Note: Descriptions are shown in the official language in which they were submitted.
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COMPOSITIONS COMPRISING HYDROPHILIC SILICA PARTICULATES
FIELD OF THE INVENTION
The present invention relates to structured surfactant compositions comprising
a detergent
surfactant and hydrophilic silica particulates to be used in granular detegent
compositions. The
preferred silica particulate is hydrophilic precipitated silica. The process
for making a structured
surfactant composition comprising a detergent surfactant and hydrophilic
silica particulates is also
included.
BACKGROUND OF THE INVENTION
It is desired to increase the active level of detergent surfactants in
compositions comprising
said surfactants in order to facilitate the manufacture of detergent
compositions containing high active
levels. In addition, it is also desirable to have surfactant compositions that
are pumpable and generally
easy to transport and transfer from one manufacturing location to a
granulation site. One way to meet
these needs is by mixing a chemical structuring agent to the detergent
surfactant. Prior art includes
EPO 508 543 published October 14, 1992 and U.S. 4,925,585 granted May I5,
1990.
It has now been found that incorporating hydrophilic, finely-divided silica
particulates as a
highly-preferred structuring agent with detergent surfactant enables the
formation of structured
surfactant compositions which have high levels of active. Preferably, the
detergent surfactant is in an
aqueous paste form. Structuring of the paste means the addition of a chemical
in a solid, liquid, or
solution form to change the structure of the paste or modify its physical
characteristics to facilitate the
manufacture of high active detergent agglomerates which otherwise are not
easily obtainable under
normal operating conditions. In addition, when such structured surfactant
compositions are mixed
with other detergent adjuvants such as additional surfactants, detergent
builders, inorganic salts, silica,
and mixtures thereof to form granular detergent compositions, such granules
are free flowing and easy
to transport and transfer.
SUMMARY OF THE INVENTION
The invention encompasses a structured surfactant composition consisting
essentially of
(a) from about 35% to about 60% of a detergent surfactant;
(b) from about 1% to about 20% of hydrophilic, finely-divided silica
particulate; and
(c) from about I S% to about 25% moisture.
SUBSTiTi.~ T E Si~iEcT (RULE 26)
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The invention further encompasses a granular detergent composition comprising:
(a) from about 2% to about 70% of a structured surfactant composition, the
surfactant
composition consisting essentially of
(i) from about 35% to about 60% of a detergent surfactant;
(ii) from about 1% to about 20% of hydrophilic, finely-divided silica
particulate; and
(iii) from about 15% to about 25% moisture; and
(b) from about 30% to about 98% other detergent adjuvanu selected from the
group
consisting of other detergent surfactants, detergent builders, silica, and
mixtures
thereof.
A process for making structured surfactant compositions is also included.
DETAILED DESCRIPT10N OF THE INVENTION
This invention relates to compositions with a detergent surfactant and
hydrophilic, finely-
divided silica particulate.
ingredients, as well as optional ingredients, as well as the process for
making a granular
detergent composition or an additive composition for a detergent composition
are descrilxd in detail
hereinafter.
Structured Surfactant Comtrosition
The structured surfactant composition of the present invention comprises by
weight:
(a) from about 35% to about 60%, preferably from about 35% to about SO%, most
preferably
from about 40% to about 45% of a detergent surfactant;
(b) from about I% to about 20%, preferably from about 1% to about 10%, most
preferably from
about 2% to about 5%, of hydrophilic, finely-divided silica particulate; and
(c) from about 15% to about 25% moisture, wherein the ratio of the silica
particulate to moisture
is from about 1 : 5 to about I : 25, more preferably from about I : 5 to about
I : 7.5.
The structured surfactant composition can be mixed with other detergent
ingredients to form
detergent compositions. If the structured surfactant is directly made into a
detergent composition, the
detergent composition would comprise from about 20% to about 65%, preferably
from about 30% to
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about 65%, most preferably from about 45% to about 65% structured surfactant
composition. The
granular detergent composition preferably has a particle size of a maximum of
5% on 14 Tyler mesh.
The particulate silica is added to the surfactant paste, which typically
contains 15% to about
25% moisture; as well as salts which are the by-product of neutralization. The
particulate silica
absorbs the water and a hardened continuous paste is formed. When shear force
is applied to the
hardened paste, the paste becomes a flowable liquid, which is easily dispersed
into fine droplets by
using any conventional high-shear agglomerating mixer. The droplets are added
with other powder
ingredients to form individual particles with have a particle size of a
maximum of 5% on 14 Tyler
mesh and a minimum of 5% through 100 Tyler mesh. The droplets form particles
inside a typical
agglomerating mixer. These droplets once formed into a particle, do not re-
form a continuous
hardened paste. This results in the formation of particle agglomerates to the
specific particle size
distribution that is required to maintain solubility, handling, etc.
Detereent Surfactant
The detergent surfactant is any surfactant selected from the group of
consisting of anionics,
zwitterionics, ampholytics, cationics, and mixtures thereof. Preferably, the
detergent surfactant is
anionic surfactant. Most preferably, the detergent surfactant is ethoxylated
anionic surfactant.
The anionic surfactant can be selected from:
(a) linear or branched chain alkyl benzene sulfonate having an C8-20 alkyl
chain, preferably
CIO-18 alkyl chain, and most preferably a C12-16 alkyl chain;
(b) alkyl sulfate having a C8-20 alkyl chain, preferably C 14-18 alkyl chain,
most preferably C 12-
16 alkyl chain;
(c) mixtures thereof.
Preferred is Alkylalkoxy sulfate comprising an alkyl portion of from 6 to 18
carbon atoms
and an alkoxy portion comprising, an average, from about 0.5 to about 20 moles
of alkoxy, preferably
ethoxy, units, more preferably from about 0.5 to about 5 ethoxy units.
An anionic surfactant that is most preferable is the alkyl ether sulfate of
the formula R-
EnS03M, wherein:
(i) R is C8-20; and preferably, C12-I5, alkyl chain (mixed chain);
(ii) E is an ethoxy unit;
v (iii) n is from I-20; preferably, n=3; and
(iv) M is a suitable cation, preferably sodium ion.
SUBSTITUTE SHEET (RULE 26)
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Useful anionic surfactants include water-soluble salts of 2-acyloxy-alkane-1-
sulfonic acids
containing from about 2 to 9 carbon atoms in the acyl group and from about 9
to about 23 carbon
atoms in the alkane moiety; water-soluble salts of olefin sulfonates
containing from about 12 to 24
carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3
carbon atoms in the
alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Water-soluble salts of the higher fatty acids, i.e., "soaps", also are useful
anionic surfactants
herein. Soaps can be made by direct saponification of fats and oils or by the
neutralization of free
fatty acids. Examples of soaps are the sodium, potassium, ammonium, and
alkylolamonium salts of
higher fatty acids containing from about 8 to about 24 carbon atoms, and
preferably from about 12 to
about 18 carbon atoms. Particularly useful are the sodium and potassium salts
of the mixtures of fatty
acids derived from coconut oil and tallow, i.e., sodium or potassium tallow
and coconut soaps.
Other anionic surfactants useful herein include:
Sodium alkyl glyceryl ether sulfonates, especially those ethers of higher
alcohols derived from
tallow and coconut oil;
Sodium coconut oil fatty acid monoglyceride sulfonates and sulfates;
Sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates, and
sodium or
potassium salts of methyl ester R-CH(S03M)-COOR', wherein R is Cg-C22 alkyl or
alkenyl, R'
is C 1-C4 alkyl, and M is a counter ion, preferably Na or K, such as disclosed
in WO-93-05013,
published March 18, 1992; sulfonates;
Alpha-sulfonated fatty acid alkyl ether surfactant of the formula R'-C(S03)H-
C(O)-OR", wherein
R' is C8-20; most preferably C8-18, alkyl chain; and R" is CI-C4 alkyl,
preferably methyl;
Secondary alkyl sulfates having an alkyl chain of from i0 to 20 carbon atoms;
and
Alkyl ethoxy carboxylates of the formula RO(CH2CH20)xCH2C00-M+, wherein R is a
C6 to
C I g alkyl; x ranges from 0 to 10, and the ethoxylate distribution is such
that on a weight basis,
the amount of material where x is 0 is less than 20%, the amount of material
where x is greater
than 7 is less than 25%, and wherein the average x is 2-4 when the average R
is C13 or less, and
is 3-6 when R is greater than C13; and M is an alkali metal, alkali earth
metal, ammonium, '
mono-, dl-, and tri-ethanol ammonium.
SUBSTITUTE SHEET (RULE 26)
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One or various aqueous pastes of the salts of anionic surfactants is preferred
for use in the
present invention, It is preferred that the moisture in the surfactant aqueous
paste is as low as possible,
while maintaining paste fluidity, and minimizing the amount of free water that
may need to be
removed, by drying for example, since low moisture leads to a higher
concentration of the surfactant
5 in the finished particle. Preferably the paste contains from about 10% to
about 40% water, more
preferably from about IS% to about 30% water, and most preferably from about
20% to about 30%
water.
The activity of the surfactant paste is at least 30% and can go up to about
90%; preferred
activities are: 70-80%.
Cationic surfactants can also be used as a detergent surfactant herein and
suitable
quaternary ammonium surfactants are selected from mono C6-C 16, preferably C6-
C I0 N-alkyl or
alkenyl ammonium surfactants wherein remaining N positions are substituted by
methyl,
hydroxyethyl or hydroxypropyl groups.
Ampholytic surfactants can also be used as a detergent surfactant herein,
which include
aliphatic derivatives of heterocyclic secondary and tertiary amines;
zwitterionic surfactants which
include derivatives of aliphatic quaternary ammonium, phosphonium and
sulfonium compounds;
water-soluble salts of esters of alpha-sulfonated fatty acids; alkyl ether
sulfates; water-soluble salts
of olefin sulfonates; beta-alkyloxy alkane sulfonates; betaines having the
formula
R(R I )2N+R2C00-, wherein R is a C6-C 1 g hydrocarbyl group, preferably a C I
0-C I 6 alkyl group
or Clp-C16 acylamido alkyl group, each RI is typically CI-C3 alkyl, preferably
methyl and R2 is a
CI-C5 hydrocarbyl group, preferably a CI-C3 alkylene group, more preferably a
CI-C2 alkylene
group. Examples of suitable betaines include coconut acylamidopropyldimethyl
betaine; hexadecyl
dimethyl betaine; C12-14 acylamidopropylbetaine; Cg_14 acylamidohexyldiethyl
betaine; 4[C14-16
acylmethylamidodiethylammonio]-I-carboxybutane; C16-18
acylamidodimethylbetaine;
C12-16 acylamidopentanediethylbetaine; and
[C12-16 acylmethylamidodimethylbetaine. Preferred betaines are C12-18 d~ethy!-
ammonio
hexanoate and the C 10-18 acylamidopropane (or ethane) dimethyl (or diethyl)
betaines; and the
sultaines having the formula (R(RI)2N+R2S03- wherein R is a C6-Clg hydrocarbyl
group,
preferably a C I0-C 16 alkyl group, more preferably a C 12-C 13 amyl ~'oup,
each R I is typically C 1-
C3 alkyl, preferably methyl, and R2 is a C1-C6 hydrocarbyl group, preferably a
CI-C3 alkylene or,
preferably, hydroxyalkylene group. Examples of suitable sultaines include C 12-
C 14
dimethylammonio-2-hydroxypropyl sulfonate, C 12-C 14 arnido propyl ammonio-2-
hydroxypropyl
sultaine, C 12-C 14 d~Y~oxyethylammonio propane sulfonate, and C 16-18
d~ethylammonio
hexane sulfonate, with C12-14 ~ido propyl ammonio-2-hydroxypropyl sultaine
being preferred.
SUBSTITUTE SHEET (RULE 26)
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Hvdrovhilic Silica Particulates
The structured surfactant compositions of the present invention contains, in
addition to a
detergent surfactant, from about 0.2% to about 20%, preferably from about I%
to about 10%, most
preferably from about 2% to about 5%, of hydrophilic, finely-divided silica
particulate. Preferably,
the particulate is a hydrophilic precipitated silica. Such materials are
extremely fine-panicle size
silicon dioxides. Its surface area ranges preferably from 140 to 550 m2/g as
measured by the BET
nitrogen adsorption method. The surface of the silica has both internal and
external surface area which
allows for the easy. absorption of liquids. Dibutyl Phthlate absorption is the
method used to determine
the absorptive capability of precepitated silica. Generally, a precipitated
silica can adsorb 2 to 3 times
its weight.
Precipitated silica materials usually appear in the form of agglomerates. The
average
agglomerate siu of the silica range from about 50 to 100 microns. The silica
agglomerates may be
milled by various known methods to reduce the agglomerate size to the range of
2 to I S microns. The
pH of the silica is normally from about 5.5 to about 7Ø
The hydrophilic silica can also be a fumed silica. Hydrophilic precipitated
silica materials
useful herein are commercially available from Degussa Corporation under the
trade marks SIPERNAT
22S, 22LS, SOS.
Deterttent Adiuvanu
Preferably, the detergent adjuvanu are from about 35% to about 99% of the
detergent
composition. The compositions herein can optionally include one or more other
detergent adjunct
materials or other materials for assisting or enhancing cleaning performance,
treatment of the substrsu
to be cleaned, or to modify the aesthetics of the detergent composition (e.g..
perfumes, coloranu, dyes,
etc.). The following are illustrative examples of such adjunct materials.
Other detergent surfactanu include surfactanu described above. In addition, a
hydrotrope,
or mixture of hydrotropes, can be present in the laundry detergent bar.
Preferred hydrotropes
include the alkali metal, preferably sodium, salts of tolune sulfonate, xylene
sulfonate, cumene
sulfonate, sulfosuccinate, and mixtures thereof. Preferably, the hydrotrope,
in either the acid form
or the salt form, and being substantially anhydrous, is added to the linear
alkyl benune sulfonic acid
prior to iu neutralization. The hydrotrope will preferably be present at from
about 0.5% to about
5% of the laundry detergent bar.
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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. When present, the compositions will typically comprise
at least about I%
builder. Liquid formulations typically comprise from about 5% to about 50%,
more typically about
5% to about 30%, by weight, of detergent builder. Granular formulations
typically comprise from
about 10% to about 80%, more typically from about I S% to about SO% by weight,
of the detergent
builder. Lower or higher levels of builder, however, are not meant to be
excluded.
Inorganic or P-containing detergent builders include, but are not limited to,
the alkali metal,
ammonium and alkanolammonium salts of polyphosphates (exemplified by the
tripolyphosphates,
pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic
acid, silicates,
carbonates (including bicarbonates and sesquicarbonates), sulphates, and
aluminosilicates. However,
non-phosphate builders are required in some locales. Importantly, the
compositions herein function
surprisingly well even in the presence of the so-called "weak" builders (as
compared with phosphates)
such as citrate, or in the so-called "underbuilt" situation that may occur
with zeolite or layered silicate
builders.
Examples of silicate builders are the alkali metal silicates, particularly
those having a
Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the
layered sodium silicates
described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-
6 is the trademark
for a crystalline layered silicate marketed by Hoechst (commonly abbreviated
herein as "SKS-6").
Unlike zeolite builders, the Na SKS-6 silicate builder does not contain
aluminum. NaSKS-6 has the
delta-Na2Si05 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+I'YH20 wherein M is sodium or hydrogen, x is a number from 1.9 to 4,
preferably 2,
and y is a number from 0 to 20, preferably 0 can be used herein. Various other
layered silicates from
Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma
forms. As noted
above, the delta-Na2SiOg (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.
- Examples of carbonate builders are the alkaline earth and alkali metal
carbonates as disclosed
in German Patent Application No. 2,321,001 published on November 15, 1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate
builders are of
great importance in most currently marketed heavy duty granular detergent
compositions, and can also
be a significant builder ingredient in liquid detergent formulations.
Aluminosilicate builders include
those having the empirical formula:
SUBSTITUTE SHEET (RULE 26)
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Mz(zAt02)y]~xH20
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 I 5 to about 264.
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), Zeolite MAP and Zeolite X. In an
especially preferred
embodiment, the crystalline aluminosilicate ion exchange material has the
formula:
Na 12~(A102) 12(Si02) 12)~xH20
wherein x is from about 20 to about 30, especially about 27. This material is
known as Zeolite A.
Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the
aluminosilicate has a particle
size of about 0.1-10 microns in diameter.
~5 Organic detergent builders suitable for the purposes of the present
invention include, but are
not restricted to, a wide variety of polycarboxylate compounds. As used
herein, "polycarboxylate"
refers to compounds having a plurality of carboxylate groups, preferably at
least 3 carboxylates.
Polycarboxylate builder can generally be added to the composition in acid
form, but can also be added
in the form of a neutralized salt. When utilized in salt form, alkali metals,
such as sodium, potassium,
and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of
useful materials.
One important category of polycarboxylate builders encompasses the ether
polycarboxylates,
including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued
April 7, 1964, and
Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also
"TMS/TDS" builders of U.S.
Patent 4,663,071, issued to Bush et al, on May 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 hydroxypolycarboxylates,
copolymers of
malefic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy
benzene-2, 4, 6-trisulphonic
acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium
and substituted
ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid
and nitrilotriacetic acid,
as well as polycarboxylates such as mellitic acid, succinic acid,
oxydisuccinic acid, polymaleic acid,
benzene 1,3,5-tricarboxylic 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 renewable resources and their biodegradability.
Citrates can also be used in
SUBSTITUTE SHEET (RULE 26)
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granular compositions. especially in combination with zeolite andlor 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-!,6-hexanedioates and the related compounds disclosed in U.S. Patent
4,566,984, Bush, issued
January 28, 1986. Useful succinic acid builders include the CS-C20 alkyl and
alkenyl succinic acids
and salts thereof. A particularly preferred compound of this type is
dodecenylsuccinic acid. Specific
examples of succinate builders include: laurylsuccinate, myrisrylsuecinate,
palmirylsuccinate, 2
dodecenylsuccinate (preferred), 2~pentadecenylsuccinate, and the like.
Laurylsuccinates are the
preferred builders of this group, and are described in European Patent
Application
0,200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,
Ctvtchfield et al,
issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7,
1967. See also Diehl U.S.
Patcnt 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 andlor the
succinate builders, to provide additional builder activity. Such use of fatty
acids will generally result
in a diminution of sudsing, which should be taken into account by the
formulator.
In situations where phosphorus-based builders can be used, and especially in
the formulation
of bars used for hand-laundering operations, the various alkali metal
phosphates such as the well-
known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate
can be used.
Phosphonate builders such as 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.
Hydrophilic silica particulates as described above is a preferred detergent
adjuvant.
her Adiunct lnQredients
Ch~latine Aeents ~ 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
ethylenediaminetetracetates,
N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenedtamtne
tetraproprtonates,
triethylenetetraaminehexacetaus, diethylenetriaminepentaacetates, and
ethanoldiglycines, alkali metal.
ammonium, and substituted ammonium salts therein and mixtures therein.
CA 02231691 2002-06-18
Amino phosphonates are also suitable for use as chelating agents in the
compositions of the
invention when at lease low levels of total phosphorus are permitted in
detergent compositions, and
include ethylenediaminetetrakis (methylenephosphonates) as DEQUESt. Preferred,
these amino
phosphonates to not contain alkyl or alkenyl groups with more than about 6
carbon atoms.
Polyfvnctionally-substituted aromatic chelating agents are also useful in the
compositions
herein. See U.S. Patent 3,812,044, issued May 2I, 1974, to Connor et al.
Preferred compounds of this
type in acid form arc dihydroxydisulfobenzenes such as 1.2-dihydroxy-
3.5~disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate ("EDDS"),
especially the [S,S] isomer as described in U.S. Patent 4,704w33, November 3.
1987, to Harman and
Perkins.
If utilized, these chelating agents will generally comprise from about 0.1% to
about 10% by
weight of the detergent compositions herein. More preferably, if utilized, the
chelating agents will
comprise from about 0.1 % to about 3.0% by weight of such compositions.
Clav Soil RemovaUAnti-redeeosition Agents - The compositions of the present
invention can also
optionally contain water-soluble ethoxylated amines having clay soil removal
and antiredeposition
properties. Granular detergent compositions which contain these compounds
typically contain from
about 0.01% to about 10.0% by weight of the water-soluble ethoxylates amines;
liquid detergent
compositions typically contain about 0.01 % to about 5%.
The most preferred soil release and anti-rcdeposition agent is ethoxylated
tetraethylene-
pentamine. Exemplary ethoxylated amines arc further described in U.S. Patent
4,597.898,
VanderMeer, issued July t, 1986. Another group of preferred clay soil
removal~antiredeposition
agents arc the cationic compounds disclosed in European Patent Application
111,965, Oh and
Gosselink, published June 27, 1984. Other clay soil removaUantiredeposition
agents which can be
used include the ethoxylated amine polymers disclosed in European Patent
Application 111,984,
Gosselink, published tune 27, 1984; the zwitterionic polymers disclosed in
European Patent Appli-
cation 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 andlor
anti redeposition agenu
known in the art can also be utilized in the compositions herein. Another type
of preferred
antiredcposition agent includes the carboxy methyl cellulose (CMC) materials.
These materials are
well known in the art.
Polymeric Disxrsina Aeents - Polymeric dispersing agenu can advantageously be
utilized at levels
from about 0.1% to about 7%, by weight, in the compositions herein, especially
in the presence of
zeolite andlor layered silicate builders. Suitable polymeric dispersing agents
include polymeric
poiycarboxylates 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 snhance
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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, malefic acid (or
malefic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic
acid, citraconic acid and
methylenemalonic acid. The presence in the polymeric polycarboxylates herein
or monomeric
segments, containing no carboxylate radicals such as vinylmethyl ether,
styrene, ethylene, etc. is
suitable provided that such segments do not constitute more than about 40% by
weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid. Such
acrylic acid-based polymers which are useful herein are the water-soluble
salts of polymerized acrylic
acid. The average molecular weight of such polymers in the acid form
preferably ranges from about
2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably
from about 4,000 to
5,000. Water-soluble salts of such acrylic acid polymers can include, for
example, the alkali metal,
ammonium and substituted ammonium salts. Soluble polymers of this type are
known materials. Use
of polyacrylates of this type in detergent compositions has been disclosed,
for example, in Diehl, U.S.
Patent 3,308,067, issued march 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred component of
the
dispersing/anti-redeposition agent. Such materials include the water-soluble
salts of copolymers of
acrylic acid and malefic acid. The average molecular weight of such copolymers
in the acid form
preferably ranges from about 2,000 to 100,000, more preferably from about
5,000 to 75,000, most
preferably from about 7,000 to 65,000. The ratio of acrylate to maleate
segments in such copolymers
will generally range from about 30:1 to about 1:1, more preferably from about
10:1 to 2:1. Water
soluble salts of such acrylic acidlmaleic acid copolymers can include, for
example, the alkali metal,
ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers
of this type are
known materials which are described in European Patent Application No. 66915,
published December
15, 1982, as well as in EP 193,360, published September 3, 1986, which also
describes such polymers
comprising hydroxypropylacrylate. Still other useful dispersing agents include
the
maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in
EP 193,360, including,
for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
Another polymeric material which can be included is polyethylene glycol (PEG).
PEG can
exhibit dispersing agent performance 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.
SUBSTITUTE SHEET (RULE 26)
CA 02231691 2002-06-18
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Polyaspartate and polyglutamate dispersing agents may also be used, especially
in
conjunction with zeolite builders. Disposing agents such as polyaspartate
preferably have a molecular
weight (avg.) of about 10.000.
Briehtener - Any optical brighteners or other brightening or whitening agents
known in the alt 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
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 Verona. Other brighteners
disclosed in this
reference include: Tinopal UNPA, Tinopal C8S and Tinopal SBM; available from
Ciba-Geigy; Artic
White CC and Artic White CWD, available from Hilton-Davis, located in Italy:
the 2-(4-stryl-phenyl)-
2H-napthol[ 1,2~d]triazoles; 4,4'-bis- ( 1.2,3-aiazol-2-yl}-stil- bones; 4,4'-
bis(stryl)bisphenyls; and the
aminocoumarins. Specific examples of these brighteners include 4-methyl-7-
diethyl- amino coumarin;
1,2-bis(-venzimidazol-2~yl)ethyiene; 1,3-diphenyl-phrazolines; 2.5-
bis(benzoxazol-2-yl)thiophene; 2-
stryl-napth-(l,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. Anionic brighteners arc
preferred herein.
Suds Suwressors - Compounds for reducing or suppressing the formation of suds
can be incorporated
into the compositions of the present invention. Suds suppression can be of
particular importance in the
so-called "high concentration cleaning process" as described in U.S. 4,489,455
and 4,489.5?4 and in
front-loading European-style washing machines.
A wide variety. of materials may be used as suds suppressers, and suds
suppressers are well
known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia
of Chemical
Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, inc.,
1979). One category
of suds suppresser of particular interest encompasses monocarboxyiie fatty
acid and soluble salts
therein. See U.S. Patent 2.954,347, issued September 27. 1960 to Wayne St.
John. The
monocarboxylic fatty acids and salts thereof used as suds suppresser 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
suppressers. These
include, for example: high molecular weight hydrocarbons such as paraffin,
fatty acid esters (r.g.,
CA 02231691 2002-06-18
13
fatty acid triglycerides), fatty acid esters of monovaient alcohols. aliphatic
Clg-C40 ketones (t.g..
stearone), etc. Other suds inhibitors include N-alkylated amino triazines such
as tri- to hexa-
alkylmelamines or di- to tetra-alkyldiamine chlorniazines formed as products
of cyanuric chloride
with two or three moles of a primary or secondary amine containing 1 to 24
carbon atoms, propylene
oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester
and monostearyl di-
alkali metal (e.g.. K, Na, and Li) phosphates and phosphate esters. The
hydrocarbons such as para~ffm
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 50°C, and a minimum boiling point not less than about 1
10°C (atmospheric pressure). It is also
known to utilize waxy hydrocarbons, preferably having a melting point below
about 100°C. The
hydrocarbons constitute a preferred category of suds suppressor for detergent
compositions.
Hydrocarbon suds suppressors are described, for example, in U.S. Patent
4,265,779, issued May 5,
1981 to Gandolfo et al. The hydrocarbons, thus, include aliphatic, alicyclic,
aromatic, and heterocyclic
saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon
atoms. The term
"paraffin," as used in this suds suppressor discussion, is intended to include
mixtures of true paraf~ins
and cyclic hydrocarbons.
Another preferred category of non-surfactant suds supprcssors 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 or fused
onto the silica. Silicone
suds suppressors are well known in the art and arc, for example, disclosed in
U.S. Patent 4,265,779,
issued May 5, 1981 to Gandolfo et al and European Patent Application No.
354016, published
February 7. 1990, by Starch, M. S.
Other silicone suds suppressors are disclosed in U.S. Patent 3.455,839 which
relates to
compositions and processes for defoaming aqueous solutions by incorporating
therein small amounts
of polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described, for instance, in
German Patent
Application DOS 2,124,526. Silicone defoamers and suds controlling agents in
granular detergent
compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in
U.S. Patent 4,652,392,
Baginski et al, issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein is a suds
suppressing amount of a
suds controlling agent consisting essentially of:
(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to
about 1,500 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)3Si01~ units of Si02 units in a ratio of from (CH3)3 SiOln
units
and to SiO~ units of from about 0.6: I to about 1.2: I; and
CA 02231691 2002-06-18
14
(iii) from about 1 to about 20 parts per 100 pans by weight of (i) of a solid
silica gel.
In the preferred silicone suds suppresser used herein, the solvent for a
continuous phase is
made up of certain polyethylene glycois or polyethylene-polypropylene glycol
copolymers or mixtures
thereof (preferred), or polypropylene glycol. The primary silicone suds
suppresser is
branched/crossiinked and preferably 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 about 0.05 to about 0.5, weight % of said silicone suds
suppresser, which
comprises ( 1 ) a nonaqueous emulsion of a primary antifoam agent which is a
mixture of (a) a
polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing
silicone compound, (c) a
finely divided filler material, and (d) a catalyst to promote the reaction of
mixture components (a), (b)
and (c), to form silanolates; (2) at least one nonionic silicone surfactant;
and (3) polyethylene glycol or
a copolymer of polyethylene-polypropylene glycol having a solubility in water
at room temperature of
more than about 2 weight %; and without polypropylene glycol, Similar amounts
can be used in
granular compositions, gels, etc. See also U.S. Patents 4,978,471, Starch,
issusd December 18, 1990,
and 4,983.316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued
February 22. 1994, and
U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46
through column 4, line 35.
The silicone suds suppresser herein preferably comprises polyethylene glycol
and a
copolymer of polyethylene glycoUpolypropylene glycol, ail 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 3 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 giycoUpolypropyiene 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 suppressers used herein do not contain
polypropylene glycol,
particularly of 4,000 molecular weight. They also preferably do not contain
block copolymers of
TM
ethylene oxide and propylene oxide, like PLURON1C LI01.
Other suds suppressers useful herein comprise the secondary alcohols (e.g., 2-
alkyl alkanols)
and mixtures of such alcohols with silicone oils, such as the silicones
disclosed in U.S. 4,798,679,
4,075, I I 8 and EP 150,872. The secondary aicohols include the C6-C 16 alkyl
sicohols having a C 1-
C 16 chain. A preferred alcohol is 2-butyl octanol, which is available from
Condea under the
trademark ISOFOL 12. Mixtures of secondary alcohols arc available under the
trademark
1SALCHEM 123 from Enichem. Mixed suds suppressers typically comprise mixtwes
of alcohol +
silicone at a weight ratio of 1:5 to 5:1.
CA 02231691 1998-03-11
WO 97/10321 PCT/US96/13448
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
5 sufficiently control the suds to result in a low-sudsing laundry detergent
for use in automatic laundry
washing machines.
The compositions herein will generally comprise from 0% to about 5% of suds
suppressor.
When utilized as suds suppressors, monocarboxylic fatty acids, and salts
therein, will be present
typically in amounts up to about 5%, by weight, of the detergent composition.
Preferably, from about
10 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized.
Silicone suds suppressors are
typically utilized in amounts up to about 2.0%, by weight, of the detergent
composition, although
higher amounts may be used. This upper limit is practical in nature, due
primarily to concern with
keeping costs minimized and effectiveness of lower amounts for effectively
controlling sudsing.
Preferably from about 0.01% to about 1% of silicone suds suppressor is used,
more preferably from
15 about 0.25% to about 0.5%. As used herein, these weight percentage values
include any silica that
may be utilized in combination with polyorganosiloxane, as well as any adjunct
materials that may be
utilized. Monostearyl phosphate suds suppressors are generally utilized in
amounts ranging from
about 0.1% to about 2%, by weight, of the composition. Hydrocarbon suds
suppressors are typically
utilized in amounts ranging from about 0.01% to about 5.0%, although higher
levels can be used. The
alcohol suds suppressors are typically used at 0.2%-3% by weight of the
finished compositions.
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,
Hams et al, issued
September 22, 1981.
Additional Adiunct Ingredients
A wide variety of other ingredients useful in detergent compositions can be
included in the
compositions herein, including other active ingredients, carriers,
hydrotropes, processing aids, dyes or
pigments, solvents for liquid formulations, solid fillers for bar
compositions, etc. If high sudsing is
desired, suds boosters such as the C10-C16 alkanolamides can be incorporated
into the compositions,
typically at 1%-10% levels. The C10-C14 monoethanol and diethanol amides
illustrate a typical class
of such suds boosters. Use of such suds boosters with high sudsing adjunct
surfactants such as the
amine oxides, betaines and sultaines noted above is also advantageous. If
desired, soluble magnesium
SUBSTITUTE SHEET (RULE 26)
CA 02231691 1998-03-11
WO 97/10321 PCT/iJS96/13448
16
salts such as MgCl2, MgS04, and the like, can be added at levels of,
typically. 0.1%-2%. to provide
additional suds and to enhance grease removal performance.
Various detersive ingredients employed in the present compositions 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 hydrophobic silica
(trademark
SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution
containing 3%-5% of C13
15 ethoxylated alcohol (E0 7) nonionic surfactant. Typically, the
enryme/surfactant 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 resulting 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 detergents,
including liquid laundry detergent compositions.
Liquid detergent compositions can contain water and other solvents as
carriers. Low
molecular weight primary or secondary alcohols exemplified by methanol,
ethanol, propanol, and
isopropanol are suitable. Monohydric alcohols are preferred for solubilizing
surfactant, but polyols
such as those containing from 2 to about 6 carbon atoms and from 2 to about 6
hydroxy groups (e.g.,
1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be
used. The compositions
may contain from 5% to 90%, typically I 0% to 50% of such carriers.
The detergent compositions herein will preferably be formulated such that,
during use in
aqueous cleaning operations, the wash water will have a pH of between about
6.5 and about I I,
preferably between about 7.5 and 10.5. Liquid dishwashing product formulations
preferably have a
pH between about 6.8 and about 9Ø Laundry products are typically at pH 9-I
1. 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.
Dve Transfer Inhibiting Aeents - The compositions of the present invention may
also include one or
more materials effective for inhibiting the transfer of dyes from one fabric
to another during the
cleaning process. Generally, such dye transfer inhibiting agents include
polyvinyl pyrrolidone
poiymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-
vinylimidazole,
manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these
agents typically comprise
from about 0.01% to about 10% by weight of the composition, preferably from
about 0.01% to about
5%, and more preferably from about 0.05% to about 2%.
SUBSTITUTE SHEET (RULE 26)
CA 02231691 2002-06-18
More specifically, the polyamine N-oxide polymers suitable for use herein
contain units
having the following structural formula: R-Ax-P; wherein P is a polymerizable
unit to which an N-O
group can be attached or the N-O group can form part of the potymerizable unit
or the N-O group can
be attached to both units; A is one of the following structures: -NC(O)~, -
C(O)D-, -S-, -O-, -N=; x is 0
or I; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or
alicyclic groups or any
combination thereof to which the nitrogen of the N-O group can be attached or
the N-O group is part of
these groups. Preferred polyamine N-oxides are those wherein R is a
heterocyclic group such as
pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
The N-O group can be represented by the following general structures:
U~NWy, UDC
,o
wherein RI, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups
or combinations thereof; x,
y and z are 0 or l; and the nitrogen of the N-O group can be attached or form
part of any of the
aforcmcntioned groups. The amine oxide unit of the polyamine N-oxides has a
pKa <10, preferably
pKa <7, more preferred pKa <6.
Any polymer backbone can be used as long as the amine oxide polymer formed is
water-
sotuble and has dye transfer inhibiting properties. Examples of suitable
polymeric backbones are
polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides,
polyacrylates and mixtures
thereof. These polymers include random or block copolymers where one monomer
type is an amine
N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers
typically have a
ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the
number of amine oxide
groups present in the polyamine oxide polymer can be varied by appropriate
copolymerization or by an
appropriate degree of N-oxidation. The polyamine oxides can be obtained in
almost any degree of
polymerization. Typically, the average molecular weight is within the range of
500 to 1,000,000; more
preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred
class of materials cant be
referred to as "PVNO".
The most preferred polyamine N-oxide useful as dye aansfer inhibiting polymers
in the
detergent compositions herein is poly(4-vinylpyridine-N-oxide) which as an
average molecular weight
of about 50.000 and an amine to amine N-oxide ratio of about I :4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as
a class as
"PVPVI") are also suitable for use herein. Preferably the PVPVI has an average
molecular weight
range from 5,000 to 1,000,000, more preferably from 5,000 to 200.000, and most
preferably from
10,000 to 20,000. (The average molecular weight range is determined by light
scattering as described in Barth, et al., Chemical Analysis, Vol. 113. "Modern
Methods of Polymer Characterization".) The PVPVI copolymers typically have a
CA 02231691 2002-06-18
18
molar ratio of N-vinylimidazole to N-vinylpyrrolidone from I :1 to 0.2: l,
more preferably from 0.8: I to
0.3:1, most preferably from 0.6:1 to 0.4: I. Those copolymers can be either
linear or branched.
The present invention also may employ as a dye transfer inhibitor a
polyvinylpyrrolidone
("PVP") having an average molecular weight of from about 5.000 to about
400.000, preferably from
about 5,000 to about 200.000, and more preferably from about 5.000 to about
50.000. PVP's are
known to persons skilled in the detergent field; see, for example. EP-A-
262.897 and EP-A-256,696.
Compositions containing PVP dye transfer inhibitors can also contain
polyethylene
glycol ("PEG") having an average molecular weight from about 500 to about
100.000, preferably from about 1,000 to about 10,000. Preferably, the ratio of
PEG to PVP on a ppm
basis delivered in wash solutions is from about 2:1 to about 50:1, and more
preferably from about 3:1
to about 10:1.
Enzymes - Enrymes can be included in the formulations herein for a wide
variety of fabric laundering
purposes, including removal of protein-based, carbohydrate-based, or
triglyceride~based stains, for
example, and for the prevention of refugee dye transfer, and for fabric
restoration. The enzymes to be
incorporated include professes, 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, thetmostability,
stability versus active detergents,
builders and so on. In this respect bactetial or fungal enzymes are preferred,
such as bacterial
amylases and professes, and fungal cellulases.
Enrymes arc 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 0.01%-I% 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 professes are the subtilisins which arc obtained from
particular strains of
8. 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 AIS under
the registered trade mark ESPERASE. The preparation of this enryme and
analogous enzymes is
described in British Patent Specification No. 1,243,784 of Novo. Proteolytic
enrymes suitable for
removing protein-based stains that are commercially available include those
sold under the trademarks
ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by
International
Bio-Synthetics, lnc. (The Netherlands). Other professes include Protease A
(see European Patent
Application 130.756, published January 9, 1985) and Protease B (see European
Patent Application
CA 02231691 2002-06-18
19
No. 251446 published January 7, 1988 and European Patent Application 130,756,
Bott et al., published
January 9, 1985).
Amylases include, for example, -amylases described in British .Patent
Specification No.
1, 296.839 (Novo). RAPIDASE. international Bio-Synthetics, Inc. and TERMAMYL.
Novo Industries.
The cellulose usable in the present invention include both bacterial or fungal
cellulose.
Preferably, they will have a pH optimum of between S and 9.5. Suitable
celtutases arc disclosed in
U.S. Patent 4,435,307, Barbesgoard et at, issued March 6, 1984, which
discloses fungal cellulose
produced from Humicola insolens and Humicota strain DSM 1800 or a cellulose ?
12-producing fungus
belonging to the genus Aeromonas, and cellulose 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. CAREZYME (Novo) is especially useful.
Suitable lipase enrymes for detsrgent usage include those produced by
microorganisms of the
Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in
British Pstent
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 mark Lipase P "Amano," hereinafter referred to as "Amano-P."
Other commercial
lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter
viscosum var.
Iipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagasa,
Japan; and further
Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth
Co., The
rM
Netherlands, and lipases ex Pseudomonas gladioli. The LIPOLASE enzyme derived
from Humicola
lanuginosa 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 arc known in the art, and include, for
example, horseradish
peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-
peroxidase. Peroxidase-
containing detergent compositions are disclosed, for example, in PCT
International Application WO
891099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries
A/S.
A wide range of enryme materials and means for their incorporation into
synthetic detergent
compositions are 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, i 981. Enzymes for use in detergents can be
stabilized by various
techniques. Enzyme stabilization techniques are disclosed and exemplified in
U.S. Patent 3.600.319,
issued August 17, 1971 to Gedge, et al, and European Patent Application
Publication No. 0 199 405,
CA 02231691 2002-06-18
published October 29, 1986, Venegas. Enzyme stabilization systems are also
described, for example,
in U.S. Patent 3,519,570.
Enzyme Stabilizers - The enrymes employed herein arc stabilized by the
presence of water-
5 soluble sources of calcium and/or magnesium ions in the finished
compositions which provide such
ions to the enrymes. (Calcium ions are generally somewhat more effective than
magnesium ions and
are preferred herein if only one type of canon is being used.) Additional
stability can be provided by
the presence of various other an-disclosed stabilizers, especially borate
species: see Severson, U.S.
4.537,706. 'Typical detergents, especially liquids, will comprise from about I
to about 30, preferably
10 from about 2 to about 20, more preferably from about 5 to about I5. 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 enryme 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
15 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
20 water. In solid detergent compositions the formulation may include a
sufficient quantity of a water.
soluble calcium ion source to provide such amounts in the laundry liquor. In
the alternative, natural
water hardness may suffice.
It is to be understood that the foregoing levels of calcium and/or magnesium
ions are
sufficient to provide enzyme stability. More calcium and/or magnesium ions can
be added to the
compositions to provide an additional measure of grease removal performance.
Accordingly, ss a
general proposition the compositions herein will typically comprise from about
0.05% to about 2% by
weight of a water-soluble source of calcium or magnesium ions, or both. The
amount can vary, of
course, with the amount and type of enryme 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 t0%, preferably from about 0.5% to
about 5%, more
preferably from about 0.75% to about 3%, by weight of boric acid or other
borate compound capable
of forming boric acid in the composition (calculated on the basis of boric
acid). Boric acid is
preferred, although other compounds such as boric oxide, borax and other
alkali metal borates (e.g..
sodium ortho-, mete. 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.
CA 02231691 2002-06-18
21
B~achine Comvounds - Bleach~n_gAJ~~r~ts and Bleach Activates . The detergent
composit'rons herein
may optionally contain bleaching agents or bleaching compositions containing a
bleaching agent and
one or mare bleach activators. When 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 uxful for
deter~tent
compositions in textile cleaning, hard surface cleaning, or other cleaning
purposes that arc 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.
Another category of bleaching agent that can be used without rcsaiction
encompasses
percarboxylic acid bleaching agents and salts thereof. Suitable examples of
this class of agents include
magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro
perbenzoic acid, 4-
nonyhunino-4-oxoperoxybutyric acid and diperoxydodecanedioit acid. Such
bleaching agents arc
disclosed in U.S. Patent No.4,483,781, Hatttnan, issued November 20, 1984,
U.S. P
No. 4,806,632, issued February 21,1989, European Patent Application 0,133,354,
Banks et al.,
published February 20, 1985, and U.S. Patent 4,412.934, Chung et a1, 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 peroxyhydrate and equivalent "percarbonate" bleaches,
sodium
pyrophosphue peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
Persulfate bleach (e.g.,
OXONE, manufactured commercially by DuPont) can also be used.
A preferred percarbonate bleach comprises dry particles having an average
particle size in the
range from about 500 micrometers to about 1,000 micrometer, not more than
about 10% by weight of
said particles being smaller than about 200 micrometers and not more than
about 10% by weight of
said particles being larger than about 1,250 micrometers. Optionally, the
percarbonate can be coated
with silicate, borate or water-soluble surfactants. Percarbonate is available
from various commercial
sources such as FMC. Solvay and Tokai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are
preferably cmnbined
with bleach activators, which lead to the in siiw 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 discloxd in U.S. Patent 4,915,854, issued April 10,
1990 to Mso et al, and
U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (HOBS) and tetraacetyl
ethylene diamine
CA 02231691 2002-06-18
22
(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.
Highly preferred amido-derived bleach activators ate those of the formulae:
R1N(RSIC(O)R2C(O)L or R1C(O)N(RS)R2C(O)L
wherein R 1 is an alkyl group containing from about 6 to about 12 carbon
atoms, R2 is an alkylene
containing from 1 to about 6 carbon atoms. RS is H or alkyl, aryl, or alkaryl
containing from about 1
to about 10 carbon atoms, and L is any suitable leaving group. A leaving group
is any group that is
displaced from the bleach activator as a consequtnce of the nucleophilic
attack on the bleach activator
by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-
octanamido-
caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-
decanamido-
caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent
4,634,551.
Another class of bleach activators comprises the benzoxazin-type activators
disclosed by
~5 Hodge et al. in U.S. Patent No. 4,966,723, issued October 30, 1990. A
highly preferred activator of
the benzoxazin-type is:
~g-OO
Still another class of preferred bleach activators includts the aeyl lactam
activators, especially
acyl caprolactams and acyl valerolactams of the formulae:
O
H O ~-C C
O ~-CHT-C ; ~ ~'~2-- H2
.~ CH2 ~--~--~C
'CH2--C!+~ H2-- ~2
,
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from 1 to about 12 carbon
atoms. Highly preferred lactam activators include benzoyl caprolactam,
octanoyi caprolactam. 3,5,5-
trimethylhexanoyl caproiactam, nonanoyl caprolactam, decanoyl caproiactam,
undecenoyl
caprolactam, benzoyl valerolactam, octanoyl vaierolactam, decanoyl
valerolactam, undccenoyl
vaierolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and
mixtures thereof. Sec
also U.S. Patent No. 4,545,784, issued to Sanderson, October 8, 1985, which
discloses aryl
caprolactams, including benzoyl capmlactam, adsorbed into sodium perborate.
Bleaching agents other than oxygen bleaching agents arc also known in the art
and can be
utilized herein. One type of non-oxygen bleathing agent of particular interest
includes photoactivated
bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines.
See U.S. Patent
CA 02231691 1998-03-11
WO 97/10321 PCT/US96/13448
23
4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent
compositions will typically
contain from about 0.025% to about 1.25%, by weight, of such bleaches,
especially sulfonate zinc
phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of a manganese
compound.
Such compounds are well known in the art and include, for example, the
manganese-based catalysts
disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416;
U.S. Pat. 5,114,606; and
European Pat. App. Pub. Nos. 549,271 A 1, 549,272A 1, 544,440A2, and 544,490A
1; Preferred
examples of these catalysts include MntV2(u-O)3(1,4,7-trimethyl-1,4,7-
triazacyclononane)2(PF6)2,
Mnttt2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2_(C104)2,
MntV4(u-O)6(1,4,7-
triazacyclononane)4(C104)4, MnIIIMnIV4(u-O)I(u-OAc)2_(1,4,7-trimethyl-1,4,7
triazacyclononane)2(C104)3, MntV(1,4,7-trimethyl-1,4,7-triazacyclononane)-
(OCH3)3(PF6), and
mixtures thereof. Other metal-based bleach catalysts include those disclosed
in U.S. Pat. 4,430,243
and U.S. Pat. 5,114,611. The use of manganese with various complex ligands to
enhance bleaching is
also reported in the following United States Patents: 4,728,455; 5,284,944;
5,246,612; 5,256,779;
5,280,117; 5,274,147; 5,153,161; and 5,227,084.
As a practical matter, and not by way of limitation, the compositions and
processes herein can
be adjusted to provide on the order of at least one part per ten million of
the active bleach catalyst
species in the aqueous washing liquor, and will preferably provide from about
0.1 ppm to about 700
ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst
species in the laundry
liquor.
Polymeric Soil Release Agent - Any polymeric soil release agent known to those
skilled in
the art can optionally be employed in the compositions and processes of this
invention. Polymeric soil
release agents are characterized by having both hydrophilic segments, to
hydrophilize the surface of
hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to
deposit upon
hydrophobic fibers and remain adhered thereto through completion of washing
and rinsing cycles and,
thus, serve as an anchor for the hydrophilic segments. This can enable stains
occurring subsequent to
treatment with the soil release agent to be more easily cleaned in later
washing procedures.
The polymeric soil release agents useful herein especially include those soil
release agents
having: (a) one or more 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 contains 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,
SUBSTITUTE SHEET (RULE 26)
CA 02231691 2002-06-18
24
said hydrophile segments preferably comprising at last about 25% oxytthyiene
units and more
preferably, especially for such components having about 20 to 30 oxypropyiene
units, at least about
50% oxyethylene units; or (b) one or more hydrophobe components comprising (i)
Cg oxyalkylene
terephthalate segments, wherein, if said hydrophobe components also comprise
oxyethyiene
tercphthalate, tht ratio of oxyethyiene tercphthaiate:C3 oxyalkylene
terephthalate units is about 2:1 or
lower, (ii) C4-C6 alkylene or oxy Cq-C6 alkylene segments, or mixtures
therein, (iii) poly (vinyl tster)
segments, preferably polyvinyl acetate), having a degree of polymerization of
at least 2, or (iv) C 1-C4
alkyl ether or Cq hydroxyalkyl ether substituents, or mixtures therein,
wherein said substituents are
present in the form of Cl-C4 alkyl ether or Cq hydroxyalkyl ether cellulose
derivatives, or mixtures
therein, and such cellulose derivatives are amphiphilic, whereby they have a
sufficient level of C1-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 (axi) will have a degree of
polymerization of
from about 200, although higher levels can be used, preferably from 3 to about
150, more preferably
from 6 to about 100. Suitable oxy Cq-CS alkylene hydrophobe segments include,
but arc not limited
to, end-caps of polymeric soil release agents such as M03S(CH2)nOCH2CH20-,
when M is sodium
and n is an inttger from 4-6, as disclosed in U.S. Patent 4,721,580, issued
January 26, 1988 to
Gosselink.
Polymeric soil release agenu useful in the present invention also include
cellulosic de-
rivatives such as hydroxyether cellulosic polymers, copolymeric blocks of
ethylene tercphthalate or
propylent terephthalate with polyethylene oxide of polypropylene oxide
terephthalate, and the like.
TM
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 C 1-Cq alkyl and C4 hydroxyalkyl cellulose: see U.S. Patent
4,000,093, issued December
28, 1976 to Nicol, et ai.
Soil release agents characterized by polyvinyl ester) hydrophobe segments
include graft
copolymers of polyvinyl ester), e.g., CI-C6 vinyl esters, preferably polyvinyl
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
TM
agents of this kind include the SOKALAN type of material, e.g.. SOKALAN HP-22,
available from
BASF (west Germany).
One type of preferred soil release agent is a copolymer having random blocks
of ethylene
terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight
of this polymeric soil
release agent is in the range of from about 25.000 to about 55.000. See U.S.
Patent 3.959.230 to Hays,
issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
CA 02231691 2002-06-18
Another preferred polymeric soil release agent is a polyester with repeat
units of ethylene
terephthalate units contains 10-t5% by weight of ethylene terephthalate units
togttherwith 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
5 ZELCON 5126 (from Dupont) and M1LEASE T (from ICl). See also U.S. Patent
4,702,857, issued
October 27. 1987 to Gosselink.
Another preferred polymeric soil release agent is a sulfonated product of a
substantially linear
ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and
oxyalkyleneoxy repeat
units and terminal moieties covalently attached to the backbone. These soil
release agents are
10 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 2?, 1987 to Gosselink.
15 Preferred polymeric soil release agenu 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 sul-
foarolyl, cnd-capped terephthalate esters.
If utilized, soil release agenu will generally comprise from about 0.01% to
about 10.0°/., by
weight, of the detergent compositions herein, typically from about 0.1% to
about 5%, preferably.from
20 about 0.2% to about 3.0%.
Still another preferred soil release agent is an oligomer with repeat uniu of
tercphthaloyl
units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene
units. The repeat units form
the backbone of the oligomer and arc preferably terminated with modified
isethionate end-caps. A
paniculariy preferred soil release agent of this type comprises about one
sulfoisophthaloyl unit, 5
25 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a
ratio of from about 1.7 to
about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxyrethanesulfonate.
Said soil release
agent also comprises from about 0.5% to about 20~/0, by weight of the
oligomer, of a crystalline-
reducing stabilizer, preferably selected from the group consisting of xylene
sulfonate, cumene
sulfonatc, toluene sulfonate, and mixtures thereof.
PROCESS
Included in the present invention is a process for making a structured
detergent composition
consisting essentially of the surfactant and the hydrophilic, finely-divided
silica. The process
comprises the step of mixing an paste of the surfactant with the finely
divided hydrophilic silica, under
adequate mixing to intimately combine the components into an homogeneous
mixture. The silica is
well-dispersed in the structured detergent composition. The resultant
detergent composition has a
hardened or firmer physical structure than the detergent surfactant.
CA 02231691 2002-06-18
26
Also included in the present invention is a process for making a structured
surfactant
composition for a detergent composition comprising the steps of:
a) Mixing from about I% to about 20% of a hydrophilic, finely-divided
particulate
silica and from about 35% to about 60% of a detergent surfactant, thereby
forming a
hardened paste;
b) Applying shear force to the hardened paste to form a ilowable liquid; and
c) Dispersing the flowable liquid into fine droplets and agglomerting with dry
detergent
powder comprising other detergent adjuvants selected from the group consisting
of
other detergent surfactant, detergent builders, silica, and mixtures thereof,
to form
particles.using a high speed mixer.
The silica particulate is preferably a hydrophilic precipitated silica and the
detergent
surfactant paste is an anionic surfactant, most preferably alkylaUcoxy sulfate
comprising an alkyl
portion of from 6 to 18 carbon atoms and an alkoxy portion comprising, an
average, from about 0.5 to
about 20 moles of alkoxy, preferably ethoxy, units, morn preferably from about
0.5 to about 5 ethoxy
units.
In order to make the structured surfactant composition, any suitable apparatus
capable of
handling viscous paste is required. Suitable apparatus includes, for example,
twin-screw extruders,
rM
Teledyne compounders, etc.
In order to make a detergent composition comprising the structured surfactant
composition, suitable
apparatus includes, for example, mixeNagglomerators can be used. In one
prtferred embodiment, the
process of the invention is continuously carried out.
The process preferably further comprises another step wherein the granulated
surfactant
composition is dusted with silica or zeolite.
EXAMPLES
xam ie 1
The structured surfactant composition can be made in the following way: the
hydrophilic silica
particulate is mixed with an alkylethoxy sulfate paste in a single-screw or
twin-screw extruder. The
pre-mot of soda ash, builder, zeolite and precipitated silica is agglomerated
with the structured
surfactant composition in a plowshare mixer. The resulting particle has a
density of 600 to 800 g11.
xa 1 2
CA 02231691 1998-03-11
WO 97/10321 PCT/US96/13448
27
Ingredient %
CFAS 21
CFA I
AE45-T O.g
Structured Surfactant Composition 3.3
*
of Example 1
STPP 22.5
Zeolite 12.6
Polymer 0.7
Other detergent adjuvants Balance
*Structured surfactant composition is comprised of AE3S at 70%, Hydrophilic
precipitated silica at
2% and water at 28%.
Example 3
Ingredient %
LAS 20.7
STPP 22.7
Carbonate 22
Zeolite 14
Structured surfactant Composition*3.3
of Example I
Other detergent adjuvants Balance
*Structured surfactant composition is comprised of AE3S at 70%, Hydrophilic
precipitated silica at
2% and water at 28%.
Examvle 4
Ingredient
LAS 24.5
STPP 17.9
Soda Ash 30
Zeolite 11.9
x Surfactant Composition (AE3S)* 3.3
of Example 1
Other detergent adjuvants Balance
SUBSTITUTE SHEET (RULE 26)
CA 02231691 1998-03-11
WO 97/10321 PCT/US96/13448
28
*Structured surfactant composition is comprised of AE3S at 70%, Hydrophilic
precipitated silica at
2% and water at 28%.
SUBSTITUTE SHEET (RULE 26)
