Note: Descriptions are shown in the official language in which they were submitted.
~O 94/24241 216 n 2 2 9 PCTIUS94/03699
MAGNESIUM-CONTAINING DETERGENT COMPOSITIONS IN STABLE LIQUID,
GEL OR OTHER FORMS WITH 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 magnesium ions to enhance sudsing and removal of
greasy/oily soils and stains.
BACKGROUND OF THE INVENTION
Most conventional detergent compositions contain mixtures of
various detersive surfactants in order to remove a wide variety of
soils and stains from surfaces. For example, various anionic
surfactants, especially the alkyl benzene sulfonates, are useful
for removing particulate soils, and various nonionic surfactants,
such as the alkyl ethoxylates and alkylphenol ethoxylates, are
useful for removing greasy soils.
~hile a review of the literature would seem to suggest that a
wide selection of anionic surfactants is available to the deter-
gent 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 ben~ene
sulfonates.
It has now been discovered that a particular sub-set of the
class of secondary alkyl sulfates, referred to herein as secondary
(2,3) alkyl sulfates (~SAS"), offers considerable advantages to
the formulator and user of detergent compositions of comparable
chain lengths. For example, the secondary alkyl (2,3) sulfates
WO 94/24241 C~9 - 2 - PCTrUS94/03699
are more soluble in aqueous media than their counterpart primary
alkyl sulfates. 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 appear to exhibit good compatibility with
detersive enzymes, especially in the presence of magnesium or
calcium ions. ~hus, 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 magnesium
ions in a properly formulated detergent composition can assist in
providing removal of greasy/oily soils and stains, as well as the
high sudsing that is often desired by users, especially in hand
dishwashing operations. However, magnesium can cause instability
problems when used with detersive surfactants, which tend to
precipitate or phase separate in liquid compositions in the
presence of magnesium ions. This is problematic under circum-
stances 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 magnesium ions than do the conventional primary alkyl
sulfates. ~he overall result is that more stable liquid and gel
compositions with higher overall sudsing and cleaning performance
can now be secured.
WO 94124241 21~ 0 2 2 9 PCT/US94/03699
-
- 3 -
BACKGROUND ART
The problems associated with the formulation of stable liquid
detergent compositions and means to enhance stability are
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, Wilms et al, July 16, 1985; U.S. 4,614,612, Reilly et
lS 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 THE INVENTION
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 magnesium ions which enhances sudsing and
cleaning performance.
The invention herein provides preferably liquid and gel, but
also granular and bar, detergent compositions, comprising:
(a) at least about 1%, preferably at least about 2X,
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 magnesium ions;(c) optionally, a detersive-active amount of a detersive
adjunct material, or mixtures thereof;
WO 94/24241 6 o ~ PCT/US94/03699
- 4 -
(d) optionally, at least about 0.05% by weight of calcium
ions to enhance removal of greasy/oily soils and stains;
and
(e) optionally, a fluid carrier.
~eight ratios of magnesium cations:anionic surfactant herein
are typically near about stoichiometric, and are conveniently in
the range of 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 formulations.
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 sur-
factants, sultaine surfactants, alkyl ethoxy carboxylate surfact-
ants, alkyl ethoxy sulfate surfactants, alkyl ethoxylate surfact-
ants, 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.
High-sudsing compositions 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 conveniently 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, compris-
ing contacting said surfaces with an aqueous medium containing an
effective amount (typically, at least about 0.01X, 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, preferably, by hand, both with
and without a presoak.
21~ 0 2 ~ 9 PCT/US94/03699
WO 94/24241
All percentages, ratios and proportions herein are by weight,
unless otherwise specified. All documents cited are incorporated
herein by reference.
DETAIEED DESCRIPTION OF THE INVENTION
S 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
ROSO3-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 HPAS~) having 10-20 carbon atoms
are also known; see, for example, European Patent Application
439,316, Smith et al, filed 21.01.91.
Conventional secondary alkyl sulfate surfactants are those
materials which have the sulfate moiety distributed randomly along
the hydrocarbyl "backbone" of the molecule. Such materials may be
depicted by the structure
CH3(CH2)n(CHOso3-M+)(cH2)mcH3
wherein m and n are integers of 2 or greater and the sum of m + n
is typically about 9 to 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+lJ 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 94/24241 ~ ,60?''1 - 6 - PCT/U594103699
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
S types of detergent compositions. For example, the primary alkyl
sulfates can disadvantageously interact with, and even be precipi-
tated by, metal cations such as magnesium and calcium. 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 magnesium or
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 magnesium or calcium ions to enhance grease cutting or
sudsing performance, or to provide enzyme stability, it has now
been found that the primary alkyl sulfates can be problematic due
to such interactions with magnesium or calcium 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 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 suds. 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 94/24241 216 0 2 2 9 PCT/US94/03699
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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)i accordingly, the secondary sulfonates are
3s not the focus of the present invention.
The preparation of the secondary (2,3) alkyl sulfates of the
type useful herein car be carried out by the addition of H2S04 to
olefins. A typical synthesis using ~-olefins and sulfuric acid is
WO 94/24241 ~60~ 8 - PCT/US94/03699
disc~osed in U.S. Patent 3,234,258, Morris, or in U.S. Patent
5,075,041, Lutz, granted December 24, 1991. The synthesis,
conducted in solvents which afford the secondary (2,3) alkyl
sulfates on cooling, yields products which, when purified to
remove the unreacted materials, randomly sulfated materials,
unsulfated by-products such as C1o and higher alcohols, secondary
olefin sulfonates, and the like, are typically 90+% pure mixtures
of 2- and 3-sulfated materials (some sodium sulfate may be pre-
sent) 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 "DANn,
e.g., ~DAN 200~ from Shell Oil Company.
If increased solubility of the "crystalline" secondary (2,3)
alkyl sulfate surfactants is desired, the formulator may wish to
employ mixtures of such surfactants having a mixture of alkyl
chain lengths. Thus, a mixture of C12-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 su1fate is an innocuous material. However, it dissolves
and adds to the ionic ~load~ in aqueous media, and this can
contribute to phase separation in the liquid compositions and to
gel breaking in the gel compositions.
Various means can be used to lower the sodium sulfate content
- - of the secondary (2,3) alkyl sulfates. For example, when theH2S04 addition to the olefin is completed, care can be taken to
remove unreacted H2S04 before the acid form of the secondary (2,3)
2160229
WO 94/24241 PCT/US94/03699
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 (2,3) 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
which is well-known to workers in the field of surfactant
sciences. Krafft temperature is described by K. Shinoda in the
text n Principles of Solution and Solubility n ~ translation in
collaboration with Paul Becher, published by Marcel Dekker, Inc.
1978 at pages 160-161. Stated succinctly, the solubility of a
surface active agent in water increases rather slowly with
temperature up to that point, i.e., the Krafft temperature, at
which the solubility evidences an extremely rapid rise. At a
temperature approximately 4-C above the Krafft temperature a
solution of almost any composition becomes a homogeneous phase.
In general, the Krafft temperature of any given type of
surfactant, such as the secondary (2,3) alkyl sulfates herein
which comprise an anionic hydrophilic sulfate group and a
hydrophobic hydrocarbyl group, will vary with the chain length of
the hydrocarbyl group. This is due to the change in water
solubility with the variation in the hydrophobic portion of the
surfactant molecule.
In the practice of the present invention the formulator may
optionally wash the secondary (2,3) alkyl sulfate surfactant which
is contaminated with sodium sulfate with water at a temperature
that is no higher than the Krafft temperature, and which is
preferably lower than the Krafft temperature, for the particular
secondary (2,3) alkyl sulfate being washed. This allows the
sodium sulfate to be dissolved and removed with the wash water,
while keeping losses of the secondary (2,3) alkyl sulfate into the
wash water to a minimum.
Under circumstances where the secondary (2,3) alkyl sulfate
surfactant herein comprises a mixture of alkyl chain lengths, it
will be appreciated that the Krafft temperature will not be a
2~ PCT/US94tO3699
- 10 -
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
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 sodium alkyl
(2,3) sulfate surfactants, it is preferred to conduct the washing
operation at temperatures below about 30-C, preferably below about
20-C. It will be appreciated that changes in the cations will
change the preferred temperatures for washing the secondary (2,3)
alkyl sulfates, due to changes in the Krafft temperature.
The washing process can be conducted batchwise by suspending
wet or dry secondary (2,3) alkyl sulfates in sufficient water to
provide 10-50% 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.
Maqnesium Ion Source - The present compositions will contain
at least about 0.05% by weight of a water-soluble source of
magnesium ions. Suitable and convenient sources include, but are
not limited to: Mg(OH)2, MgC12, MgS04, and the formate, citrate,
malate and maleate salts of magnesium, or mixtures thereof. Usage
7eve7s range from 0.05% to 2% of the compositions herein.
Detersive Adiunct Materials
EnzYmes - Detersive enzymes can optionally be included in the
detergent formulations herein for a wide variety of fabric laund-
ering purposes, including removal of protein-based, carbohydrate-
based, or triglyceride-based stains, for example, and for the
prevention of refugee -dye transfer, and for fabric restoration.
The enzymes to be incorporated include proteases, amylases,
WO 94/24241 21 6 0 2 ~ ~ PCT/US94103699
_,
lipa-ses, 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
baclerial amylases and proteases, and fungal cellulases.
Enzymes are normally incorporated at levels sufficient to
provide up to about 5 mg by weight, more typically about 0.01 mg
to about 3 mg, of active enzyme per gram of the composition.
Stated otherwise, the compositions herein will typically comprise
from about 0.001% to about 5%, preferably O.01X-lX, by weight of a
commercial enzyme preparation. Protease enzymes are usually
present in such commercial preparations at levels sufficient to
provide from 0.005 to 0.1 Anson units (AU) of activity per gram of
composition.
Suitable examples of proteases are the subtilisins which are
obtained from particular strains of B.subtilis and B.licheniforms.
Another suitable protease is obtained from a strain of Bacillus,
having maximum activity throughout the pH range of 8-12, developed
and sold by Novo Industries A/S under the registered trade name
ESPERASE. The preparation of this enzyme and analogous enzymes is
described in British Patent Specification No. 1,243,784 of Novo.
Proteolytic enzymes suitable for removing protein-based stains
that are commercially available include those sold under the
tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark)
and MAXATASE by International Bio-Synthetics, Inc. (The
Netherlands). Other proteases include Protease A (see European
Patent Application 130,756, published January 9, 1985) and
Protease B (see European Patent Application Serial No. 87303761.8,
filed April 28, 1987, and European Patent Application 130,756,
Bott et al, published January 9, 1985).
Amylases include, for example, ~-amylases described in
British Patent Specification No. 1,296,839 (Novo), RAPIDASE,
International Bio-Synthetics, Inc. and IEh.l~lYL, Novo Industries.
The cellulases usable in the present invention include both
bacterial or fungal cellulase. Preferably, they will have a pH
WO 94/24241 ~ ~z~,~ PCT/US94/03699
optimum of between S and 9.5. Suitable cellulases are disclosed
in-U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984,
which discloses fungal cellulase produced from Humicola insolens
and Humicola strain DSM1800 or a cellulase 212-producing fungus
belonging to the genus Aeromonas, and cellulase extracted from the
hepatopancreas of a marine mollusk (Dolabella Auricula Solander).
Suitable cellulases are also disclosed in GB-A-2.075.028;
GB-A-2.095.275 and DE-OS-2.247.832.
Suitable lipase enzymes for detergent usage include those
produced by microorganisms of the Pseudomonas group, such as
Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent
1,372,034. See also lipases in Japanese Patent Application
53-20487, laid open to public inspection on February 24, 1978.
This lipase is available from Amano Pharmaceutical Co. Ltd.,
Nagoya, Japan, under the trade name Lipase P ~Amano, n hereinafter
referred to as ~Amano-P.~ Other commercial lipases include
Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter
viscosum var. 7ipo7yticum 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 Humico1a 7anuginosa and commercially available
from Novo (see also EPO 341,947) is a preferred lipase for use
herein.
Peroxidase enzymes are used in combination with oxygen
sources, e.g., percarbonate, perborate, persulfate, hydrogen
peroxide, etc. They are used for "solution bleaching," i.e. to
prevent transfer of dyes or pigments removed from substrates
during wash operations to other substrates in the wash solution.
Peroxidase enzymes are known in the art, and include, for example,
horseradish peroxidase, ligninase, and haloperoxidase such as
chloro- and bromo-peroxidase. Peroxidase-containing detergent
compositions are disclosed, for example, in PCT International
Application ~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 ().
WO 94/24241 21 6 0 ~ ~ 3 PCT/l~S94/03699
- 13 -
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. 0 199 405, 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 optionally employed herein
can be 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
WO 94/24241 21 ~ PCT/US94/03699
- 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. More calcium
ions can be added to the compositions to provide an additional
measure of grease removal performance. Accordingly, the composi-
tions herein may optionally comprise from about 0.05% to about 2X
by weight of a water-soluble source of calcium ions.
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 0.25X to about 10%, preferably from
about 0.5% to about SX, more preferably from about 0.75% to about
3X, 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, color-
ants, 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
duty" liquids such as those used for dishwashing, typically no
builder is present. ~hen present, the compositions will typically
comprise at least about 1% builder. Liquid formulations typically
WO 94/24241 21 8 ~ 2 ~ 9 PCT/US94/03699
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- 15 -
comprise from about 5% to about SOX, more typically about SX to
about 30X, 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
S builders, generally no more than about 5%-lOX. Granular and bar
compositions can contain from 10% to 60% by weight of builder.
If a solid or bar product is desired, 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 alumino-
silicate ion exchange material has the formula:
Nal2[(Alo2)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 O to 20, preferably O can be used herein. Various
other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and
NaSKS-11, as the alpha, beta and gamma forms. As noted above, the
delta-Na2SiOs (NaSKS-6-form) is most preferred for use herein.
WO 94/24241 PCTtUS94103699
,,.6~~ 16-
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
5carboxylate 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.
10Included 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
153,635,830, 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.
20Other 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
25such 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.
30Citrate builders, e.g., citric acid and soluble salts thereof
(particularly sodium saltJ, 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
35compositions, especially in combination with zeolite and/or
layered silicate builders. Oxydisuccinates are also especially
useful in such compositions and combinations.
WO 94/24241 2I ~ 9 PCT/USg4/03699
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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, 8ush, 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-1-hydroxy-1,1-diphosphonate and other known phosphonates
(see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021;
3,400,148 and 3,422,137) can also be used.
Bleachinq 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, especial~y for fabric laundering. If present, the
amount of bleach activators will typically be from about 0.1% to
WO 94/24241 PCT/US94/03699
2~ 18 -
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 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
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 sulfon-
ate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are
WO 94/24241 21 6 ~ ~ ~ g PCT/US94/03699
- 19 -
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 1.25X, by weight, of
sulfonated zinc phthalocyanine.
Polymeric Soil Release Aqent - Any polymeric soil release
agent known to those skilled in the art can optionally be employed
in the 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,
said hydrophile segments preferably comprising at least about 25%
WO 94/24241 PCT~US94/03699
2~ 9 - 20-
oxyethylene units and more preferably, especially for such compon-
ents having about 20 to 30 oxypropylene units, at least about 50X
oxyethylene units; or (b) one or more hydrophobe components
comprising (i) C3 oxyalkylene terephthalate segments, wherein, if
said hydrophobe components also comprise oxyethylene terephthal-
ate, the ratio of oxyethylene terephthalate:C3 oxyalkylene tere-
phthalate units is about 2:1 or lower, (ii) C4-C6 alkylene or oxy
C4-C6 alkylene segments, or mixtures therein, (iii) poly (vinyl
ester) segments, preferably poly(vinyl acetate), having a degree
of polymerization of at least 2, or (iv) Cl-C4 alkyl ether or C4
hydroxyalkyl ether substituents, or mixtures therein, wherein said
substituents are present in the form of Cl-C4 alkyl ether or C4
hydroxyalkyl ether cellulose derivatives, or mixtures therein, and
such cellulose derivatives are amphiphilic, whereby they have a
lS 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 l00. Suitable oxy C4-C6 alkylene hydrophobe
segments include, but are not limited to, end-caps of polymeric
soil release agents such as MO3S(CH2)nOCH2CH2O-, 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
propy1ene 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 94124241 PCT/US94/03699
21S~229
- 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
S 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-S,OO0. 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.
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.
PCTrUS94103699
WO 94/24241 ~ ~ 9
2 ~6~ 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 0.01X to about 10.07., by weight, of the detergent composi-
tions herein, typically from about 0.1X to about 5%, preferably
from about 0.2X to about 3.0X.
ClaY Soil Removal/Anti-rede w 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 0.01X
to about 10.0X by weight of the water-soluble ethoxylated amines;
liquid detergent compositions typically contain about 0.01% to
about 5X.
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,
i ssued 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
anti redeposition 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 94/24241 21 6 0-22 9 PCT/US94/03699
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- 23 -
November 3, 1987, to Hartman and Perkins. Other suitable
chelating agents are known in the trade and patent literature.
PolYmeric 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.
Polymeric polycarboxylate materials can be prepared by
polymerizing or copolymerizing suitable unsaturated monomers,
preferably in their acid form. Unsaturated monomeric acids that
can be polymerized to form suitable polymeric polycarboxylates
include acrylic acid, maleic acid (or maleic anhydride), fumaric
acid, itaconic acid, aconitic acid, mesaconic acid, citraconic
acid and methylenemalonic acid. The presence in the polymeric
polycarboxylates herein of monomeric segments, containing no
carboxylate radicals such as vinylmethyl ether, styrene, ethylene,
etc. is suitable provided that such segments do not constitute
more than about 40% by weight.
Particularly suitable polymeric polycarboxylates can be
derived from acrylic acid. Such acrylic acid-based polymers which
are useful herein are the water-soluble salts of polymerized
acrylic acid. The average molecular weight of such polymers in
the acid form preferably ranges from about 2,000 to 10,000, more
preferab1y from about 4,000 to 7,000 and most preferably from
about 4,000 to 5,000. Water-soluble salts of such acrylic acid
polymers can include, for example, the alkali metal, ammonium and
substituted ammonium salts. Soluble polymers of this type are
known materials. Use of polyacrylates of this type in detergent
compositions has been disclosed, for example, in Diehl, U.S.
Patent 3,308,067, issued March 7, 1967.
W O 94/24241 PCTrUS94/03699
~60~ 24 -
Acrylic/maleic-based copolymers may also be used as a pre-
ferred component of the dispersing/anti-redeposition agent. Such
materials include the water-soluble salts of copolymers of acrylic
acid and maleic acid. The average molecular weight of such
S copolymers in the acid form preferably ranges from about 2,000 to
100,000, more preferably from about 5,000 to 75,000, most prefer-
ably from about 7,000 to 65,000. The ratio of acrylate to maleate
segments in such copolymers will generally range from about 30:1
to about 1:1, more preferably from about 10:1 to 2:1. Water-
soluble salts of such acrylic acid/maleic acid copolymers can
include, for example, the alkali metal, ammonium and substituted
ammonium salts. Soluble acrylate/maleate copolymers of this type
are known materials which are described in European Patent Appli-
cation No. 66915, published December 15, 1982.
Another polymeric material which can be included is poly-
ethylene glycol (PEG). PEG can exhibit dispersing agent perform-
ance as well as act as a clay soil removal/antiredeposition agent.
Typical molecular weight ranges for these purposes range from
about 500 to about 100,000, preferably from about 1,000 to about
50,000, more preferably from about 1,500 to about 10,000.
Polyaspartate and polyglutamate dispersing agents may also be
used, especially in conjunction with zeolite builders.
Briqhtener - Any optical brighteners or other brightening or
whitening agents known in the art can be incorporated at levels
typically from about 0.05X to about 1.2X, 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", 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
brighteners include the PHORWHITE series of brighteners from
PCTIUS94/03699
WO 94/24241 2 1 6 0 2 2 ~
_ - 25 -
Verona. Other brighteners disclosed in this reference include:
Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-
Geigy; Arctic ~hite 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.
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.
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, some adjunct surfactants, e.g., the
betaines, sultaines and amine oxides are especially useful when
WO 94/24241 PCT/US94/03699
2 Z g - 26 -
high sudsing is desired, i.e., especially in hand dishwashing
operations.
Nonlimiting examples of optional surfactants useful herein
include the conventional Cll-Clg alkyl benzene sulfonates and
primary and random alkyl sulfates (having due regard for the
enzyme stability issues noted above), the Clo-Clg alkyl alkoxy
sulfates (especially EO 1-5 ethoxy sulfates), the Clo-C18 alkyl
alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates),
the Clo-Clg alkyl polyglycosides and their corresponding sulfated
polyglycosides, C12-Clg alpha-sulfonated fatty acid esters,
C12-Clg alkyl and alkyl phenol alkoxylates (especially ethoxylates
and mixed ethoxy/propoxy), C12-Clg betaines and sulfobetaines
(~sultainesn), Clo-Clg 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: Rl is H, Cl-Cg hydrocarbyl, 2-hydroxyethyl, 2-hydroxy-
propyl, or a mixture thereof, preferably Cl-C4 alkyl, more prefer-
ably Cl or C2 alkyl, most preferably Cl 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 Cll-Clg 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
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
3s 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 under-
WO 94/24241 21 6 0 2 ~ g PCT/IJS94/03699
- 27 -
stood that it is by no means intended to exclude other suitable
raw materials. Z preferably will be selected from the group
consisting of -CH2-(CHOH)n-CH20H, -CH(CH20H)-(CHOH)n 1-CH20H,
-CH2-(CHOH)2(CHOR')(CHOH)-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, R1 is preferably methyl
or hydroxyalkyl. If lower 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.
While polyhydroxy fatty acid amides can be made by the
process of Schwartz, U.S. 2,703,798, contamination with cyclized
by-products and other colored materials can be problematic. As an
overall proposition, the preparative methods described in
W0-9,206,154 and ~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.OYo) 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
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.
WO 94/24241 PCTfUS94/03699
J 6~Z~lt~ - 28 -
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 SO3/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/AE/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
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 solubil ity 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
~vn 94124241 2 1 G O ~ z q PCT/US94/03699
.--
- 29 -
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.
Alternatively, if desired, suds controlling agents such as
secondary C1o-C1g alcohols, hydrocarbons, fatty acids and
silicones can be used in the compositions at levels of 0.1%-3X, by
weight.
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-5% of C13 15 ethoxylated
alcohol E0(7) nonionic surfactant. Typically, the enzyme/surfact-
ant solution is 2.5 X the weight of silica. The resulting powder
is dispersed with stirring in silicone oil (various silicone oil
viscosities in the range of 500-12,500 can be used). The result-
ing silicone oil dispersion is emulsified or otherwise added to
the final detergent matrix. By this means, ingredients such as
the aforementioned enzymes, bleaches, bleach activators, bleach
catalysts, photoactivators, dyes, fluorescers, fabric conditioners
and hydrolyzable surfactants can be "protected" for use in deter-
gents, including liquid laundry detergent compositions.
Liquid detergent compositions can contain water and other
so1vents 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 90X, typically 10% to 50% of such carriers.
WO 94/24241 PCTrUS94/03699
30 -
The detergent compositions herein will preferably be formu-
lated such that during use in laundry cleaning operations the wash
water will have a pH of between about 6.5 and about 11, preferably
between about 7.5 and about 10.5. Liquid dishwashing formulations
preferably have a pH between about 6.8 and about 9.0, more
preferably between about 6.8 and about 7.5. 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.
~he following are typical, nonlimiting examples which illus-
trate the detergent compositions and uses of the secondary (2,3)
alkyl sulfates according to this invention. For most purposes,
the preferred compositions herein 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
Mg++ (as MgCl2) 0.2
Ca++ (as CaCl2)
Water Balance
*Purified to contain less than 1% Na2S04.
EXAMPLE Il (A and B)
A B
Ingredient % (wt.)% (wt.
C14 secondary (2,3) alkyl sulfate 11.5 10
C12 13 alkyl ether (aYg. 1) sulfate 17.0 --
C12 13 alkyl dimethyl amine oxide 1.0 2
216 0 2 2 ~ PCT/US94/03699
94/24241
-- - 31 -
C12 13 alkyl ether (avg. 3) sulfate -- 3.0
C12-14 alkyl monoethanolamide 3.0 --
C12 N-methylglucamide -- 8
Mg++ (as Mg Cl2) 0.9 0.6
Ca++ (as Ca Cl2) ~~ 0-3
11 EO(9)~ 5
Sodium xylene sulfonate 2 2
~ater, dye, perfume, minors, enzyme~ --- Balance ---
*As NEODOL 1E9
**Optional
Compositions of the foregoing type exhibit good grease
removal 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
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.
W O 94/24241~9 PCTrUS94/03699
- 32 -
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. Materi-
als such as urea and urea derivatives can also be used to form
gels.
The incorporation of 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 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 0.5Z and greater, generally up to about
2%, typically 0.5X-1.5%, 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)z 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.
In yet another mode which is designed to enhance the grease
removal performance of the instant compositions, magnesium ions,
or, more preferably, a mixture of magnesium and calcium ions, are
incorporated into the 4el. Levels of magnesium or mixed magne-
sium/calcium ions up to about 2%, typically from about 0.4% to
21 8 0 Z 2 ~ PCT/US94/03699
~V() 94/24241
- 33 -
about 1.5%, provide superior grease removal in a hand dishwashing
operation. Ratios of Mg:Ca 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, hydrox-
ides, and the like, can be used.
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 (30Y, active, Albright-
Wilson, United Kingdom) dissolved in 25 grams of water, 8 grams of
C91-8T Dobanol (100X 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 97.6% active coconut N-methyl glucamide and
28 grams of sodium C16 secondary (2,3) alkyl sulfate are added and
agitation is continued. (Ingredients such as detersive enzymes
can be added when the temperature of the liquid reaches about
35-40-C.) The final liquid product forms a gel on cooling.
In an alternate mode, a gel is provided 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, 0.50
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)
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.
While 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 herein.
EXAMPLE IV
A laundry bar suitable for hand-washing soiled fabrics is
prepared by standard extrusion processes and comprises the
following:
WO 94124241 PCT/US94/03699
~6~ Inqredient % (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) 0.2
Brightener, perfume 0.2
Protease 0.3
Ca S04
Mg S04
~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
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)
~") 94/24241 2~1 6 ~ ~ 2 9 PCT/US94/03699
-
- 35 -
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. Water, 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 0.1X-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
W O 94/24241 PCTrUS94/03699
36 -
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 9/1 iter - 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.
SteD 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
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.
2160229
WO 94124241 PCT/US94/03699
- 37 -
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 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 to a final moisture
content of the particles from about 4Z 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 2-6X Zeolite
A (median particle size 2-5~m) during the mixing. The mixing is
- continued until the desired median particle size of from about
1200 to about 400 microns is achieved (typically from about 5
seconds to about 45 seconds). At this point, from about 0.1% 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.
WO 94/24241 PCT/US94/03699
38 -
The following illustrates a laundry detergent composition
prepared in the foregoing manner.
EXAMPLE V
A wlomerate
% (wt.) in X (wt.) in
final Droduct aqqlomerate
C14 l5 alkyl sulfate, Na 5.8 6.8
C16 secondary (2,3) alkyl sulfate, Na17.3 20.4
C12-Cl3 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
lS Citric acid/SKS-61 11.5 13.5
Sodium carbonate 12.2 14.4
EDDS2 0 4 0 5
Mg sulfate 0-4 0-5
Optical brightener 0.1 0.1
Moisture 7.6 8.9
Silica3 0.4 O.S
Balance (unreacted and Na2S04) 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
Savinase 0.3
SDraY-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
The following are additional, nonlimiting examples of liquid
compositions according to this invention.
2160~29
WO 94124241 PCT/US94/03699
~_ 39
EXAMPLE VI
Inqredient % (wt.)
C12 N-methyl glucamide 9.o
C12 ethoxy (1) sulfate 6.0
DAN 214 SAS (Shell) 6.0
2-methyl undecanoic acid 4.5
C12 ethoxy (3) carboxylate 4.5
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
~ater Balance
EXAMPLE VII
The C12 ethoxy(1)sulfate in Example YI is replaced by an
equivalent amount of DAN 216 SAS (Shell).
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
follows.
A B C
Surfactants X (wt.) X (wt.~ % (wt.
C16 secondary (2,3) alkyl sulfate, Na 6.92 9.00 7.60
C16/18 primary alkyl sulfate 2.05 3.00 1.30
C12-Cls alkyl ethoxy (1-3) sulfate 0.17 0.40 0.10
C14-C1s alkyl ethoxylate (E07) 4.02 5.00 1.30
C16-Clg AE11 alkyl ethoxylate (E011) 1.10 1.40 1.10
C16-Clg AE25 alkyl ethoxylate (E025) 0.85 -- 0.66
Oimethylmonoethoxy C12-14
alkylammonium chloride -- -- 1.40
Builders
Citrate 5.20 10.00 S.00
Zeolite 4A 20.50 37.20 17.90
Carbonate (Na) 15.00 5.50 12.10
Amorphous silicate 2.0 3.00 2.00 3.10
W O 94/24241 PCTrUS94/03699
6 0 ~ 19 - 40 -
SOKALAN CP51 4.00 4.90 3.20
Carboxymethylcellulose 0.31 0.39 0.20
Bleach
Perborate monohydrate &.77 -- 5.80
Perborate tetrahydrate 11.64 -- 7.40
C03/S04 coated percarbonate -- 12.0 --
TAED2 5.00 3 40
Zinc phthalocyanine 20 ppm -- 20 ppm
DEQUEST 2060 (Monsanto) 0.36 0.60 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
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, ibid.
4M.~. 4,000,000 range.
~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 C10-cl8 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 typically comprise from 1% to 15X by weight of the
compositions herein.
