otherwise added to
the final detergent matrix. By this means, ingredients such as
the aforementioned enzymes, bleaches, bleach activators, bleach
catalysts, photoactivators, dyes, fluorescers, fabric conditioners
and hydrolyzable surfactants can be ~protected~ for use in deter-
- gents, including liquid laundry detergent compositions.
216û108
WO 94/~4238 : ` PCT/US94/03728
Liquid detergent compositions can contain water and other
solvents as carriers. Low molecular weight primary or secondary
alcohols exemplified by methanol, ethanol, propanol, and isopro-
panol are suitable. Monohydric alcohols are preferred for solu-
bilizing surfactant, but polyols such as those containing from 2
to about 6 carbon atoms and from 2 to about 6 hydroxy groups
(e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-
propanediol) can also be used. The compositions may contain from
5X to 90%, typically 10% to 50X of such carriers.
The detergent compositions herein will preferably be formu-
lated such that, during use in aqueous cleaning operations, the
wash water will have a p~ of between about 7.5 and about 11,
preferably pH 9-11 . Techniques for controlling pH at recommended
usage l~vels include the use of buffers, alkalis, acids, etc., and
are well known to those skilled in the art.
The following are typical, nonlimiting examples which illus-
trate the detergent compositions and uses of the secondary (2,3)
alkyl sulfates according to this invention. Preferred composi-
tions for most purposes contain no phosphates.
In general terms, particulate detergents herein comprising
the secondary (2,3) alkyl sulfate surfactants can be prepared
using a variety of well-known processes. For example, particles
can be formed by agglomeration, wherein solids (including the
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
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
W O 94/24238 216 ~10 ~ PCTrUS94/03728
- 35 -
(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.
ln 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 O.lX-5% by weight of the
finished particles.
If desired, fillers such as hydratable and nonhydratable
salts, crystalline and glassy solids, various detersive ingredi-
ents such as zeolites and the like, can be incorporated in the
particles. If used, such fillers typically comprise up to about
20% by weight of the particles.
Particles prepared in the foregoing manner can be subse-
quently dried or cooled to adjust their strength, physical proper-
ties and final moisture content, according to the desires of the
formulator.
The preferred overall making process for particulate products
herein involves three distinct Steps: (1) agglomeration of the
ingredients to form the base formula, followed by; (2) admixing
various ingredients with the agglomerates formed in Step (1)
WO 94/24238 216 0 1 a 8 PCT/US94/03728
- 36 -
(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
s order to prevent degradation of some of the heat sensitive
surfactants. The resulting product is a high density (ranging
from 600 9/1 iter - 800 g/liter) free flowing detergent mix that
cafi 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 (NIRO, 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 - ~he objective is
to combine the surfactants and liquids in the compositions into a
common mix in order to aid in surfactant solubilization and
agglomeration. In this Step, the surfactants and other liquid
components in the composition are mixed together in a Sigma Mixer
at 140-F (60-C) at about 40 rpm to about 75 rpm for a period of
from 15 minutes to about 30 minutes to provide a paste having the
general consistency of 20,000-40,000 centipoise. Once thoroughly
mixed, the paste is stored at 140-F (60-C) until agglomeration
Step (B) is ready to be conducted. The ingredients used in this
Step include surfactants, acrylate/maleic polymer (m.w. 70,000)
and polyethylene glycol 4000-8000.
SteD B - Aqqlomeration of Powders with Surfactant Paste - ~he
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
WO 94/24238 21~ û i 0 8 PCT/US94/03728
_,
- 37 -
Step, the powders including the layered silicate builder (as
SKS-6), optional citrate and zeolite adjunct builders, sodium
carbonate, ethylenediaminedisuccinate, magnesium sulfate and
optical brightener) are charged into the Eirich Mixer (R-Series)
s 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 size 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 off 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 acceptable
flowability. In this Step, the dried agglomerates from Step C are
charged into the Eirich Mixer (R-Series) and mixed at a rate of
about 1500 rpm to about 3000 rpm while adding 2-6% 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.
2160108
WO 94/24238 ` PCT/US94/03728
EXAMPLE II
Aqqlomerate
% (wt.) in X (wt.) in
final Droduct aqqlomerate
C14 15 alkyl sulfate, Na S.8 6.8
C16 secondary (2,3) alkyl sulfate, Na 17.3 20.4
C12-C1i ethoxylated alcohol (E03) 4.7 5.S
C12 14 N-methylglucamide 4.7 5.5
Acrylate/maleate copolymer 6.2 7.3
Polyethylene glycol 1.4 1.7
Aluminosilicate (zeolite) 8.8 10.3
Sodium citrate 1.9 2.2
Citric acid/SKS-61 11.S 13.S
Sodium carbonate 12.2 14.4
1S EDDS2 0.4 0.5
Mg sulfate 0.4 O.S
Optical brightener 0.1 0.1
Moisture 7.6 8.9
Silica3 0.4 O.S
Balance (unreacted and Na2S04 .1.6 1.9
Agglomerate total 8S.0 100.0
DrY Mix
Percarbonate, Na 7.8
NoBS4 5.9
AE-flake 0.3
Lipolase 0.3
Savinase 0.3
SDrav-on
Perfume 0.4
Finished product total 100.0
lCo-particle of citric acid and layered silicate (2.0 ratio)
2Ethylenediamine disuccinate
3Hydrophobic precipitated silica (trade name SIPERNAT D-ll)
4Sodium nonanoyloxybenzene sulfonate
EXAMPLE III
A laundry bar suitable for hand-washing soiled fabrics is
prepared by standard- extrusion processes and comprises the
following:
WO 94/24238 21~ 01~ 8 PCT/US94/03728
- 39 -
Ingredient X (wt.
C16 secondary (2,3) alkyl sulfate, Na 30
C12 14 N-methylglucamide 5
SKS-6 (Na) 34
Zeolite A (0.1-10~) 10
Coconut monoethanolamide 2
Carboxymethylcellulose 0. 2
Polyacrylate (m.w. 1400) 0.2
Brightener, perfume 0. 2
Protease 0-3
CaS04
~gS04
~ater 4
Filler* --- Balance ---
*Can be selected from convenient materials such as CaC03, talc,
clay, silicates, and the like.
EXAMPLE IV
A granular detergent herein comprises the following.
Inqredient % ~wt.)
Secondary (2,3) alkyl sulfate* 5.0
SKS-6 26.0
C12 14 primary alkyl sulfate, Na salt S.O
Sodium citrate 5.0
Sodium carbonate 20.0
Optical brightener 0.1
Detersive enzyme*~ 1.0
Sodium sulfate 15.0
MgS04 1.0
CaS04 1.0
~ater and minors ---- Balance ----
*C14-C1g average chain length; Na salt.
**1:1 mixture LIPOLASE/ESPERASE.
EXAMPLE VII
The compositions of Example I and II are modified by
including 0.5% of a commercial amylase preparation (TERMAMYL)
therein.
WO 94/24238 2 1 ~ O 1 0 8 : !` ' ' PCT/US94/03728
- 40 -
EXAMPLE VIII
Additional examples of particulate laundry detergents with
mixed surfactants especially suitable for use in front-loading
washing machines such as those commonly used in Europe are as
S follows.
A B C
Surfactants % (wt.) % (wt.~ X (wt.)
C16 secondary (2,3) alkyl sulfate, Na6.92 9.00 7.60
C16/18 primary alkyl sulfate 2.05 3.00 1.30
C12-C1s alkyl ethoxy (1-3) sulfate 0.17 0.40 0.10
C14-C1s alkyl ethoxylate (E07) 4.02 5.00 1.30
C16-C1g AE11 alkyl ethoxylate (E011) 1.10 1.40 1.10
C16-C1g AE25 alkyl ethoxylate (E025) 0.85 -- 0.66
DimethylmonoethOxy C12-14
alkylammonium chloride -- -- 1.40
Builders
Citrate 5.20 10.00 5.00
Zeolite 4A 20.50 16.00 16.00
SKS-6 18.00 28.50 17.10
SOKALAN cp51 4.00 4.90 3.20
Carboxymethylcellulose 0.31 0.39 0.20
Bleach
Perborate monohydrate 8.77 -- 5.80
Perborate tetrahydrate 11.64 -- 7.40
CO3/S04 coated percarbonate -- 12.0 --
TAED2 5.00 -- 3.40
Zinc phthalocyanine 20 ppm -- 20 ppm
DEQUEST 2060 (Monsanto) 0.36 0.60 0.38
MgS04 0.40 0.40 0.40
LIPOLASE (100,000LU/g) 0.36 0.25 0.15
Savinase (4.0 KNPU) 1.40 1.60 1.40
Cellulase (1000CEVU/g) 0.13 0.13 0.26
Soil release polymer3 0.20 0.20 0.15
Anionic optical brightener 0.19 -- 0.15
Polyvinyl pyrrolidone -- 0.15 --
Bentonite clay -- -- 12.50
Polyethyleneglycol4 -- -- 0.30
Glycerol -- -- 0.62
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Perfume 0.43 0.43 0.43
Silicone + dispersant (antifoam) 0.49 0.60 0.49
Moisture, minors ---- Balance ----
lCopolymer acrylic/maleic acid; mol. wt. range 70,000; Na salt.
2Tetraacetylethylenediamine.
3Anionic polyester reaction product of sulfobenzoic acid, tere-
phthalic acid, propane-1,2-diol, ethylene glycol, sulfoisophthalic
acid per Maldonado, ib id .
4M.~. 4,000,000 range.
EXAMPLE IX
A nonphosphate granular laundry detergent composition herein
which comprises biodegradable or biologically inert ingredients is
as follows.
Inqredient % (wt.)
C16 secondary (2,3) alkyl sulfate, Na 20.0
C12-l4 N-methyl glucamide 10.0
SKS-6, Na 15.0
Zeolite A (1 micron) 8.0
Sodium citrate 5-0
Polyaspartate (m.w. avg. 10,000) 3.0
EDDS, Na 1.5
Sodium percarbonate 12.5
Sodium sulfate 5.0
Sodium carbonate 10.0
~ater and nil-P minors Balance
ComDarison Tests
Having described the compositions and processes herein in
substantial detail, the following illustrates the performance
benefits of the compositions herein comprising the layered sili-
cate builder/secondary (2,3) alkyl sulfate vs. more conventional
compositions which contain, for example, zeolite/primary alkyl
sulfate ingredients.
Inqredient % (wt.)
A B C D
C16 secondary (2,3) alkyl sulfate 26.0 -- --
C14 15 primary alkyl sulfate -- 28.5 28.5 28.5
SKS-6 - 22.0 22.0
Citric acid 4.5 4.5 -- --
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Zeolite A -- -- 39.9 26.5
Sodium carbonate 35.0 35.0 25.0 25.0
Suds suppressor 2.6 2.6 2.6 2.6
C14 15 ethoxylate (E07) 4.0 4.0 4.0 4.0
Sodium sulfate 5.9 5.9 0.0 5.9
Test Methodoloqv - Performance of the above compositions is
tested in a Launderometer with stain tracer swatches using 3.3 9
of test product in 400 ml water pots. ~ater hardness is 25-
German (3:1 Ca:Mg ratio). Four replicates per product are used.
~he wash cycle is 30-C for 45 minutes. At the end of the cycle,
the stain tracer swatches (dirty motor oili shoe polish; cosmetics
on polyester/cotton swatches; clay soil on cotton swatch) are
manually rinsed in clean water and visually graded.
In such tests the results are as follows.
Formulation A vs. B
A B
Dirty motor oil +0.63 0
Shoe polish +0.75 (s) 0
Cosmetics -0.25 0
Clay +1.00 (s) 0
Positive numbers (+) are in favor of Formulation A.
Formulation A vs. C
A C
Dirty motor oil (DM0) -0.75 0
Shoe polish +0.25 0
Cosmetics +0.25 0
Clay +0.88 (s) 0
Average greasy:(DM0 + shoe polish
+ cosmetics) -0.08 0
Positive numbers are in favor of Formulation A.
Formulation A vs. D
A D
Dirty motor oil +0.88 0
Shoe polish +1.50 0
Cosmetics +0.50
Clay +0.75 (S) 0
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Average greasy:(DM0 + shoe polish
+ cosmetics) +0.96 (s) 0
Positive numbers are in favor of Formulation A.
In the tests (s) indicates significance at the LSD 95% level.
