Note: Descriptions are shown in the official language in which they were submitted.
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1
LOW DENSITY ENZYME GRANULATES
AND COMPOSITIONS EMPLOYING SAME
FIELD OF THE INVENTION
This invention relates to laundry detergent products, such as heavy duty
aqueous
and/or non-aqueous and/or gelled liquid laundry detergents and powder laundry
detergents, which include one or more enzyme granulates comprising one or more
enzyme granulate density-reducing components and one or more enzymes, and
optionally
one or more conventional cleaning adjunct materials.
BACKGROUND OF THE INVENTION
The incorporation of conventional enzymes into conventional liquid laundry
detergents has been problematic due to the tendency of enzymes, typically in
the form of
enzyme granulates, to sediment and/or settle out of liquid detergent products,
especially
during storage and/or transportation of the liquid detergent products. This
problem is
also present, although usually not to the same extent, in granular and/or
powder laundry
detergents wherein the enzyme granulates tend to sediment and/or settle out of
the
granular and/or powder detergent products during storage, transportation
and/or any other
activity that results in sifting of the products.
In light of the foregoing, it is evident that formulators of liquid laundry
detergent
comprising enzymes have encounter a challenge to stably suspend the enzymes in
the
form of granulates in the liquid laundry detergents.
There is a need to formulate liquid laundry detergent compositions having
stably
suspended enzymes in the form of enzyme granulates.
There is a need to formulate granular and/or powder laundry detergent
compositions having stably suspended enzymes in the form of enzyme granulates.
There is a need to provide methods for producing the enzyme granulates that
can
be stably suspended in laundry detergent compositions.
Accordingly, there is a need to identify materials and procedures which can be
used to stably suspend and/or incorporate enzymes in the form of enzyme
granulates into
liquid and/or granular and/or powder laundry detergent products.
SUMMARY OF THE INVENTION
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The present invention fulfills the needs identified above by providing enzyme
granulates that have properties such that the tendency of such enzyme
granulates to
sediment or settle out of liquid and/or granular and/or powder laundry
detergent products
is reduced; methods of making such enzyme granulates; compositions comprising
such
enzyme granulates; and products comprising such enzyme granulates.
Surprisingly it has been found that by incorporating enzyme granulate density-
reducing components into the enzyme granulates, the enzyme granulates of the
present
invention can be stably suspended into liquid and/or granular and/or powder
laundry
detergent products.
By stably suspending the enzyme granulates of the present invention in the
liquid
and/or granular and/or powder laundry detergent products, the enzyme
granulates of the
present invention have a reduced tendency to sediment and/or settle out of the
laundry
detergent products during storage and/or transportation.
As a result of the enzyme granulates having a reduced tendency to sediment
and/or settle out of the laundry detergent products, consumers can have more
conistent
doses with respect to the level of actives, especially the enzyme granulates,
per dose.
In one aspect of the present invention an enzyme granulate comprising an
enzyme
granulate density-reducing component is provided.
In another aspect of the present invention a liquid and/or granular and/or
powder
laundry detergent composition comprising the enzyme granulate of the present
invention
is provided.
In still another aspect of the present invention a liquid and/or granular
and/or
powder laundry detergent product comprising the enzyme granulate of the
present
invention is provided.
In yet another aspect of the present invention a method for producing the
enzyme
granulate of the present invention is provided.
In still yet another aspect of the present invention a method for laundering
fabrics
comprising contacting the fabrics with the enzyme granulate of the present
invention,
preferably a liquid and/or granular and/or powder laundry detergent comprising
the
enzyme granulate of the present invention, is provided.
It is an object of the present invention to formulate enzyme granulates that
have
properties such that the tendency of such enzyme granulates to sediment or
settle out of
liquid and/or granular and/or powder laundry detergent products is reduced.
These and other aspects, objects, features and advantages will be clear from
the
following detailed description, examples and appended claims.
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All percentages, ratios and proportions herein are on a weight basis unless
otherwise indicated. All documents cited herein are hereby incorporated by
reference.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to enzyme granulates that comprising enzyme
granulated density-reducing components which reduce the tendency of such
enzyme
granulates to sediment and/or settle out of liquid and/or granular and/or
powder laundry
detergent compositions.
"Enzyme granulate" as used herein is meant to encompass any solid form into
which one or more enzymes are physically and/or chemically incorporated.
Typically,
enzyme granulates are low-dusting, free-flowing granules, with a diameter
between about
200 and 1000~m. Such enzyme granulates can be formed by any suitable
granulation
process. For example, the enzyme granulate may be a T-granulate, such as the T-
granulates made by the process described in U.S. Patent Nos. 4,106,991,
4,661,452 and
4,876,198 all to Novo Nordisk A/S; a granulate made by the spray-chilling or
prilling
process as described by H. A. Herrmann, I. Good, A. Laufer in Surfactant
Science Series,
Vol. 69, Enzymes in Detergency, Marcel Dekker, Inc., New York, 1997, pp. 281-
286,
314; a granulate made by an extrusion and optionally spheronization process,
such as the
MOM process as described in U.S. Patent No. 4,242,219 to Gist-Brocades, U.S.
Patent
No. 4,661,452 to Novo Nordisk A/S, GB Patent No. 1 362 365 and/or as described
by H.
A. Hemnann, I. Good, A. Laufer in Surfactant Science Series, Vol. 69, Enzymes
in
Detergency, Marcel Dekker, Inc., New York, 1997, pp. 286-287, 314-31 S; a
granulate
made by a fluidized bed spray coating process as described in U.S. Patent No.
4,689,297
to Miles Laboratories, U.S. Patent No. 5,324,649 to Genencor International
and/or by H.
A. Herrmann, I. Good, A. Laufer in Surfactant Science Series, Vol. 69, Enzymes
in
Detergency, Marcel Dekker, Inc., New York, 1997, pp. 287-293, 316-318; or a
granulate
made by the fast mixer process as described by H. A. Herrmann, I. Good, A.
Laufer in
Surfactant Science Series, Vol. 69, Enzymes in Detergency, Marcel Dekker,
Inc., New
York, 1997, pp. 280-281.
"Enzyme granulate density-reducing components" herein is meant any component
that when incorporated into the enzyme granulate results in the enzyme
granulate having
a reduced density compared to the density of the enzyme granulate prior to the
incorporation of the enzyme granulate density-reducing component(s). Suitable
examples of enzyme granulate density-reducing components include, but are not
limited
to, microspheres (liquid hydrocarbon-containing and/or gas-containing
depending upon
temperature, and/or hollow), cavities, pores, and other components that result
in a
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reduction of the density of an enzyme granulate compared to the density of the
enzyme
granulate prior to incorporation of the component(s).
ENZYME GRANULATE
The enzyme granulate of the present invention comprises
(a) one or more enzyme granulate density-reducing components of the present
invention; and
(b) one or more enzymes.
Enzyme Granulate Density-Reducing Components - Preferably, the enzyme
granulate density-reducing components are selected from the group consisting
of:
microspheres, cavity-forming components, pore-forming components and mixtures
thereof. More preferably, the enzyme granulate density-reducing component is
selected
from the group consisting of microspheres, preferably liquid hydrocarbon-
containing
and/or gas-containing microspheres, more preferably liquid hydrocarbon-
containing
and/or gas-containing microspheres made of one or more materials selected from
the
group consisting of: plastics; proteins; silicaceous materials; ceramics and
mixtures
thereof.
Plastic microspheres of the present invention are preferably made of one or
more
plastics selected from the group consisting o~ thermoplastics; acylonitrile;
methacrylonitrile; polyacrylonitrile; polymethacrylonitrile and mixtures
thereof.
Silicaceous microspheres of the present invention are preferably made of one
or
more silicaceous materials selected from the group consisting of glass.
It is desirable that the microspheres of the present invention are capable of
expanding such that the microspheres' volume increases. It is even more
desirable that
the microspheres of the present invention are made of a material such that the
density of
the expanded microsphere is less than about 0.4 g/mL, more preferably less
than about
0.2 g/mL, most preferably less than about 0.1 g/mL.
In order to aid in the expansion of the microspheres, it is desirable that the
microspheres contain a suitable expanding agent. The expanding agent can be
selected
from the group consisting of liquid hydrocarbons, gases, and mixtures thereof.
Suitable
liquid hydrocarbons are liquid hydrocarbons that are vaporizable at a
temperature lower
than the softening point of the microsphere material. Examples include, but
are not
limited to, propane, propylene, butene, n-butane, isobutane, isopentane,
neopentane, n-
pentane, hexane, heptane, petroleum ether, halogenized methane,
tetraalkylsilane and the
like. In addition to the liquid hydrocarbons, which may be in gas form
depending upon
the temperature, the expanding agents may also be selected from the group
consisting of
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S
nitrogen, carbon dioxide, oxygen, and mixtures thereof. Preferably, the
expanding agent
is isobutane.
Commercially available microspheres are available from Expancel of Sweden (an
Akzo Nobel company) under the trademark EXPANCEL~; PQ Corp. under the trade
names PM 6545, PM 6550, PM 7220, PM 7228, EXTENDOSPHERES~, LUXSIL,~, Q-
CEL~, SPHERICEL~; and Malinckrodt under the trademark ALBUMEX~.
The enzyme granulates of the present invention preferably have a particle
density
of from about 0.8 to about 2.1 g/mL, more preferably from about 0.8 to about
1.5 g/mL,
most preferably from about 0.9 to about 1.2 g/mL.
Enzymes - With respect to the enzymes in the enzyme granulate of the present
invention, any suitable enzyme can be used. The preferred enzymes for use in
the
enzyme granulates of the present invention are selected from proteases,
amylases,
cellulases and mixtures thereof. Nonlimiting examples of other suitable
enzymes include
the following:
Examples of suitable enzymes include, but are not limited to, hemicellulases,
peroxidases, proteases, cellulases, xylanases, lipases, phospholipases,
esterases,
cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases,
lipoxygenases,
ligninases, pullulanases, tannases, pentosanases, malanases,13-glucanases,
arabinosidases,
hyaluronidase, chondroitinase, laccase, mannanases, more preferably plant cell
wall
degrading enzymes and non-cell wall-degrading enzymes (WO 98/39403 A) and can,
more specifically, include pectinase (WO 98/06808 A, JP10088472 A, JP10088485
A);
pectolyase (W098/06805 Al); pectin lyases free from other pectic enzymes
(W09806807 Al); chondriotinase ( EP 747,469 A); xylanase ( EP 709,452 A, WO
98/39404 A, W098/39402 A) including those derived from microtetraspora
Jleruosa
(US 5683911); isopeptidase (WO 98/16604 A); keratinase (EP 747,470 A, WO
98/40473 A); lipase ( GB 2,297,979 A; WO 96/16153 A; WO 96/12004 A; EP 698,659
A; WO 96/16154 A); cellulase or endoglucanase (GB 2,294,269 A; WO 96/27649 A;
GB 2,303,147 A; W098/03640 A; see also neutral or alkaline cellulases derived
from
chrysosporium lucknowense strain VKM F-3500D as disclosed in W09815633 A);
polygalacturonase (WO 98/06809 A); mycodextranase (WO 98/13457 A); thermitase
(WO 96/28558 A); cholesterol esterase (WO 98 28394 A); or any combination
thereof;
and known amylases; oxidoreductases; oxidases or combination systems including
same
(DE19523389 Al ); mutant blue copper oxidases (W09709431 A1), peroxidases (see
for
example US 5,605,832, W097/31090 A1), mannanases (W09711164 A1); laccases, see
W09838287 Al or W09838286 A1 or for example, those laccase variants having
amino
acid changes in myceliophthora or scytalidium laccase(s) as described in
W09827197 Al
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or mediated laccase systems as described in DE19612193 A1), or those derived
from
coprinus strains (see, for example W09810060 A1 or W09827198 Al), phenol
oxidase
or polyphenol oxidase (JP10174583 A) or mediated phenol oxidase systems
(W09711217 A); enhanced phenol oxidase systems (WO 9725468 A W09725469 A);
phenol oxidases fused to an amino acid sequence having a cellulose binding
domain
(W09740127 Al, W09740229 A1) or other phenol oxidases (W09708325 A,
W09728257 Al) or superoxide dismutases. Oxidoreductases and/or their
associated
antibodies can be used, for example with H202, as taught in WO 98/07816 A.
Depending
on the type of detergent composition, other redox-active enzymes can be used,
even, for
example, catalases (see, for example JP09316490 A).
Also useful herein are any oxygenases of extracellular origin, especially
fungal
oxygenase such as dioxygenase of extracellular origin. The latter is most
especially
quercetinase, catechinase or an anthocyanase, optionally in combination with
other
suitable oxidase, peroxidase or hydrolytic enzymes, all a taught in W09828400
A2.
Examples of such suitable enzymes and/or levels of use are disclosed in U.S.
Patent Nos. 5,705,464, 5,710,115, 5,576,282, 5,728,671 and 5,707,950
The cellulases useful in the present invention include both bacterial or
fungal
cellulases. Preferably, they will have a pH optimum of between 5 and 12 and a
specific
activity above 50 CEVU/mg (Cellulose Viscosity Unit). Suitable cellulases are
disclosed
in U.S. Patent 4,435,307, J61078384 and W096/02653 which discloses fungal
cellulase
produced respectively from Humicola insolens, Trichoderma, Thielavia and
Sporotrichum. EP 739 982 describes cellulases isolated from novel Bacillus
species.
Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-
OS-
2.247.832 and W095/26398.
Examples of such cellulases are cellulases produced by a strain of Humicola
insolens (Humicola grisea var. thermoidea), particularly the Humicola strain
DSM 1800.
Other suitable cellulases are cellulases originated from Humicola insolens
having
a molecular weight of about SOKDa, an isoelectric point of 5.5 and containing
415 amino
acids; and a "43kD endoglucanase derived from Humicola insolens, DSM 1800,
exhibiting cellulase activity; a preferred endoglucanase component has the
amino acid
sequence disclosed in WO 91/17243. Also suitable cellulases are the EGIII
cellulases
from Trichoderma longibrachiatum described in W094/21801 to Genencor.
Especially
suitable cellulases are the cellulases having color care benefits. Examples of
such
cellulases are cellulases described in European patent application No.
91202879.2, filed
November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are
especially
useful. See also W091/17244 and W091/21801. Other suitable cellulases for
fabric care
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and/or laundry properties are described in W096/34092, W096/17994 and
W095/24471.
Peroxidase enzymes are used in combination with oxygen sources, e.g.
percarbonate, perborate, persulfate, hydrogen peroxide, etc and with a
phenolic substrate
as bleach enhancing molecule. 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. Suitable peroxidases and peroxidase-containing detergent
compositions are disclosed, for example, in U.S. Patent Nos. 5,705,464,
5,710,115,
5,576,282, 5,728,671 and 5,707,950, PCT International Application WO
89/099813,
W089/09813 and in European Patent application EP No. 91202882.6, filed on
November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable
is the
laccase enzyme.
Suitable enhancers are selected from the group consisting of substituted
phenthiazine and phenoxasine 10-Phenothiazinepropionicacid (PPT), 10-
ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP)
and
10-methylphenoxazine (described in WO 94/12621), substitued syringates (C3-CS
substitued alkyl syringates), phenols and mixtures thereof. Sodium
percarbonate or
perborate are preferred sources of hydrogen peroxide.
Enzymatic systems may be used as bleaching agents. The hydrogen peroxide may
also be present by adding an enzymatic system (i.e. an enzyme and a substrate
therefore)
which is capable of generating hydrogen peroxide at the beginning or during
the washing
and/or rinsing process. Such enzymatic systems are disclosed in EP Patent
Application
91202655.6 filed October 9, 1991.
Other preferred enzymes that can be included in the laundry compositions of
the
present invention include lipases. 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. Suitable
lipases include
those which show a positive immunological cross-reaction with the antibody of
the
lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This
lipase
is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the
trade name
Lipase P "Amano," hereinafter referred to as "Amano-P". Other suitable
commercial
lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter
viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan;
Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth
Co.,
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The Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable
lipases are
lipases such as M1 LipaseR and LipomaxR (Gist-Brocades) and LipolaseR and
Lipolase
UltraR(Novo) which have found to be very effective when used in combination
with the
compositions of the present invention. Also suitable are the lipolytic enzymes
described
in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578,
WO 95/35381 and WO 96/00292 by Unilever.
Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special
kind of lipase, namely lipases which do not require interfacial activation.
Addition of
cutinases to laundry compositions have been described in e.g. WO-A-88/09367
(Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964
(Unilever).
In addition to the above referenced lipases, phospholipases may be
incorporated
into the laundry compositions of the present invention. Nonlimiting examples
of suitable
phospholipases included: EC 3.1.1.32 Phospholipase A1; EC 3.1.1.4
Phospholipase A2;
EC 3.1.1.5 Lysopholipase; EC 3.1.4.3 Phospholipase C; EC 3.1.4.4. Phospolipase
D.
Commercially available phospholipases include LECITASE~ from Novo Nordisk A/S
of
Denmark and Phospholipase A2 from Sigma. When phospolipases are included in
the
compositions of the present invention, it is preferred that amylases are also
included.
Without desiring to be bound by theory, it is believed that the combined
action of the
phospholipase and amylase provide substantive stain removal, especially on
greasy/oily,
starchy and highly colored stains and soils. Preferably, the phospholipase and
amylase,
when present, are incorporated into the compositions of the present invention
at a pure
enzyme weight ratio between 4500:1 and 1:5, more preferably between 50:1 and
1:1.
Suitable proteases are the subtilisins which are obtained from particular
strains of
B. subtilis and B. liclZeniformis (subtilisin BPN and BPN'). One suitable
protease is
obtained from a strain of Bacillus, having maximum activity throughout the pH
range of
8-12, developed and sold as ESPERASE~ by Novo Industries A/S of Denmark,
hereinafter "Novo". The preparation of this enzyme and analogous enzymes is
described
in GB 1,243,784 to Novo. Proteolytic enzymes also encompass modified bacterial
serine
proteases, such as those described in European Patent Application Serial
Number 87
303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which
is called
herein "Protease B", and in European Patent Application 199,404, Venegas,
published
October 29, 1986, which refers to a modified bacterial serine proteolytic
enzyme which is
called "Protease A" herein. Suitable is the protease called herein "Protease
C", which is a
variant of an alkaline serine protease from Bacillus in which Lysine replaced
arginine at
position 27, tyrosine replaced valine at position 104, serine replaced
asparagine at
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9
position 123, and alanine replaced threonine at position 274. Protease C is
described in
EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991.
Genetically
modified variants, particularly of Protease C, are also included herein.
A preferred protease referred to as "Protease D" is a carbonyl hvdrolase as
described in U.S. Patent No. 5,677,272, and W095/10591. Also suitable is a
carbonyl
hydrolase variant of the protease described in W095/10591, having an amino
acid
sequence derived by replacement of a plurality of amino acid residues replaced
in the
precursor enzyme corresponding to position +210 in combination with one or
more of the
following residues : +33, +62, +67, +76, +100, +101, +103, +104, +107, +128,
+129,
+130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218,
and
+222, where the numbered position corresponds to naturally-occurring
subtilisin from
Bacillus amyloliguefaciens or to equivalent amino acid residues in other
carbonyl
hydrolases or subtilisins, such as Bacillus lentus subtilisin (co-pending
patent application
US Serial No. 60/048,550, filed June 04, 1997 and PCT International
Application Serial
No. PCT/IB98/00853).
Also suitable for the present invention are proteases described in patent
applications EP 251 446 and WO 91/06637, protease BLAP~ described in
W091/02792
and their variants described in WO 95/23221.
See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO
93/18140 A to Novo. Enzymatic detergents comprising protease, one or more
other
enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to
Novo.
When desired, a protease having decreased adsorption and increased hydrolysis
is
available as described in WO 95/07791 to Procter & Gamble. A recombinant
trypsin-
like protease for detergents suitable herein is described in WO 94/25583 to
Novo. Other
suitable proteases are described in EP 516 200 by Unilever.
Particularly useful proteases are described in PCT publications: WO 95/30010;
WO 95/30011; and WO 95/29979. Suitable proteases are commercially available as
ESPERASE~, ALCALASE~, DURAZYM~, SAVINASE~, EVERLASE~ and
KANNASE~ all from Novo Nordisk A/S of Denmark, and as MAXATASE~,
MAXACALO, PROPERASE~ and MAXAPEM~ all from Genencor International
(formerly Gist-Brocades of The Netherlands).
Preferred proteases useful herein include certain variants ( WO 96/2866 A; WO
96/28557 A; WO 96/28556 A; WO 96/25489 A).
Other particularly useful proteases are multiply-substituted protease variants
comprising a substitution of an amino acid residue with another naturally
occurring
amino acid residue at an amino acid residue position corresponding to position
103 of
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WO 00/46332 PCT/US00/02666
Bacillus amyloliquefaciens subtilisin in combination with a substitution of an
amino acid
residue with another naturally occurring amino acid residue at one or more
amino acid
residue positions corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16,
17, 18, 19, 20,
21, 22, 24, 27, 33, 37, 38, 42, 43, 48, SS, S7, S8, 61, 62, 68, 72, 7S, 76,
77, 78, 79, 86, 87,
89, 97, 98, 99, 101, 102, 104, 106, 107, 109, 111, 114, 116, 117, 119, 121,
123, 126, 128,
130, 131, 133, 134, 137, 140, 141, 142, 146, 147, 158, 159, 160, 166, 167,
170, 173, 174,
177, 181, 182, 183, 184, 185, 188, 192, 194, 198, 203, 204, 205, 206, 209,
210, 21 l, 212,
213, 214, 215, 216, 217, 218, 222, 224, 227, 228, 230, 232, 236, 237, 238,
240, 242, 243,
244, 245, 246, 247, 248, 249, 251, 252, 253, 254, 2SS, 256, 257, 258, 259,
260, 261, 262,
263, 265, 268, 269, 270, 271, 272, 274 and 275 of Bacillus amyloliquefacierts
subtilisin;
wherein when said protease variant includes a substitution of amino acid
residues at
positions corresponding to positions 103 and 76, there is also a substitution
of an.amino
acid residue at one or more amino acid residue positions other than amino acid
residue
positions corresponding to positions 27, 99, 101, 104, 107, 109, 123, 128,
166, 204, 206,
210, 216, 217, 218, 222, 260, 265 or 274 of Bacillus amyloliquefacierts
subtilisin and/or
multiply-substituted protease variants comprising a substitution of an amino
acid residue
with another naturally occurnng amino acid residue at one or more amino acid
residue
positions corresponding to positions 62, 212, 230, 232, 252 and 257 of
Bacillus
amyloliquefaciens subtilisin as described in PCT Application Nos.
PCT/LTS98/22588,
PCT/US98/22482 and PCT/LJS98/22486 all filed on October 23, 1998 from The
Procter
& Gamble Company (P&G Cases 7280&, 7281 & and 7282L, respectively). More
preferably the protease variant includes a substitution set selected from the
group
consisting o~
12/76/ 103/ 104/130/222/245/261;
62/103/104/1 59/232/236/245/248/252;
62/103/104/1 59/213/232/236/245/248/252;
62/101/103/104/1 59/212/213/232/236/245/248/252;
68/ 103/ 104/ 1 S 9/232/236/245;
68/103/104/159/230/232/236/245;
68/103/104/159/209/232/236/245;
68/103/104/1 59/232/236/245/257;
68/76/103/104/1 59/213/232/236/245/260;
68/103/104/159/213/232/236/245/248/252;
68/103/104/1 59/183/232/236/245/248/252;
68/103/104/159/185/232/236/245/248/252;
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WO 00/46332 PCT/US00/02666
11
68/103/104/159/185/210/232/23G/245/248/252;
G8/103/104/159/210/232/236/245/248/252;
68/103/104/159/213/232/236/245;
98/103/104/159/232/236/245/248/252;
98/102/103/104/159/212/232/236/245/248/252;
1 O 1 / 103/ 104/ 159/232/236/245/248/252;
102/103/104/159/232/236/245/248/252;
103/ 104/ 159/230/236/245;
103/104/159/232/236/245/248/252;
103/104/159/217/232/236/245/248/252;
103/104/130/159/232/236/245/248/252;
103/104/131/159/232/236/245/248/252;
103/104/159/213/232/236/245/248/252; and
103/ 104/ 159/232/236/245.
Still even more preferably the protease variant includes a substitution set
selected from
the group consisting of:
12R/76D/103A/ 104T/130T/222S/245R/261 D;
62D/103A/104I/159D/232V/236H/245R/248D/252K;
62D/103A/104I/159D/213R/232V/236H/245R/248D/252K;
68A/103A/104I/159D/209W/232V/236H/245R;
68A/76D/103A/104I/159D/213R/232V/23GH/245R/2GOA;
68A/103A/104I/159D/213E/232V/236H/245R/248D/252K;
68A/103A/104I/159D/183D/232V/236H/245R/248D/252K;
68A/103A/104I/159D/232V/236H/245R;
68A/103A/104I/159D/230V/232V/236H/245R;
68A/103A/104I/159D/232V/236H/245R/257V;
68A/103A/104I/159D/213G/232V/236H/245R/248D/252K;
68A/103A/104I/159D/185D/232V/23GH/245R/248D/252K;
68A/ 103A/ 104I/ 159D/ 185D/21 OL/232V/236H/245R/248D/252K;
68A/103A/104I/159D/210L/232V/236H/245R/248D/252K;
68A/103A/104I/159D/213G/232V/236H/245R;
98L/103A/104I/159D/232V/23GH/245R/248D/252K;
98L/102A/103A/104I/159D/212G/232V/236H/245R/248D/252K;
1 O l G/ 103A/ 104I/ 15 9D/232 V/236H/245R/248D/252K;
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WO 00/46332 PCT/US00/02666
12
102A/103A/104I/159D/232V/236H/245R/248D/252K;
103A/104I/159D/230V/236H/245R;
103A/104I/159D/232V/236H/245R/248D/252K;
103A/104I/159D/217E/232V/236H/245R/248D/252K;
103A/104I/1306/159D/232V/236H/245R/248D/252K;
103A/104I/131 V/159D/232V/236H/245R/248D/252K;
103A/104I/159D/213R/232V/236H/245R/248D/252K; and
103A/104I/159D/232V/236H/245R.
Most preferably the protease variant includes the substitution set
101/103/104/159/232/236/245/248/252, preferably lOIG/103A/104I/159D/232V/
236H/245R/248D/252K.
Bleach/amylase/protease combinations (EP 755,999 A; EP 756,001 A; EP
756,000 A) are also useful.
Also in relation to enzymes herein, enzymes and their directly linked
inhibitors,
e.g., protease and its inhibitor linked by a peptide chain as described in WO
98/13483 A,
are useful in conjunction with the present hybrid builders. Enzymes and their
non-linked
inhibitors used in selected combinations herein include protease with protease
inhibitors
selected from proteins, peptides and peptide derivatives as described in WO
98/13461 A,
WO 98/13460 A, WO 98/13458 A, WO 98/13387 A.
Amylases can be used with amylase antibodies as taught in WO 98/07818 A and
WO 98/07822 A, lipases can be used in conjunction with lipase antibodies as
taught in
WO 98/07817 A and WO 98/06810 A, proteases can be used in conjunction with
protease antibodies as taught in WO 98/07819 A and WO 98/06811 A, Cellulase
can be
combined with cellulase antibodies as taught in WO 98/07823 A and WO 98/07821
A.
More generally, enzymes can be combined with similar or dissimilar enzyme
directed
antibodies, for example as taught in WO 98/07820 A or WO 98/06812 A.
The preferred enzymes herein can be of any suitable origin, such as vegetable,
animal, bacterial, fungal and yeast origin.
Preferred selections are influenced by factors such as pH-activity and/or
stability
optima, thermostability, and stability to active detergents, builders and the
like. In this
respect bacterial or fungal enzymes are preferred, such as bacterial amylases
and
proteases, and fungal cellulases.
Amylases (a and/or 13) can be included for removal of carbohydrate-based
stains.
W094/02597 describes laundry compositions which incorporate mutant amylases.
See
also W095/10603. Other amylases known for use in laundry compositions include
both
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WO 00/46332 PCT/US00/02666
13
a- and (3-amylases. a-Amylases are known in the art and include those
disclosed in US
Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP
525,610;
EP 368,341; and British Patent specification no. 1,296,839 (Novo). Other
suitable
amylases are stability-enhanced amylases described in W094/18314 and
W096/05295,
Genencor, and amylase variants having additional modification in the immediate
parent
available from Novo Nordisk A/S, disclosed in WO 95/10603. Also suitable are
amylases described in EP 277 216.
Examples of commercial a-amylases products are Purafect Ox Am~ from
Genencor and Termamyl~, Ban~ ,Fungamyl~ and Duramyl~, all available from Novo
Nordisk A/S Denmark. W095/26397 describes other suitable amylases : a-amylases
characterised by having a specific activity at least 25% higher than the
specific activity of
Termamyl~ at a temperature range of 25°C to 55°C and at a pH
value in the range of 8
to 10, measured by the Phadebas~ a-amylase activity assay. Suitable are
variants of the
above enzymes, described in W096/23873 (Novo Nordisk). Other amylolytic
enzymes
with improved properties with respect to the activity level and the
combination of
thermostability and a higher activity level are described in W095/35382.
The above-mentioned enzymes may be of any suitable origin, such as vegetable,
animal, bacterial, fungal and yeast origin. Origin can further be mesophilic
or
extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic,
alkalophilic,
acidophilic, halophilic, etc.). Purified or non-purified forms of these
enzymes may be
used. Nowadays, it is common practice to modify wild-type enzymes via protein
/ genetic
engineering techniques in order to optimize their performance efficiency in
the laundry
detergent and/or fabric care compositions of the invention. For example, the
variants may
be designed such that the compatibility of the enzyme to commonly encountered
ingredients of such compositions is increased. Alternatively, the variant may
be designed
such that the optimal pH, bleach or chelant stability, catalytic activity and
the like, of the
enzyme variant is tailored to suit the particular laundry application.
In particular, attention should be focused on amino acids sensitive to
oxidation in
the case of bleach stability and on surface charges for the surfactant
compatibility. The
isoelectric point of such enzymes may be modified by the substitution of some
charged
amino acids, e.g. an increase in isoelectric point may help to improve
compatibility with
anionic surfactants. The stability of the enzymes may be further enhanced by
the creation
of e.g. additional salt bridges and enforcing calcium binding sites to
increase chelant
stability.
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WO 00/46332 PCT/US00/02666
14
Other suitable detergent ingredients that can be added are enzyme oxidation
scavengers. Examples of such enzyme oxidation scavengers are ethoxylated
tetraethylene
polyamines.
A range of enzyme materials are also disclosed in WO 9307263 and WO
9307260 to Genencor International, WO 8908694, and U.S. 3,553,139, January 5,
1971
to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, and in U.S.
4,507,219. Enzyme materials particularly useful for liquid detergent
formulations, and
their incorporation into such formulations, are disclosed in U.S. 4,261,868.
GRANULATION PROCESSES
The enzyme granulates of the present invention can be made by any conventional
granulation process known in the art, including but not limited to fluid-bed
agglomeration/coating; mechanical agglomeration; extrusion; spray-drying; etc.
Further,
the enzyme granulate density-reducing components of the present invention may
be
incorporated into the enzyme granulates of the present invention at any step
in the
granulation process.
A preferred granulation process is the T-granulation process an example of
which
is described in U.S. Patent Nos. 4,106,991, 4,661,452 and 4,876,198 all to
Novo Nordisk
A/S.
The T-granulation process consists of (1) an agglomerator, preferably a
"ploughshare" type mixer or Schugi type mixer with horizontal or vertical
shafts,
equipped with blenders, wherein fibrous cellulose is agglomerated with
enzymes; and
optionally, (2) a top-spray fluid bed coater, wherein the enzyme granulate
produced from
step (1) is coated with protective coatings, such as PEG 4000, TiOz, and
sodium
thiosulfate.
The enzyme granulate density-reducing components of the present invention may
be incorporated into the enzyme granulates during the agglomeration step or
the coating
step of the T-granulation process, preferably the agglomeration step.
Another preferred granulation process is the fluidized bed top-spray coating
process, an example of which is described in U.S. Patent No. 5,324,649 to
Genencor
International.
The fluidized bed top-spray coating process consists of suspending one or more
sugar particles (300-SOO~m) in the coater with the use of air, and then
coating the sugar
particles with various layers of materials, such as a sugar/starch layer, an
enzyme solution
layer, another sugar/starch layer and a polymeric layer. The enzyme granulate
density-
reducing components may be incorporated into the enzyme granulates at any step
and at
any layer in this process.
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LAUNDRY COMPOSITIONS
The laundry compositions of the present invention also comprise, in addition
to
one or more enzyme granulates of the present invention described hereinbefore,
one or
more cleaning adjunct materials, preferably compatible with the enzymes in the
enzyme
granulate(s). The term "cleaning adjunct materials", as used herein, means any
liquid,
solid or gaseous material selected for the particular type of laundry
composition desired
and the form of the product (e.g., liquid; granule; powder; gel composition),
which
materials are also preferably compatible with the enzymes in the enzyme
granulates of
the present invention. Granular compositions can also be in "compact" form and
the
liquid compositions can also be in a "concentrated" form.
The specific selection of cleaning adjunct materials are readily made by
considering the surface, item or fabric to be cleaned, and the desired form of
the
composition for the laundry conditions during use (e.g., through the wash
detergent use).
The term "compatible", as used herein, means the cleaning adjunct materials do
not reduce the enzymatic activity of the enzymes in the enzyme granulates to
such an
extent that the enzymes are not effective as desired during normal use
situations.
Examples of suitable cleaning adjunct materials include, but are not limited
to,
surfactants, builders, bleaches, bleach activators, bleach catalysts, other
enzymes, enzyme
stabilizing systems, chelants, optical brighteners, soil release polymers, dye
transfer
agents, dispersants, suds suppressors, dyes, perfumes, colorants, filler
salts, hydrotropes,
photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants,
perservatives,
anti-oxidants, anti-shrinkage agents, anti-wrinkle agents, germicides,
fungicides, color
speckles, silvercare, anti-tarnish and/or anti-corrosion agents, alkalinity
sources,
solubilizing agents, Garners, processing aids, pigments and pH control agents
as
described in U.S. Patent Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679,
5,686,014 and
5,646,101. Specific cleaning adjunct materials are exemplified in detail
hereinafter.
If the cleaning adjunct materials are not compatible with the enzymes in the
enzyme granulates within the laundry compositions, then suitable methods of
keeping the
cleaning adjunct materials and the enzymes in the enzyme granulates separate
(not in
contact with each other) until combination of the two components is
appropriate can be
used. Suitable methods can be any method known in the art, such as gelcaps,
encapulation, tablets, physical separation, etc.
Preferably an effective amount of one or more enzyme granulates described
above
are included in compositions useful for laundering a variety of fabrics in
need of
cleaning.
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WO 00/46332 PCT/US00/02666
16
As used herein, "effective amount of one or more enzyme granulates" refers to
the
quantity of enzyme granulates of the present invention described hereinbefore
necessary
to achieve the enzymatic activity necessary in the specific laundry
composition. Such
effective amounts are readily ascertained by one of ordinary skill in the art
and is based
on many factors, such as the particular enzyme used, the laundry application,
the specific
composition of the laundry composition, and whether a liquid or dry (e.g.,
granular,
powder) composition is required, and the like.
The laundry detergent compositions of the present invention comprise:
(a) an enzyme granulate in accordance with the present invention; and
(b) one or more cleaning adjunct materials.
Preferably, a laundry detergent composition of the present invention comprises
one or more enzyme granulates of the present invention such that the density
difference
between the density of the laundry detergent composition and the density of
the enzyme
granulates is less than about 0.2 g/mL, more preferably less than about 0.1
g/mL, most
preferably less than about 0.05 g/mL.
Preferably, the laundry compositions comprise from about 0.0001%, preferably
from about 0.001%, more preferably from about 0.01% by weight of the laundry
compositions of one or more enzyme granulates of the present invention, to
about 10%,
preferably to about 1 %, more preferably to about 0.1 %.
Preferably, the enzyme granulates of the present invention comprise one or
more
enzymes of the present invention such that the enzymes are present in the
laundry
compositions of the present invention at a level of from about 0.0001% to
about 2%,
more preferably from about 0.001 % to about 2%, most preferably from about
0.01 % to
about 1 % of pure enzyme by weight of the laundry composition.
Several examples of various laundry compositions wherein the enzyme granulates
of the present invention may be employed are discussed in further detail
below. Also, the
laundry compositions may include from about 1 % to about 99.9% by weight of
the
composition of the cleaning adjunct materials.
As used herein, "fabric laundry compositions" include hand and machine laundry
detergent compositions including laundry additive compositions and
compositions
suitable for use in the soaking and/or pretreatment of stained fabrics.
When the laundry compositions of the present invention are formulated as
compositions suitable for use in a laundry machine washing method, the
compositions of
the present invention preferably contain both a surfactant and a builder
compound and
additionally one or more cleaning adjunct materials preferably selected from
organic
polymeric compounds, bleaching agents, additional enzymes, suds suppressors,
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17
dispersants, lime-soap dispersants, soil suspension and anti-redeposition
agents and
corrosion inhibitors. Laundry compositions can also contain softening agents,
as
additional cleaning adjunct materials.
The compositions of the present invention can also be used as detergent
additive
products in solid or liquid form. Such additive products are intended to
supplement or
boost the performance of conventional detergent compositions and can be added
at any
stage of the laundry process.
If needed the density of the laundry detergent compositions herein ranges from
400 to 1200 g/litre, preferably 500 to 950 g/litre of composition measured at
20°C.
The "compact" form of the laundry compositions herein is best reflected by
density and, in terms of composition, by the amount of inorganic filler salt;
inorganic
filler salts are conventional ingredients of detergent compositions in powder
form; in
conventional detergent compositions, the filler salts are present in
substantial amounts,
typically 17-35% by weight of the total composition. In the compact
compositions, the
filler salt is present in amounts not exceeding 15% of the total composition,
preferably
not exceeding 10%, most preferably not exceeding 5% by weight of the
composition. The
inorganic filler salts, such as meant in the present compositions are selected
from the
alkali and alkaline-earth-metal salts of sulfates and chlorides. A preferred
filler salt is
sodium sulfate.
Liquid laundry compositions according to the present invention can also be in
a
"concentrated form", in such case, the liquid laundry compositions according
the present
invention will contain a lower amount of water, compared to conventional
liquid
detergents. Typically the water content of the concentrated liquid laundry
composition is
preferably less than 40%, more preferably less than 30%, most preferably less
than 20%
by weight of the laundry composition.
A. Liauid Laundry Detergent Compositions
NON-AQUEOUS BASED HEAVY DUTY LIQUID DETERGENTS
SURFACTANT-CONTAINING LIQUID PHASE
Non-aqueous, liquid, heavy-duty detergent compositions in accordance with the
present invention are in the form of a stable suspension of solid,
substantially insoluble
particulate material dispersed throughout a structured, surfactant-containing
liquid phase.
Such detergent compositions comprise from about 49% to 99.95% by weight of the
composition of a structured, surfactant-containing liquid phase formed by
combining:
i) from about 1 % to 80% by weight of said liquid phase of one or more
nonaqueous organic diluents; and
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WO 00/46332 PCT/US00/02666
18
ii) from about 20% to 99% by weight of said liquid phase of a surfactant
system
comprising surfactants selected from the group consisting of anionic,
nonionic,
cationic surfactants and combinations thereof.
The surfactant-containing, non-aqueous liquid phase of the non-aqueous liquid
laundry detergent compositions of the present invention will generally
comprise from
about 52% to about 98.9% by weight of the detergent compositions herein. More
preferably, this liquid phase is surfactant-structured and will comprise from
about 55% to
98% by weight of the compositions. Most preferably, this non-aqueous liquid
phase will
comprise from about 55% to 70% by weight of the compositions herein. Such a
surfactant-containing liquid phase will frequently have a density of from
about 0.6 to 1.4
g/cc, more preferably from about 0.9 to 1.3 g/cc. The liquid phase of the
detergent
compositions herein is preferably formed from one or more non-aqueous organic
diluents
into which is mixed a surfactant structuring agent which is preferably a
specific type of
anionic surfactant-containing powder.
i. Non-aqueous Organic Diluents
The major component of the liquid phase of the detergent compositions herein
comprises one or more non-aqueous organic diluents. The non-aqueous organic
diluents
used in this invention may be either surface active, i.e., surfactant, liquids
or non-
aqueous, non-surfactant liquids referred to herein as non-aqueous solvents.
The term
"solvent" is used herein to connote the non-surfactant, non-aqueous liquid
portion of the
compositions herein. While some of the essential and/or optional components of
the
compositions herein may actually dissolve in the "solvent"-containing liquid
phase, other
components will be present as particulate material dispersed within the
"solvent"-
containing liquid phase. Thus the term "solvent" is not meant to require that
the solvent
material be capable of actually dissolving all of the detergent composition
components
added thereto.
The non-aqueous liquid diluent component will generally comprise from about
SO% to 100%, more preferably from about 50% to 80%, most preferably from about
55%
to 75%, of a structured, surfactant-containing liquid phase. Preferably the
liquid phase of
the compositions herein, i.e., the non-aqueous liquid diluent component, will
comprise
both non-aqueous liquid surfactants and non-surfactant non-aqueous solvents.
ii. Non-aqueous Surfactant Liquids
Suitable types of non-aqueous surfactant liquids which can be used to form the
liquid phase of the compositions herein include the alkoxylated alcohols,
ethylene oxide
(EO)-propylene oxide (PO) block polymers, polyhydroxy fatty acid amides,
alkylpolysaccharides, and the like. Such normally liquid surfactants are those
having an
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WO 00/46332 PCT/US00/02666
19
HLB ranging from 10 to 16. Most preferred of the surfactant liquids are the
alcohol
alkoxylate nonionic surfactants.
Alcohol alkoxylates are materials which correspond to the general formula:
R1 ~CmH2m0)nOH
wherein R1 is a Cg - C16 alkyl group, m is from 2 to 4, and n ranges from
about 2 to 12.
Preferably R1 is an alkyl group, which may be primary or secondary, that
contains from
about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms.
Preferably also the alkoxylated fatty alcohols will be ethoxylated materials
that contain
from about 2 to 12 ethylene oxide moieties per molecule, more preferably from
about 3
to 10 ethylene oxide moieties per molecule.
The alkoxylated fatty alcohol materials useful in the liquid phase will
frequently
have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17.
More
preferably, the HLB of this material will range from about 6 to 1 S, most
preferably from
about 8 to 15.
Examples of fatty alcohol alkoxylates useful in or as the non-aqueous liquid
phase
of the compositions herein will include those which are made from alcohols of
12 to 15
carbon atoms and which contain about 7 moles of ethylene oxide. Such materials
have
been commercially marketed under the trade names Neodol 25-7 and Neodol 23-6.5
by
Shell Chemical Company. Other useful Neodols include Neodol 1-S, an
ethoxylated
fatty alcohol averaging 1 I carbon atoms in its alkyl chain with about 5 moles
of ethylene
oxide; Neodol 23-9, an ethoxylated primary C12 - C13 alcohol having about 9
moles of
ethylene oxide and Neodol 91-10, an ethoxylated Cg-C11 primary alcohol having
about
moles of ethylene oxide. Alcohol ethoxylates of this type have also been
marketed by
Shell Chemical Company under the Dobanol tradename. Dobanol 91-5 is an
ethoxylated
Cg-C 11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-
7 is an
ethoxylated C12-C15 fatty alcohol with an average of 7 moles of ethylene oxide
per mole
of fatty alcohol.
Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7 and
Tergitol 15-S-9 both of which are linear secondary alcohol ethoxylates that
have been
commercially marketed by Union Carbide Corporation. The former is a mixed
ethoxylation product of C11 to C15 linear secondary alkanol with 7 moles of
ethylene
oxide and the latter is a similar product but with 9 moles of ethylene oxide
being reacted.
Other types of alcohol ethoxylates useful in the present compositions are
higher
molecular weight nonionics, such as Neodol 45-11, which are similar ethylene
oxide
condensation products of higher fatty alcohols, with the higher fatty alcohol
being of 14-
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WO 00/46332 PCT/US00/02666
1 S carbon atoms and the number of ethylene oxide groups per mole being about
11.
Such products have also been commercially marketed by Shell Chemical Company.
If alcohol alkoxylate nonionic surfactant is utilized as part of the non-
aqueous
liquid phase in the detergent compositions herein, it will preferably be
present to the
extent of from about 1 % to 60% of the composition structured liquid phase.
More
preferably, the alcohol alkoxylate component will comprise about 5% to 40% of
the
structured liquid phase. Most preferably, an alcohol alkoxylate component will
comprise
from about 5% to 35% of the detergent composition structured liquid phase.
Utilization
of alcohol alkoxylate in these concentrations in the liquid phase corresponds
to an
alcohol alkoxylate concentration in the total composition of from about 1 % to
60% by
weight, more preferably from about 2% to 40% by weight, and most preferably
from
about 5% to 25% by weight, of the composition.
Another type of non-aqueous surfactant liquid which may be utilized in this
invention are the ethylene oxide (EO) - propylene oxide (PO) block polymers.
Materials
of this type are well known nonionic surfactants which have been marketed
under the
tradename Pluronic. These materials are formed by adding blocks of ethylene
oxide
moieties to the ends of polypropylene glycol chains to adjust the surface
active properties
of the resulting block polymers. EO-PO block polymer nonionics of this type
are
described in greater detail in Davidsohn and Milwidsky; Synthetic Detergents,
7th Ed.;
Longman Scientific and Technical (1987) at pp. 34-36 and pp. 189-191 and in
U.S.
Patents 2,674,619 and 2,677,700. All of these publications are incorporated
herein by
reference. These Pluronic type nonionic surfactants are also believed to
function as
effective suspending agents for the particulate material which is dispersed in
the liquid
phase of the detergent compositions herein.
Another possible type of non-aqueous surfactant liquid useful in the
compositions
herein comprises polyhydroxy fatty acid amide surfactants. If present, the
polyhydroxy
fatty acid amide surfactants are preferably present in a concentration of from
about 0.1 to
about 8%. Materials of this type of nonionic surfactant are those which
conform to the
formula:
O i pH2p+1
R-C-N-Z
wherein R is a C9_17 alkyl or alkenyl, p is from 1 to 6, and Z is glycityl
derived from a
reduced sugar or alkoxylated derivative thereof. Such materials include the C
12-C 1 g N-
methyl glucamides. Examples are N-methyl N-1-deoxyglucityl cocoamide and N-
methyl
N-1-deoxyglucityl oleamide. Processes for making polyhydroxy fatty acid,
amides are
know and can be found, for example, in Wilson, U.S. Patent 2,965,576 and
Schwartz,
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WO 00/46332 PCT/US00l02666
21
U.S. Patent 2,703,798, the disclosures of which are incorporated herein by
reference.
The materials themselves and their preparation are also described in greater
detail in
Honsa, U.S. Patent 5,174,937, Issued December 26, 1992, which patent is also
incorporated herein by reference.
The amount of total liquid surfactant in the preferred surfactant-structured,
non-
aqueous liquid phase herein will be determined by the type and amounts of
other
composition components and by the desired composition properties. Generally,
the
liquid surfactant can comprise from about 35% to 70% of the non-aqueous liquid
phase
of the compositions herein. More preferably, the liquid surfactant will
comprise from
about 50% to 65% of a non-aqueous structured liquid phase. This corresponds to
a non-
aqueous liquid surfactant concentration in the total composition of from about
15% to
70% by weight, more preferably from about 20% to 50% by weight, of the
composition.
iii. Non-surfactant Non-agueous Organic Solvents
The liquid phase of the detergent compositions herein may also comprise one or
more non-surfactant, non-aqueous organic solvents. Such non-surfactant non-
aqueous
liquids are preferably those of low polarity. For purposes of this invention.
"low-
polarity" liquids are those which have little, if any, tendency to dissolve
one of the
preferred types of particulate material used in the compositions herein, i.e.,
the peroxygen
bleaching agents, sodium perborate or sodium percarbonate. Thus relatively
polar
solvents such as ethanol are preferably not utilized. Suitable types of low-
polarity
solvents useful in the non-aqueous liquid detergent compositions herein do
include non-
vicinal C4-Cg alkylene glycols, alkylene glycol mono lower alkyl ethers, lower
molecular
weight polyethylene glycols, lower molecular weight methyl esters and amides,
and the
like.
A preferred type of non-aqueous, low-polarity solvent for use in the
compositions
herein comprises the non-vicinal C4-Cg branched or straight chain alkylene
glycols.
Materials of this type include hexylene glycol (4-methyl-2,4-pentanediol), 1,6-
hexanediol, 1,3-butylene glycol and 1,4-butylene glycol. Hexylene glycol is
the most
preferred.
Another preferred type of non-aqueous, low-polarity solvent for use herein
comprises the mono-, di-, tri-, or tetra- C2-C3 alkylene glycol mono C2-C6
alkyl ethers.
The specific examples of such compounds include diethylene glycol monobutyl
ether,
tetraethylene glycol monobutyl ether, dipropolyene glycol monoethyl ether, and
dipropylene glycol monobutyl ether. Diethylene glycol monobutyl ether,
dipropylene
glycol monobutyl ether and butoxy-propoxy-propanol (BPP) are especially
preferred.
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Compounds of the type have been commercially marketed under the trade names
Dowanol, Carbitol, and Cellosolve.
Another preferred type of non-aqueous, low-polarity organic solvent useful
herein
comprises the lower molecular weight polyethylene glycols (PEGs). Such
materials are
those having molecular weights of at least about 150. PEGS of molecular weight
ranging
from about 200 to 600 are most preferred.
Yet another preferred type of non-polar, non-aqueous solvent comprises lower
molecular weight methyl esters. Such materials are those of the general
formula: R1-
C(O)-OCH3 wherein R1 ranges from 1 to about 18. Examples of suitable lower
molecular weight methyl esters include methyl acetate, methyl propionate,
methyl
octanoate, and methyl dodecanoate.
The non-aqueous, generally low-polarity, non-surfactant organic solvents)
employed should, of course, be compatible and non-reactive with other
composition
components, e.g., bleach and/or activators, used in the liquid detergent
compositions
herein. Such a solvent component is preferably utilized in an amount of from
about 1 % to
70% by weight of the liquid phase. More preferably, a non-aqueous, low-
polarity, non-
surfactant solvent will comprise from about 10% to 60% by weight of a
structured liquid
phase, most preferably from about 20% to 50% by weight, of a structured liquid
phase of
the composition. Utilization of non-surfactant solvent in these concentrations
in the
liquid phase corresponds to a non-surfactant solvent concentration in the
total
composition of from about 1% to 50% by weight, more preferably from about 5%
to 40%
by weight, and most preferably from about 10% to 30% by weight, of the
composition.
iv. Blends of Surfactant and Non-surfactant Solvents
In systems which employ both non-aqueous surfactant liquids and non-aqueous
non-surfactant solvents, the ratio of surfactant to non-surfactant liquids,
e.g., the ratio of
alcohol alkoxylate to low polarity solvent, within a structured, surfactant-
containing
liquid phase can be used to vary the rheological properties of the detergent
compositions
eventually formed. Generally, the weight ratio of surfactant liquid to non-
surfactant
organic solvent will range about 50:1 to 1:50. More preferably, this ratio
will range from
about 3:1 to 1:3, most preferably from about 2:1 to 1:2.
v. Surfactant Structurant
The non-aqueous liquid phase of the detergent compositions of this invention
is
prepared by combining with the non-aqueous organic liquid diluents
hereinbefore
described a surfactant which is generally, but not necessarily, selected to
add structure to
the non-aqueous liquid phase of the detergent compositions herein. Structuring
surfactants can be of the anionic, nonionic, cationic, and/or amphoteric
types.
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Preferred structuring surfactants are the anionic surfactants such as the
alkyl
sulfates, the alkyl polyalkxylate sulfates and the linear alkyl benzene
sulfonates. Another
common type of anionic surfactant material which may be optionally added to
the
detergent compositions herein as structurant comprises carboxylate-type
anionics.
Carboxylate-type anionics include the C 10-C 1 g alkyl alkoxy carboxylates
(especially the
EO 1 to 5 ethoxycarboxylates) and the C 10-C 1 g sarcosinates, especially
oleoyl
sarcosinate. Yet another common type of anionic surfactant material which may
be
employed as a structurant comprises other sulfonated anionic surfactants such
as the Cg-
Clg paraffin sulfonates and the Cg-Clg olefin sulfonates. Structuring anionic
surfactants
will generally comprise from about 1 % to 30% by weight of the compositions
herein.
As indicated, one preferred type of structuring anionic surfactant comprises
primary or secondary alkyl sulfate anionic surfactants. Such surfactants are
those
produced by the sulfation of higher Cg-C20 fatty alcohols.
Conventional primary alkyl sulfate surfactants have the general formula
ROS03-M+
wherein R is typically a linear Cg - C20 hydrocarbyl group, which may be
straight chain
or branched chain, and M is a water-solubilizing canon. Preferably R is a C10-
14 alkyl,
and M is alkali metal. Most preferably R is about C 12 and M is sodium.
Conventional secondary alkyl sulfates may also be utilized as a structuring
anionic surfactant for the liquid phase of the compositions herein.
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(CHOS03-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.
If utilized, alkyl sulfates will generally comprise from about 1 % to 30% by
weight
of the composition, more preferably from about 5% to 25% by weight of the
composition. Non-aqueous liquid detergent compositions containing alkyl
sulfates,
peroxygen bleaching agents, and bleach activators are described in greater
detail in Kong-
Chan et al.; WO 96/10073; Publiched April 4, 1996, which application is
incorporated
herein by reference.
Another preferred type of anionic surfactant material which may be optionally
added to the non-aqueous laundry compositions herein as a structurant
comprises the
alkyl polyalkoxylate sulfates. Alkyl polyalkoxylate sulfates are also known as
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alkoxylated alkyl sulfates or alkyl ether sulfates. Such materials are those
which
correspond to the formula
R2-O-(CmH2m0)n-S03M
wherein R2 is a C10-C22 alkyl group, m is from 2 to 4, n is from about 1 to
15, and M is
a salt-forming canon. Preferably, R2 is a C 12-C 1 g alkyl, m is 2, n is from
about 1 to 10,
and M is sodium, potassium, ammonium, alkylammonium or alkanolammonium. Most
preferably, R2 is a C12-C16, m is 2, n is from about 1 to 6, and M is sodium.
Ammonium, alkylammonium and alkanolammonium counterions are preferably avoided
when used in the compositions herein because of incompatibility with peroxygen
bleaching agents.
If utilized, alkyl polyalkoxylate sulfates can also generally comprise from
about
1% to 30% by weight of the composition, more preferably from about 5% to 25%
by
weight of the composition. Non-aqueous liquid detergent compositions
containing alkyl
polyalkoxylate sulfates, in combination with polyhydroxy fatty acid amides,
are described
in greater detail in Boutique et al; PCT Application No. PCT/US96/04223, which
application is incorporated herein by reference.
The most preferred type of anionic surfactant for use as a structurant in the
compositions herein comprises the linear alkyl benzene sulfonate (LAS)
surfactants. In
particular, such LAS surfactants can be formulated into a specific type of
anionic
surfactant-containing powder which is especially useful for incorporation into
the non-
aqueous liquid detergent compositions of the present invention. Such a powder
comprises two distinct phases. One of these phases is insoluble in the non-
aqueous
organic liquid diluents used in the compositions herein; the other phase is
soluble in the
non-aqueous organic liquids. It is the insoluble phase of this preferred
anionic surfactant-
containing powder which can be dispersed in the non-aqueous liquid phase of
the
preferred compositions herein and which forms a network of aggregated small
particles
that allows the final product to stably suspend other solid particulate
materials in the
composition.
Such a preferred anionic surfactant-containing powder is formed by co-drying
an
aqueous slurry which essentially contains a) one of more alkali metal salts of
C10-16
linear alkyl benzene sulfonic acids; and b) one or more non-surfactant diluent
salts. Such
a slurry is dried to a solid material, generally in powder form, which
comprises both the
soluble and insoluble phases.
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The linear alkyl benzene sulfonate (LAS) materials used to form the preferred
anionic surfactant-containing powder are well known materials. Such
surfactants and
their preparation are described for example in U.S. Patents 2,220,099 and
2,477,383,
incorporated herein by reference. Especially preferred are the sodium and
potassium
linear straight chain alkylbenzene sulfonates in which the average number of
carbon
atoms in the alkyl group is from about 11 to 14. Sodium C11-14~ e~g~~ C12~ LAS
is
especially preferred. The alkyl benzene surfactant anionic surfactants are
generally used
in the powder-forming slurry in an amount from about 20 to 70% by weight of
the slurry,
more preferably from about 20% to 60% by weight of the slurry.
The powder-forming slurry also contains a non-surfactant, organic or inorganic
salt component that is co-dried with the LAS to form the two-phase anionic
surfactant-
containing powder. Such salts can be any of the known sodium, potassium or
magnesium halides, sulfates, citrates, carbonates, sulfates, borates,
succinates, sulfo-
succinates and the like. Sodium sulfate, which is generally a bi-product of
LAS
production, is the preferred non-surfactant diluent salt for use herein. Salts
which
function as hydrotropes such as sodium sulfo-succinate may also usefully be
included.
The non-surfactant salts are generally used in the aqueous slurry, along with
the LAS, in
amounts ranging from about 1 to SO% by weight of the slurry, more preferably
from
about 5% to 40% by weight of the slurry. Salts that act as hydrotropes can
preferably
comprise up to about 3% by weight of the slurry.
The aqueous slurry containing the LAS and diluent salt components hereinbefore
described can be dried to form the anionic surfactant-containing powder
preferably added
to the non-aqueous diluents in order to prepare a structured liquid phase
within the
compositions herein. Any conventional drying technique, e.g., spray drying,
drum
drying, etc., or combination of drying techniques, may be employed. Drying
should take
place until the residual water content of the solid material which forms is
within the
range of from about 0.5% to 4% by weight, more preferably from about 1% to 3%
by
weight.
The anionic surfactant-containing powder produced by the drying operation
constitutes two distinct phases, one of which is soluble in the inorganic
liquid diluents
used herein and one of which is insoluble in the diluents. The insoluble phase
in the
anionic surfactant-containing powder generally comprises from about 10% to 4~%
by
weight of the powder, more preferably from about 15% to 35% by weight of a
powder.
The anionic surfactant-containing powder that results after drying can
comprise
from about 45% to 94%, more preferably from about 60% to 94%, by weight of the
powder of alkyl benzene sulfonic acid salts. Such concentrations are generally
sufficient
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to provide from about 0.5% to 60%, more preferably from about 15% to 60%, by
weight
of the total detergent composition that is eventually prepared, of the alkyl
benzene
sulfonic acid salts. The anionic surfactant-containing powder itself can
comprise from
about 0.45% to 45% by weight of the total composition that is eventually
prepared. After
drying, the anionic surfactant-containing powder will also generally contain
from about
2% to 50%, more preferably from about 2% to 25% by weight of the powder of the
non-
surfactant salts.
After it is dried to the requisite extent, the combined LAS/salt material can
be
converted to flakes or powder form by any known suitable milling or
comminution
process. Generally at the time such material is combined with the non-aqueous
organic
solvents to form the structured liquid phase of the compositions herein, the
particle size
of this powder will range from 0.1 to 2000 microns, more preferably from about
0.1 to
1000 microns.
A structured, surfactant-containing liquid phase of the preferred detergent
compositions herein can be prepared by combining the non-aqueous organic
diluents
hereinbefore described with the anionic surfactant-containing powder as
hereinbefore
described. Such combination results in the formation of a structured
surfactant-
containing liquid phase. Conditions for making this combination of preferred
structured
liquid phase components are described more fully hereinafter in the
"Composition
Preparation and Use" section. As previously noted, the formation of a
structured,
surfactant-containing liquid phase permits the stable suspension of colored
speckles and
additional functional particulate solid materials within the preferred
detergent
compositions of this invention.
Additional suitable surfactants for use in the present invention included
nonionic
surfactants, specifically, polyhydroxy fatty acid amides of the formula:
R-C-N-Z
wherein R is a Cg-17 alkyl or alkenyl, R1 is a methyl group and Z is glycityl
derived
from a reduced sugar or alkoxylated derivative thereof. Examples are N-methyl
N-1-
deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl oleamide. Processes for
making polyhydroxy fatty acid amides are known and can be found in Wilson,
U.S.
Patent 2,965,576 and Schwartz, U.S. Patent 2,703,798, the disclosures of which
are
incorporated herein by reference.
Preferred surfactants for use in the detergent compositions described herein
are
amine based surfactants of the general formula:
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27
R3
R 1-X-(CH2)n-N
R4
wherein R1 is a C6-C12 alkyl group; n is from about 2 to about 4, X is a
bridging group
which is selected from NH, CONH, COO, or O or X can be absent; and R3 and R4
are
individually selected from H, C1-C4 alkyl, or (CH2-CH2-O(RS)) wherein RS is H
or
methyl. Especially preferred amines based surfactants include the following:
R1-(CH2)2-NH2
R 1-O-(CH2)3-NH2
Rl-C(O)-~-(CH2)3-N(CH3)2
CH2-CH(OH)-RS
R1-N
CH2-CH(OH)-RS
wherein R1 is a Cb-C12 alkyl group and RS is H or CH3. Particularly preferred
amines
for use in the surfactants defined above include those selected from the group
consisting
of octyl amine, hexyl amine, decyl amine, dodecyl amine, Cg-C 12
bis(hydroxyethyl)amine, Cg-C12 bis(hydroxyisopropyl)amine, Cg-C12 amido-propyl
dimethyl amine, or mixtures thereof.
In a highly preferred embodiment, the amine based surfactant is described by
the
formula:
R1-C(O)-NH-(CH2)3-N(CH3)2
wherein R1 is Cg-C12 alkyl.
vi. Solid Particulate Materials
The non-aqueous detergent compositions herein preferably comprise from about
0.01 % to 50% by weight, more preferably from about 0.2% to 30% by weight, of
solid
phase particulate material which is dispersed and suspended within the liquid
phase.
Generally such particulate material will range in size from about 0.1 to 1500
microns,
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more preferably from about 0.1 to 900 microns. Most preferably, such material
will
range in size from about 5 to 200 microns.
The particulate material utilized herein can comprise one or more types of
detergent composition components which in particulate form are substantially
insoluble
in the non-aqueous liquid phase of the composition. The types of particulate
materials
which can be utilized are described in detail as follows:
AQUEOUS BASED HEAVY DUTY LIOUID DETERGENTS
SURFACTANTS
The present invention also comprises aqueous based liquid detergent
compositions. The aqueous liquid detergent compositions preferably comprise
from
about 10% to about 98%, preferably from about 30% to about 95%, by weight of
an
aqueous liquid carrier which is preferably water. Additionally, the aqueous
liquid
detergent compositions of the present invention comprise a surfactant system
which
preferably contains one or more detersive co-surfactants in addition to the
branched
surfactants disclosed above. The additional co-surfactants can be selected
from nonionic
detersive surfactant, anionic detersive surfactant, zwitterionic detersive
surfactant, amine
oxide detersive surfactant, and mixtures thereof. The surfactant system
typically
comprises from about S% to about 70%, preferably from about 15% to about 30%,
by
weight of the detergent composition.
i. Anionic Surfactant
Anionic surfactants include C11-Clg alkyl benzene sulfonates (LAS) and
primary, branched-chain and random C 10-C20 alkyl sulfates (AS), the C 10-C 18
secondary (2,3) alkyl sulfates of the formula CH3(CH2)x(CHOS03 M+) CH3 and CH3
(CH2)y(CHOS03 M+) CH2CH3 where x and (y + 1) are integers of at least about 7,
preferably at least about 9, and M is a water-solubilizing canon, especially
sodium,
unsaturated sulfates such as oleyl sulfate, the C10-Clg alkyl alkoxy sulfates
("AExS";
especially EO 1-7 ethoxy sulfates), C 10-C 1 g alkyl alkoxy carboxylates
(especially the EO
1-5 ethoxycarboxylates), the C 10-18 glycerol ethers, the C 10-C 1 g alkyl
polyglycosides
and their corresponding sulfated polyglycosides, and C 12-C 1 g alpha-
sulfonated fatty acid
esters.
Generally speaking, anionic surfactants useful herein are disclosed in U.S.
Patent
No. 4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent No.
3,919,678,
Laughlin et al, issued December 30, 1975.
Useful anionic surfactants include the water-soluble salts, particularly the
alkali
metal, ammonium and alkylolammonium (e.g., monoethanolammonium or
triethanolammonium) salts, of organic sulfuric reaction products having in
their
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molecular structure an alkyl group containing from about 10 to about 20 carbon
atoms
and a sulfonic acid or sulfuric acid ester group. (Included in the term
"alkyl" is the alkyl
portion of aryl groups.) Examples of this group of synthetic surfactants are
the alkyl
sulfates, especially those obtained by sulfating the higher alcohols (Cg-Clg
carbon
atoms) such as those produced by reducing the glycerides of tallow or coconut
oil.
Other anionic surfactants herein are the water-soluble salts of alkyl phenol
ethylene oxide ether sulfates containing from about 1 to about 4 units of
ethylene oxide
per molecule and from about 8 to about 12 carbon atoms in the alkyl group.
Other useful anionic surfactants herein include the water-soluble salts of
esters of
a-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the
fatty acid
group and from about 1 to 10 carbon atoms in the ester group; 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 b-
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.
Particularly preferred anionic surfactants herein are the alkyl polyethoxylate
sulfates of the formula:
RO(C2H40)xS03-M+
wherein R is an alkyl chain having from about 10 to about 22 carbon atoms,
saturated or
unsaturated, M is a canon which makes the compound water-soluble, especially
an alkali
metal, ammonium or substituted ammonium canon, and x averages from about 1 to
about
15.
Preferred alkyl sulfate surfactants are the non-ethoxylated C12-15 primary and
secondary alkyl sulfates. Under cold water washing conditions, i.e., less than
abut 65°F
(18.3°C), it is preferred that there be a mixture of such ethoxylated
and non-ethoxylated
alkyl sulfates. Examples of fatty acids include capric, lauric, myristic,
palmitic, stearic,
arachidic, and behenic acid. Other fatty acids include palmitoleic, oleic,
linoleic,
linolenic, and ricinoleic acid.
ii. Nonionic Surfactant
Conventional nonionic and amphoteric surfactants include C 12-C 18 alkyl
ethoxylates (AE) including the so-called narrow peaked alkyl ethoxylates and
C6-C12
alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy).
The C10-
C 1 g N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples
include
the C 12-C 1 g N-methylglucamides. See WO 9,206,154. Other sugar-derived
surfactants
include the N-alkoxy polyhydroxy fatty acid amides, such as C10-Clg N-(3-
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methoxypropyl) glucamide. The N-propyl through N-hexyl C 12-C 1 g glucamides
can be
used for low sudsing. C10-C20 conventional soaps may also be used. If high
sudsing is
desired, the branched-chain C10-C16 soaps may be used. Examples of nonionic
surfactants are described in U.S. Patent No. 4,285,841, Barrat et al, issued
August 25,
1981.
Preferred examples of these surfactants include ethoxylated alcohols and
ethoxylated alkyl phenols of the formula R(OC2H4)nOH, wherein R is selected
from the
group consisting of aliphatic hydrocarbon radicals containing from about 8 to
about 15
carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from
about 8 to
about 12 carbon atoms, and the average value of n is from about 5 to about 15.
These
surfactants are more fully described in U.S. Patent No. 4,284,532, Leikhim et
al, issued
August 18, 1981. Particularly preferred are ethoxylated alcohols having an
average of
from about 10 to abut 1 S carbon atoms in the alcohol and an average degree of
ethoxylation of from about 6 to about 12 moles of ethylene oxide per mole of
alcohol.
Mixtures of anionic and nonionic surfactants are especially useful.
Other conventional useful surfactants are listed in standard texts, including
C12-
C 1 g betaines and sulfobetaines (sultaines).
iii. Amine Oxide Surfactants
The compositions herein also contain amine oxide surfactants of the formula:
R1(EO)x(PO)y(BO)zN(O)(CH2R~)2~qH20 (I)
In general, it can be seen that the structure (I) provides one long-chain
moiety
R1(EO)x(PO)y(BO)z and two short chain moieties, CH2R'. R' is preferably
selected
from hydrogen, methyl and -CH20H. In general R1 is a primary or branched
hydrocarbyl
moiety which can be saturated or unsaturated, preferably, R1 is a primary
alkyl moiety.
When x+y+z = 0, R1 is a hydrocarbyl moiety having chainlength of from about 8
to about
18. When x+y+z is different from 0, R1 may be somewhat longer, having a
chainlength
in the range C12-C24. The general formula also encompasses amine oxides
wherein
x+y+z = 0, R1 = Cg-Clg, R' is H and q is 0-2, preferably 2. These amine oxides
are
illustrated by C12-14 alkyldimethyl amine oxide, hexadecyl dimethylamine
oxide,
octadecylamine oxide and their hydrates, especially the dihydrates as
disclosed in U.S.
Patents 5,075,501 and 5,071,594, incorporated herein by reference.
The invention also encompasses amine oxides wherein x+y+z is different from
zero, specifically x+y+z is from about 1 to about 10, R1 is a primary alkyl
group
containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon
atoms; in
these embodiments y + z is preferably 0 and x is preferably from about 1 to
about 6, more
preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents
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31
propyleneoxy; and BO represents butyleneoxy. Such amine oxides can be prepared
by
conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates
with
dimethylamine followed by oxidation of the ethoxylated amine with hydrogen
peroxide.
Highly preferred amine oxides herein are solids at ambient temperature, more
preferably they have melting-points in the range 30°C to 90°C.
Amine oxides suitable for
use herein are made commercially by a number of suppliers, including Akzo
Chemie,
Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-
Othmer
review article for alternate amine oxide manufacturers. Preferred commercially
available
amine oxides are the solid, dehydrate ADMOX 16 and ADMOX 18, ADMOX 12 and
especially ADMOX 14 from Ethyl Corp.
Preferred embodiments include dodecyldimethylamine oxide dehydrate,
hexadecyldimethylamine oxide dehydrate, octadecyldimethylamine oxide
dehydrate,
hexadecyltris(ethyleneoxy)dimethyl-amine oxide, tetradecyldimethylamine oxide
dehydrate, and mixtures thereof.
Whereas in certain of the preferred embodiments R' is H, there is some
latitude
with respect to having R' slightly larger than H. Specifically, the invention
further
encompasses embodiments wherein R' is CH20H, such as hexadecylbis(2-
hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-
hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
HEAVY DUTY GEL LAUNDRY DETERGENT COMPOSITIONS
The present invention encompasses a heavy duty gel laundry detergent
compositions comprising, by weight of the composition:
a) from about 15% to about 40% of an anionic surfactant component which
comprises, by weight of the composition:
(i) from about S% to about 25% of alkyl polyethoxylate sulfates wherein the
alkyl group contains from about 10 to about 22 carbon atoms and the
polyethoxylate chain contains from 0.5 to about 1 S, preferably from 0.5 to
about S, more preferably from 0.5 to about 4, ethylene oxide moieties; and
(ii) from about 5% to about 20% of fatty acids; and
b) one or more of the following ingredients: detersive amine, modified
polyamine, polyamide-polyamine, polyethoxylated-polyamine polymers,
quaternary ammonium surfactants, suitable electrolyte or acid equivalents
thereof, and mixtures thereof.
The compositions herein may further contain one or more additional detersive
additives selected from the group consisting of non-citrate builders, optical
brighteners,
soil release polymers, dye transfer inhibitors, polymeric dispersing agents,
enzymes, suds
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32
suppressers, dyes, perfumes, colorants, filler salts, hydrotropes,
antiredeposition agents,
antifading agent, dye fixative agents, prill/fuzzing reducing agents, and
mixtures thereof.
The compositions herein have a viscosity at 20 s-1 shear rate of from about
100
cp to about 4,000 cp, preferably from about 300 cp to about 3,000 cp, more
preferably
from about 500 cp to about 2,000 cp and are stable upon storage.
The compositions herein are structured and have a specific rheology. The
rheology can be modeled by the following formula:
~1 - rlo + KY(n-1)
where rl is the viscosity of the liquid at a given shear rate, rlo is the
viscosity at infinite
shear rate, Y is the shear rate, n is the shear rate index, and K is the
consistency index. As
used herein, the term "structured" indicates a heavy duty liquid composition
having a
liquid crystalline lamellar phase and an infinite shear viscosity (r~o) value
between 0 and
about 3,OOOcp (centipoise), a shear index (n) value of less than about 0.6, a
consistency
index value, K, of above about 1,000, and a viscosity (r)) measured at 20 s-1
of less than
about 10,000cp, preferably less than about S,OOOcp. Under low stress levels, a
"zero
shear" viscosity is above about 100,000cp wherein "zero shear" is meant a
shear rate of
0.001 s-1 or less. The yield value of the compositions herein, obtained by
plotting
viscosity versus stress, is larger than 0.2Pa. These rheology parameters can
be measured
with any commercially available rheometer, such as the Carnmed CSL 100 model.
The compositions herein are clear or translucent, i.e. not opaque.
Electrol~rtes - Without being limited by theory, it is believed that the
presence of
electrolytes acts to control the viscosity of the gel compositions. Thus, the
gel nature of
the compositions herein are affected by the choice of surfactants and by the
amount of
electrolytes present. In preferred embodiments herein, the compositions will
further
comprise from 0% to about 10%, more preferably from about 1 % to about 8%,
even more
preferably from about 2% to about 6%, of a suitable electrolyte or acid
equivalent thereof.
Sodium citrate is a highly preferred electrolyte for use herein.
The compositions herein may optionally contain from about 0% to about 10%, by
weight, of solvents and hydrotropes. Without being limited by theory, it is
believed that
the presence of solvents and hydrotropes can affect the structured versus
isotropic nature
of the compositions; By "solvent" is meant the commonly used solvents in the
detergent
industry, including alkyl monoalcohol, di-, and tri-alcohols, ethylene glycol,
propylene
glycol, propanediol, ethanediol, glycerine, etc. By "hydrotrope" is meant the
commonly
used hydrotropes in the detergent industry, including short chain surfactants
that help
solubilize other surfactants. Other examples of hydrotropes include cumene,
xylene, or
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33
toluene sulfonate, urea, Cg or shorter chain alkyl carboxylates, and Cg or
shorter chain
alkyl sulfate and ethoxylated sulfates.
Modified polvamine - The compositions herein may comprise at least about
0.05%, preferably from about 0.05% to about 3%, by weight, of a water-soluble
or
dispersible, modified polyamine agent, said agent comprising a polyamine
backbone
corresponding to the formula:
[ ~R2 ) 2 -N] W- [R1-N] X- [RZ _N] ~,- [Rl _N] Z
B R2 ( R2 ) 2
wherein each R1 is independently C2-CS alkylene, alkenylene or arylene; each
R2 is
independently H, or a moiety of formula OH[(CH2)x0]Il, wherein x is from about
1 to
about 8 and n is from about 10 to about 50; w is 0 or l; x+y+z is from about 5
to about
30; and B represents a continuation of this structure by branching; and
wherein said
polyamine before alkylation has an average molecular weight of from about 300
to about
1,200.
In preferred embodiments, R1 is C2-C4 alkylene, more preferably ethylene; R2
is
OH[CH2CH20]n, wherein n is from about 15 to about 30, more preferably n is
about 20.
The average Molecular Weight of the polyamine before alkylation is from about
300 to
about 1200, more preferably from about 500 to about 900, still more preferably
from
about 600 to about 700, even more preferably from about 600 to about 650.
In another preferred embodiment, R1 is C2-C4 alkylene, more preferably
ethylene; R2 is OH[CH2CH20Jn, wherein n is from about 10 to about 20, more
preferably n is about 15. The average Molecular Weight of the polyamine before
alkylation is from about 100 to about 300, more preferably from about 150 to
about 250,
even more preferably from about 180 to about 200.
Polyamide-Polyamines - The polyamide-polyamines useful herein will generally
comprise from about 0.1 % to 8% by the weight of the composition. More
preferably,
such polyamide-polyamine materials will comprise from about 0.5% to 4% by
weight of
the compositions herein. Most preferably, these polyamide-polyamines will
comprise
from about 1 % to 3% by weight of the composition.
The polyamide-polyamine materials used in this invention are those which have
repeating, substituted amido-amine units which correspond to the general
Structural
Formula No. I as follows:
O O R+
-EC-R~-C-NH-R2-N-RS-NH~
R4
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34
Structural Formula No. I
In Structural Formula No. I, Rl, R2 and RS are each independently Cl_4
alkylene, Cl_4 alkarylene or arylene. It is also possible to eliminate Rl
entirely so that
the polyamide-polyamine is derived from oxalic acid.
Also in Structural Formula No. I, R3 is H, epichlorohydrin, an azetidinium
group, an epoxypropyl group or a dimethylaminohydroxypropyl group, and R4 can
be H,
C 1 _4 alkyl, C 1 _4 alkaryl, or aryl. R4 may also be any of the foregoing
groups condensed
with C1-4 alkylene oxide.
Rl is preferably butylene, and R2 and RS are preferably ethylene. R3 is
preferably epichlorohydrin. R4 is preferably H.
The polyamide-polyamine materials useful herein can be prepared by reacting
polyamines such as diethylenetriamine, triethylenetetraamine,
tetraethylenepentamine or
dipropylenetriamine with C2-C12 dicarboxylic acids such as oxalic, succinic,
glutaric,
adipic and diglycolic acids. Such materials may then be further derivatized by
reaction
with, for example, epichlorohydrin. Preparation of such materials is described
in greater
detail in Keim, U.S. Patent 2,296,116, Issued February 23, 1960; Keim, U.S.
Patent
2,296,154, Issued February 23, 1960 and Keim, U.S. Patent 3,332,901, Issued
July 25,
1967.
The polyamide-polyamine agents preferred for use herein are commercially
marketed by Hercules, Inc. under the tradename Kymene~ . Especially useful are
Kymene 557H~ and Kymene 557LX~ which are epichlorohydrin adducts of
polyamide-polyamines which are the reaction products of diethylenetriamine and
adipic
acid. Other suitable materials are those marketed by Hercules under the
tradenames
RetenO and Delsette~~ and by Sandoz under the tradename
Cartaretin~. These polyamide-polyamine materials are marketed in the form of
aqueous
suspensions of the polymeric material containing, for example, about 12.5% by
weight
of solids.
Detersive Amine - Suitable amine surfactants for use herein include detersive
amines according to the formula:
R3
RI-X-(CH2)"-N
R4
wherein Rl is a C6-C12 alkyl group; n is from about 2 to about 4, X is a
bridging group
which is selected from NH, CONH, COO, or O or X can be absent; and R3 and R4
are
individually selected from H, Cl-C4 alkyl, or (CH2-CH2-O(RS)) wherein RS is H
or
methyl.
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Preferred amines include the following:
R1-(CH2)~-NH2 (1)
R1-O-(CH2)3-~2 (2)
R1-C(O)-~-(CH2)3-N(CH3)2 (3)
CH2-CH(OH)-RS
R1-N (4)
CH2-CH(OH)-RS
wherein R1 is a C6-C12 alkyl group and RS is H or CH3.
In a highly preferred embodiment, the amine is described by the formula:
Rl-C(O)-~-(CH2)3-N(CH3)2
wherein R1 is Cg-C12 alkyl.
Particularly preferred amines include those selected from the group consisting
of
octyl amine, hexyl amine, decyl amine, dodecyl amine, Cg-C12
bis(hydroxyethyl)amine,
Cg-C12 bis(hydroxyisopropyl)amine, and Cg-C12 amido-propyl dimethyl amine, and
mixtures.
If utilized the detersive amines comprise from about 0.1 % to about 10%,
preferably from about 0.5% to about S%, by weight of the composition.
Quaternary Ammonium Surfactants - from about 1 % to about 6% of a quaternary
ammonium surfactant having the formula
R4\ ~ R1
a
/ \
R3 R2
wherein R1 and R2 are individually selected from the group consisting of C1-C4
alkyl,
C1-Cq. hydroxy alkyl, benzyl, and -(C2H40)xH where x has a value from about 2
to
about 5; X is an anion; and ( 1 ) R3 and R4 are each a C~-C 14 alkyl or (2) R3
is a C6-C 1 g
alkyl, and R4 is selected from the group consisting of C1-C10 alkyl, C1-C10
hydroxy
alkyl, benzyl, and -(C2H40)xH where x has a value from 2 to 5.
Preferred quaternary ammonium surfactants are the chloride, bromide, and
methylsulfate salts. Examples of preferred mono-long chain alkyl quaternary
ammonium
surfactants are those wherein R1, R2, and R4 are each methyl and R3 is a Cg-
C16 alkyl;
or wherein R3 is Cg-lg alkyl and R1, R2, and R4 are selected from methyl and
hydroxy-
alkyl moieties. Lauryl trimethyl ammonium chloride, myristyl trimethyl
ammonium
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36
chloride, palmityl trimethyl ammonium chloride, coconut trimethylammonium
chloride,
coconut trimethylammonium methylsulfate, coconut dimethyl-monohydroxyethyl-
ammonium chloride, coconut dimethyl-monohydroxyethylammonium methylsulfate,
steryl dimethyl-monohydroxy-ethylammonium chloride, steryl dimethylmonohydroxy-
ethylammonium methylsulfate, di- C 12-C 14 alkyl dimethyl ammonium chloride,
and
mixtures thereof are particularly preferred. ADOGEN 412T'~, a lauryl trimethyl
ammonium chloride commercially available from Witco, is also preferred. Even
more
highly preferred are the lauryl trimethyl ammonium chloride and myristyl
trimethyl
ammonium chloride.
Alkoxylated quaternary ammonium (AQA) surfactants useful in the present
invention are of the general formula:
R~ /ApRa
\N X
R2~ ~R3
I
Rl /ApR3
R2~ ~A~qR4
II
wherein R1 is an alkyl or alkenyl moiety containing from about 8 to about 18
carbon
atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10
to about
14 carbon atoms; R2 and R3~ are each independently alkyl groups containing
from one to
about three carbon atoms, preferably methyl; R3 and R4 can vary independently
and are
selected from hydrogen (preferred), methyl and ethyl, X- is an anion such as
chloride,
bromide, methylsulfate, sulfate, or the like, to provide electrical
neutrality; A is selected
from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH20-), propoxy, butoxy and
mixtures
thereof;and for formula I, p is from 2 to about 30, preferably 2 to about 15,
most
preferably 2 to about 8; and for formula II, p is from 1 to about 30,
preferably 1 to about
4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably
both p and q
are 1.
Other quaternary surfactants include the ammonium surfactants such as
alkyldimethylammonium halogenides, and those surfactants having the formula:
[R2(OR3)y~ [R4(OR3)y~2RSN+X_
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37
wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18
carbon
atoms in the alkyl chain, each R3 is selected from the group consisting of -
CH2CH2-, -
CH2CH(CH3)-, -CH2CH(CH20H)-, -CH2CH2CH2-, and mixtures thereof; each R4 is
selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl,
ring
structures formed by joining the two R4 groups, -CH2CHOHCHOHCOR6CHOH-
CH20H wherein R6 is any hexose or hexose polymer having a molecular weight
less
than about 1000, and hydrogen when y is not O; RS is the same as R4 or is an
alkyl chain
wherein the total number of carbon atoms of R2 plus RS is not more than about
18; each
y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and
X is any
compatible anion.
Pol ey thoxylated-Polyamine Polymers - Another polymer dispersant form use
herein includes polyethoxyated-polyamine polymers (PPP). The preferred
polyethoxylated-polyamines useful herein are generally polyalkyleneamines
(PAA's),
polyalkyleneimines (PAI's), preferably polyethyleneamine (PEA's),
polyethyleneimines
(PEI's). A common polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are
obtained by reactions involving ammonia and ethylene dichloride, followed by
fractional
distillation. The common PEA's obtained are triethylenetetramine (TETA) and
teraethylenepentamine (TEPA). Above the pentamines, i.e., the hexamines,
heptamines,
octamines and possibly nonamines, the cogenerically derived mixture does not
appear to
separate by distillation and can include other materials such as cyclic amines
and
particularly piperazines. There can also be present cyclic amines with side
chains in
which nitrogen atoms appear. See U.S. Patent 2,792,372, Dickinson, issued May
14,
1957, which describes the preparation of PEA's.
Polyethoxylated polyamines can be prepared, for example, by polymerizing
ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium
bisulfate,
sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
Specific methods
for preparing these polyamine backbones are disclosed in U.S. Patent
2,182,306, Ulrich
et al., issued December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued
May 8, 1962;
U.S. Patent 2,208,095, Esselmann et al., issued July 16, 1940; U.S. Patent
2,806,839,
Crowther, issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued
May
21, 1951
Optionally, but preferred polyethoxyated-polyamine polymers useful for this
invention are alkoxylated quaternary diamines of the general formula:
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38
A A
R~-N~ R-N~ RI 2X~
A A
where R is selected from linear or branched C2-C 12 alkylene, C3-C 12
hydroxyalkylene,
C4-C12 dihydroxyalkylene, Cg-C12 dialkylarylene, [(CH2CH20)qCH2CH2]- and -
CH2CH(OH)CH20-(CH2CH20)qCH2CH(OH)CH2]- where q is from about 1 to about
100. Each R1 is independently selected from C1-C4 alkyl, C~-C12 alkylaryl, or
A. A is
of the formula:
(CH-CH2-O)nB
R3
where R3 is selected from H or C1-C3 alkyl, n is from about 5 to about 100,
and B is
selected from H, C1-Cq alkyl, acetyl, or benzoyl; X is a water soluble anion.
In preferred embodiments, R is selected from C4 to Cg alkylene, R1 is selected
from C1-C2 alkyl or C2-C3 hydroxyalkyl, and A is:
(CH-CH2-O) nH
R3
where R3 is selected from H or methyl, and n is from about 10 to about 50.
In another preferred embodiment R is linear or branched C6, R1 is methyl, R3
is
H, and n is from about 20 to about 50.
Additional alkoxylated quaternary polyamine dispersants which can be used in
the present invention are of the general formula:
A A A
~O ~O ~O O
R~-N-R N-R N-R1 (m + 2) X
A R~ m A
where R is selected from linear or branched C2-C 12 alkylene, C3-C 12
hydroxyalkylene,
C4-C 12 dihydroxyalkylene, Cg-C 12 dialkylarylene, [(CH2CH20)qCH2CH2]- and -
CH2CH(OH)CH20-(CH2CH20)qCH2CH(OH)CH2]- where q is from about 1 to about
100. If present, Each R1 is independently selected from C1-C4 alkyl, C~-C12
alkylaryl,
or A. R1 may be absent on some nitrogens; however, at least three nitrogens
must be
quaternized.
A is of the formula:
(CH-CH2-O)nB
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39
R3
where R3 is selected from H or C1-C3 alkyl, n is from about S to about 100 and
B is
selected from H, C1-C4 alkyl, acetyl, or benzoyl; m is from about 0 to about
4, and
X is a water soluble anion.
In preferred embodiments, R is selected from C4 to Cg alkylene, R1 is selected
from C1-C2 alkyl or C2-C3 hydroxyalkyl, and A is:
(CH-CH2-O)nH
R3
where R3 is selected from H or methyl, and n is from about 10 to about 50; and
m is 1.
In another preferred embodiment R is linear or branched C6, R1 is methyl, R3
is
H, and n is from about 20 to about 50, and m is 1.
The levels of these polyethoxyated-polyamine polymers used can range from
about 0.1% to about 10%, typically from about 0.4% to about 5%, by weight.
These
polyethoxyated-polyamine polymers can be synthesized following the methods
outline in
U.S. Patent No. 4,664,848, or other ways known to those skilled in the art.
Anionic Surfactant - The anionic surfactant component contains alkyl
polyethoxylate sulfates and may contain other non-soap anionic surfactants or
mixtures
thereof.
Generally speaking, anionic surfactants useful herein are disclosed in U.S.
Patent
No. 4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent No.
3,919,678,
Laughlin et al, issued December 30, 1975, both incorporated herein by
reference.
Useful anionic surfactants include the water-soluble salts, particularly the
alkali
metal, ammonium and alkylolammonium (e.g., monoethanolammonium or
triethanolammonium) salts, of organic sulfuric reaction products having in
their
molecular structure an alkyl group containing from about 10 to about 20 carbon
atoms
and a sulfonic acid or sulfuric acid ester group. (Included in the term
"alkyl" is the alkyl
portion of aryl groups.) Examples of this group of synthetic surfactants are
the alkyl
sulfates, especially those obtained by sulfating the higher alcohols (Cg-C 1 g
carbon
atoms) such as those produced by reducing the glycerides of tallow or coconut
oil.
Especially valuable are linear straight chain alkylbenzene sulfonates in which
the average
number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated
as C> >-
C13LAS.
Other anionic surfactants herein are the water-soluble salts of alkyl phenol
ethylene oxide ether sulfates containing from about 1 to about 4 units of
ethylene oxide
per molecule and from about 8 to about 12 carbon atoms in the alkyl group.
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Other useful anionic surfactants herein include the water-soluble salts of
esters of
a-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the
fatty acid
group and from about 1 to 10 carbon atoms in the ester group; 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 (3-
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.
The alkyl polyethoxylate sulfates useful herein are of the formula
RO(C2H40)xS03-M+
wherein R is an alkyl chain having from about 10 to about 22 carbon atoms,
saturated or
unsaturated, M is a cation which makes the compound water-soluble, especially
an alkali
metal, ammonium or substituted ammonium canon, and x averages from about 0.5
to
about 15.
Preferred alkyl sulfate surfactants are the non-ethoxylated C12-15 primary and
secondary alkyl sulfates. Under cold water washing conditions, i.e., less than
abut 65°F
(18.3°C), it is preferred that there be a mixture of such ethoxylated
and non-ethoxylated
alkyl sulfates.
Fatty Acids - Moreover, the anionic surfactant component herein comprises
fatty
acids. These include saturated and/or unsaturated fatty acids obtained from
natural
sources or synthetically prepared. Examples of fatty acids include capric,
lauric, myristic,
palmitic, stearic, arachidic, and behenic acid. Other fatty acids include
palmitoleic, oleic,
linoleic, linolenic, and ricinoleic acid.
Nonionic Detergent Surfactants - Suitable nonionic detergent surfactants are
generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December
30, 1975,
and U.S. Patent No. 4,285,841, Barrat et al, issued August 25, 1981.
Exemplary, non-
limiting classes of useful nonionic surfactants include: Cg-C 1 g alkyl
ethoxylates ("AE"),
with EO about 1-22, including the so-called narrow peaked alkyl ethoxylates
and C6-C12
alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy),
alkyl
dialkyl amine oxide, alkanoyl glucose amide, and mixtures thereof.
If nonionic surfactants are used, the compositions of the present invention
will
preferably contain up to about 10%, preferably from 0% to about 5%, more
preferably
from 0% to about 3%, by weight of an nonionic surfactant. Preferred are the
ethoxylated
alcohols and ethoxylated alkyl phenols of the formula R(OC2H4)nOH, wherein R
is
selected from the group consisting of aliphatic hydrocarbon radicals
containing from
about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl
groups
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41
contain from about 8 to about 12 carbon atoms, and the average value of n is
from about
S to about 15. These surfactants are more fully described in U.S. Patent No.
4,284,532,
Leikhim et al, issued August 18, 1981. Particularly preferred are ethoxylated
alcohols
having an average of from about 10 to abut 15 carbon atoms in the alcohol and
an
average degree of ethoxylation of from about 6 to about 12 moles of ethylene
oxide per
mole of alcohol.
Other nonionic surfactants for use herein include:
The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl
phenols. In general, the polyethylene oxide condensates are preferred. These
compounds
include the condensation products of alkyl phenols having an alkyl group
containing
from about 6 to about 12 carbon atoms in either a straight chain or branched
chain
configuration with the alkylene oxide. In a preferred embodiment, the ethylene
oxide is
present in an amount equal to from about 5 to about 25 moles of ethylene oxide
per mole
of alkyl phenol. Commercially available nonionic surfactants of this type
include
Igepal~ CO-630, marketed by the GAF Corporation; and Triton~ X-45, X-114, X-
100,
and X-102, all marketed by the Rohm & Haas Company. These compounds are
commonly referred to as alkyl phenol alkoxylates, (e.g., alkyl phenol
ethoxylates).
The condensation products of aliphatic alcohols with from about 1 to about 25
moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either
be straight or
branched, primary or secondary, and generally contains from about 8 to about
22 carbon
atoms. Particularly preferred are the condensation products of alcohols having
an alkyl
group containing from about 10 to about 20 carbon atoms with from about 2 to
about 18
moles of ethylene oxide per mole of alcohol. Examples of commercially
available
nonionic surfactants of this type include Tergitol~ 1 S-S-9 (the condensation
product of
C11-C15 linear secondary alcohol with 9 moles ethylene oxide), Tergitol~ 24-L-
6
NMW (the condensation product of C 12-C 14 primary alcohol with 6 moles
ethylene
oxide with a narrow molecular weight distribution), both marketed by Union
Carbide
Corporation; Neodol~ 45-9 (the condensation product of C 14-C 15 linear
alcohol with 9
moles of ethylene oxide), Neodol~ 23-6.5 (the condensation product of C 12-C
13 linear
alcohol with 6.5 moles of ethylene oxide), Neodol~ 45-7 (the condensation
product of
C14-C15 linear alcohol with 7 moles of ethylene oxide), Neodol~ 45-4 (the
condensation product of C 14-C 15 linear alcohol with 4 moles of ethylene
oxide),
marketed by Shell Chemical Company, and Kyro~ EOB (the condensation product of
C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble
Company. Other commercially available nonionic surfactants include Dobanol 91-
8C
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42
marketed by Shell Chemical Co. and Genapol UD-080~ marketed by Hoechst. This
category of nonionic surfactant is referred to generally as "alkyl
ethoxylates."
The condensation products of ethylene oxide with a hydrophobic base formed by
the condensation of propylene oxide with propylene glycol. The hydrophobic
portion of
these compounds preferably has a molecular weight of from about 1500 to about
1800
and exhibits water insolubility. The addition of polyoxyethylene moieties to
this
hydrophobic portion tends to increase the water solubility of the molecule as
a whole,
and the liquid character of the product is retained up to the point where the
polyoxyethylene content is about 50% of the total weight of the condensation
product,
which corresponds to condensation with up to about 40 moles of ethylene oxide.
Examples of compounds of this type include certain of the commercially-
available
Pluronic~ surfactants, marketed by BASF.
The condensation products of ethylene oxide with the product resulting from
the
reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of
these
products consists of the reaction product of ethylenediamine and excess
propylene oxide,
and generally has a molecular weight of from about 2500 to about 3000. This
hydrophobic moiety is condensed with ethylene oxide to the extent that the
condensation
product contains from about 40% to about 80% by weight of polyoxyethylene and
has a
molecular weight of from about 5,000 to about 11,000. Examples of this type of
nonionic surfactant include certain of the commercially available Tetronic~
compounds,
marketed by BASF.
Semi-polar nonionic surfactants are a special category of nonionic surfactants
which include water-soluble amine oxides containing one alkyl moiety of from
about 10
to about 18 carbon atoms and 2 moieties selected from the group consisting of
alkyl
groups and hydroxyalkyl groups containing from about 1 to about 3 carbon
atoms; water-
soluble phosphine oxides containing one alkyl moiety of from about 10 to about
18
carbon atoms and 2 moieties selected from the group consisting of alkyl groups
and
hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-
soluble sulfoxides containing one alkyl moiety of from about 10 to about 18
carbon
atoms and a moiety selected from the group consisting of alkyl and
hydroxyalkyl
moieties of from about 1 to about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine oxide surfactants
having the formula
O
T
R3 ~OR4)XN~RS )z
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43
wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures
thereof
containing from about 8 to about 22 carbon atoms; R4 is an alkylene or
hydroxyalkylene
group containing from about 2 to about 3 carbon atoms or mixtures thereof; x
is from 0
to about 3; and each RS is an alkyl or hydroxyalkyl group containing from
about 1 to
about 3 carbon atoms or a polyethylene oxide group containing from about 1 to
about 3
ethylene oxide groups. The RS groups can be attached to each other, e.g.,
through an
oxygen or nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include C 10-C 1 g alkyl dimethyl
amine oxides and Cg-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
Alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued
January
21, 1986, having a hydrophobic group containing from about 6 to about 30
carbon atoms,
preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g.,
a
polyglycoside, hydrophilic group containing from about 1.3 to about 10,
preferably from
about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide
units. Any
reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose,
galactose
and galactosyl moieties can be substituted for the glucosyl moieties.
(Optionally the
hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a
glucose or
galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds
can be,
e.g., between the one position of the additional saccharide units and the 2-,
3-, 4-, and/or
6- positions on the preceding saccharide units.
Optionally, and less desirably, there can be a polyalkylene-oxide chain
joining the
hydrophobic moiety and the polysaccharide moiety. The preferred alkyleneoxide
is
ethylene oxide. Typical hydrophobic groups include alkyl groups, either
saturated or
unsaturated, branched or unbranched containing from about 8 to about 18,
preferably
from about 10 to about 16, carbon atoms. Preferably, the alkyl group is a
straight chain
saturated alkyl group. The alkyl group can contain up to about 3 hydroxy
groups and/or
the polyalkyleneoxide chain can contain up to about 10, preferably less than
5,
alkyleneoxide moieties. Suitable alkyl polysaccharides are octyl, nonyl,
decyl,
undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and
octadecyl,
di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides,
glucoses, fructosides,
fructoses and/or galactoses. Suitable mixtures include coconut alkyl, di-, tri-
, tetra-, and
pentaglucosides and tallow alkyl tetra-, penta-, and hexa-glucosides.
The preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(glYcosyl)x
wherein R2 is selected from the group consisting of alkyl, alkyl-phenyl,
hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from about
CA 02360657 2001-07-20
WO 00/46332 PCT/US00/02666
44
to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3,
preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3
to about 10,
preferably from about 1.3 to about 3, most preferably from about 1.3 to about
2.7. The
glycosyl is preferably derived from glucose. To prepare these compounds, the
alcohol or
alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a
source of
glucose, to form the glucoside (attachment at the 1-position). The additional
glycosyl
units can then be attached between their 1-position and the preceding glycosyl
units 2-, 3-
4- and/or 6-position, preferably predominantly the 2-position.
Fatty acid amide surfactants having the formula:
O
R6-C-N(R7)2
wherein R6 is an alkyl group containing from about 7 to about 21 (preferably
from about
9 to about 17) carbon atoms and each R7 is selected from the group consisting
of
hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H40)xH where x varies from
about 1 to about 3.
Preferred amides are Cg-C20 ammonia amides, monoethanolamides, dietha-
nolamides, and isopropanolamides.
Cationic/amphoteric - Non-quaternary, cationic detersive surfactants can also
be
included in detergent compositions of the present invention. Cationic
surfactants useful
herein are described in U.S. Patent 4,228,044, Cambre, issued October 14,
1980.
Ampholytic surfactants can be incorporated into the detergent compositions
hereof. These surfactants can be broadly described as aliphatic derivatives of
secondary
or tertiary amines, or aliphatic derivatives of heterocyclic secondary and
tertiary amines
in which the aliphatic radical can be straight chain or branched. One of the
aliphatic
substituents contains at least about 8 carbon atoms, typically from about 8 to
about 18
carbon atoms, and at least one contains an anionic water-solubilizing group,
e.g.,
carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al.,
issued
December 30, 1975 at column 19, lines 18-35 for examples of ampholytic
surfactants.
Preferred amphoteric include C 12 -C 1 g alkyl ethoxylates ("AE") including
the so-called
narrow peaked alkyl ethoxylates and C6-C 12 alkyl phenol alkoxylates
(especially
ethoxylates and mixed ethoxy/propoxy), C 12-C 1 g betaines and sulfobetaines
("sultaines"), C 10-C 1 g amine oxides, and mixtures thereof.
Polyhydroxy Fatty Acid Amide Surfactant - The detergent compositions hereof
may also contain polyhydroxy fatty acid amide surfactant. The polyhydroxy
fatty acid
amide surfactant component comprises compounds of the structural formula:
CA 02360657 2001-07-20
WO 00/46332 PCT/US00/02666
O R1
R2-C-N-Z
wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a
mixture
thereof, preferably C1-C4 alkyl, more preferably C1 or C2 alkyl, most
preferably C1
alkyl (i.e., methyl); and R2 is a CS-C31 hydrocarbyl, preferably straight
chain C7-C19
alkyl or alkenyl, more preferably straight chain Cg-C 17 alkyl or alkenyl,
most preferably
straight chain C11-C15 alkyl or alkenyl, or mixtures thereof; and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3
hydroxyls
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 will be a glycityl. Suitable reducing
sugars
include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
As raw
materials, high dextrose corn syrup, high fructose corn syrup, and high
maltose corn
syrup can be utilized as well as the individual sugars listed above. These
corn syrups
may yield a mix of sugar components for Z. It should be understood that it is
by no
means intended to exclude other suitable raw materials. Z preferably will be
selected
from the group consisting of -CH2-(CHOH)n CH20H, -CH(CH20H)-(CHOH)n-1-
CH20H, -CH2-(CHOH)2(CHOR')(CHOH)-CH20H, and alkoxylated derivatives
thereof, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic
or aliphatic
monosaccharide. Most preferred are glycityls wherein n is 4, particularly -CH2-
(CHOH)4-CH20H.
R can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-
hydroxy ethyl, or N-2-hydroxy propyl.
R2-CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide,
myristamide, capricamide, palmitamide, tallowamide, etc.
Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl,
1-
deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
Methods for making polyhydroxy fatty acid amides are known in the art. In
general, they can be made by reacting an alkyl amine with a reducing sugar in
a reductive
amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then
reacting
the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a
condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid
amide
product. Processes for making compositions containing polyhydroxy fatty acid
amides
are disclosed, for example, in G.B. Patent Specification 809,060, published
February 18,
1959, by Thomas Hedley & Co., Ltd., U.S. Patent 2,965,576, issued December 20,
1960
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46
to E. R. Wilson, and U.S. Patent 2,703,798, Anthony M. Schwartz, issued March
8,
1955, and U.S. Patent 1,985,424, issued December 25, 1934 to Piggott, each of
which is
incorporated herein by reference.
B. Granular and/or Powder Laundry Detergent Compositions
Granular and/or powder laundry detergent compositions preferably comprise, in
addition to the enzyme granulates of the present invention, one or more
cleaning adjunct
materials as described herein.
CLEANING ADJUNCT MATERIALS
The laundry detergent compositions of the present invention as described
hereinbefore may optionally include, in addition to the enzyme granulates of
the present
invention, cleaning adjunct materials described below.
Biode agr dably branched surfactants
The present invention includes important embodiments comprising at least one
biodegradably branched and/or crystallinity disrupted and/or mid-chain
branched
surfactant or surfactant mixture. The terms "biodegradably branched" and/or
"crystallinity disrupted" and/or "mid-chain branched" (acronym "MCB" used
hereinafter)
indicate that such surfactants or surfactant mixtures are characterized by the
presence of
surfactant molecules having a moderately non-linear hydrophobe; more
particularly,
wherein the surfactant hydrophobe is not completely linear, on one hand, nor
is it
branched to an extent that would result in unacceptable biodegradation. The
preferred
biodegradably branched surfactants are distinct from the known commercial LAS,
ABS,
Exxal, Lial, etc. types, whether branched or unbranched. The biodegradably
branched
materials comprise particularly positioned light branching, for example from
about one to
about three methyl, and/or ethyl, and/or propyl or and/or butyl branches in
the
hydrophobe, wherein the branching is located remotely from the surfactant
headgroup,
preferably toward the middle of the hydrophobe. Typically from one to three
such
branches can be present on a single hydrophobe, preferably only one. Such
biodegradably branched surfactants can have exclusively linear aliphatic
hydrophobes, or
the hydrophobes can include cycloaliphatic or aromatic substitution. Highly
preferred are
MCB analogs of common linear alkyl sulfate, linear alkyl poly(alkoxylate) and
linear
alkylbenzenesulfonate surfactants. said surfactant suitably being selected
from mid-
chain-C,-C4-branched Cg-C1g-alkyl sulfates, mid-chain-CI-C4-branched C8-C18-
alkyl
ethoxylated, propoxylated or butoxylated alcohols, mid-chain-C1-C4-branched C8-
C~g-
alkyl ethoxysulfates, mid-chain-C1-C4-branched Cg-C»-alkyl benzenesulfonates
and
mixtures thereof. When anionic, the surfactants can in general be in acid or
salt, for
example sodium, potassium, ammonium or substituted ammonium, form. The
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47
biodegradably branched surfactants offer substantial improvements in cleaning
performance and/or usefulness in cold water and/or resistance to water
hardness and/or
economy of utilization. Such surfactants can, in general, belong to any known
class of
surfactants, e.g., anionic, nonionic, cationic, or zwitterionic. The
biodegradably branched
surfactants are synthesized through processes of Procter & Gamble, Shell, and
Sasol.
These surfactants are more fully disclosed in W098/23712 A published 06/04/98;
W097/38957 A published 10/23/97; W097/38956 A published 10/23/97; W097/39091
A published 10/23/97; W097/39089 A published 10/23/97; W097/39088 A published
10/23/97; W097/39087 Al published 10/23/97; W097/38972 A published 10/23/97;
WO 98/23566 A Shell, published 06/04/98; technical bulletins of Sasol; and the
following pending patent applications assigned to Procter & Gamble:
Preferred biodegradably branched surfactants herein in more detail include MCB
surfactants as disclosed in the following references:
W098/23712 A published 06/04/98 includes disclosure of MCB nonionic
surfactants including MCB primary alkyl polyoxyalkylenes of formula (1):
CH3CH2(CHZ)WC(R)H(CHZ)XC(Rl)H(CHZ)yC(RZ)H(CHZ)Z(EO/PO)mOH (1), where the
total number of carbon atoms in the branched primary alkyl moiety of this
formula,
including the R, Rl and R2 branching, but not including the carbon atoms in
the EO/PO
alkoxy moiety, is preferably 14-20, and wherein further for this surfactant
mixture, the
average total number of carbon atoms in the MCB primary alkyl hydrophobe
moiety is
preferably 14.5-17.5, more preferably 15-17; R, Rl and RZ are each
independently
selected from hydrogen and 1-3C alkyl, preferably methyl, provided R, R' and
RZ are not
all hydrogen and, when z is 1, at least R or R' is not hydrogen; w is an
integer of 0-13; x
is an integer of 0-13; y is an integer of 0-13; z is an integer of at least 1;
w+x+y+z is 8-
14; and EO/PO are alkoxy moieties preferably selected from ethoxy, propoxy and
mixed
ethoxy/propoxy groups, where m is at least 1, preferably 3-30, more preferably
5-20,
most preferably 5-15. Such MCB nonionics can alternately include butylene
oxide
derived moieties, and the -OH moiety can be replaced by any of the well-known
end-
capping moieties used for conventional nonionic surfactants.
W097/38957 A published 10/23/97 includes disclosure of mid- to near-mid-
chain branched alcohols of formulae R-CHZCHZCH(Me)CH-R'-CHZOH (I) and HOCHZ-
R-CHZ-CHZ-CH(Me)-R' (II) comprising: (A) dimerising alpha -olefins of formula
RCH=CHZ and RICH=CHZ to form olefins of formula R(CHZ)z-C(R')=CHZ and
Rl(CHZ)2-C(R)=CH2; (B) (i) isomerising the olefins and then reacting them with
carbon
monoxide/hydrogen under Oxo conditions or (ii) directly reacting the olefins
from step
(A) with CO/HZ under Oxo conditions. In the above formulae, R, R' = 3-7C
linear alkyl.
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48
W097/38957 A also discloses (i) production of MCB alkyl sulphate surfactants
by
sulphating (I) or (II); (ii) preparation of MCB alkylethoxy sulphates which
comprises
ethoxylating and then sulphating (I) or (II); (iii) preparation of MCB alkyl
carboxylate
surfactants which comprises oxidising (I) or (II) or their aldehyde
intermediates and (iv)
preparation of MCB acyl taurate, MCB acyl isethionate, MCB acyl sarcosinate or
MCB
acyl N-methylglucamide surfactants using the branched alkyl carboxylates as
feedstock.
W097/38956 A published 10/23/97 discloses the preparation of mid- to near
mid-chain branched alpha olefins which is effected by: (a) preparing a mixture
of carbon
monoxide and hydrogen; (b) reacting this mixture in the presence of a catalyst
under
Fischer-Tropsch conditions to prepare a hydrocarbon mixture comprising. the
described
olefins; and (c) separating the olefins from the hydrocarbon mixture.
W097/38956 A
further discloses the preparation of mid- to near mid-chain branched alcohols
by reacting
the olefins described with CO/HZ under Oxo conditions. These alcohols can be
used to
prepare (1) MCB sulphate surfactants by sulphating the alcohols; (2) MCB alkyl
ethoxy
sulphates by ethoxylating, then sulphating, the alcohols; or (3) branched
alkyl
carboxylate surfactants by oxidising the alcohols or their aldehyde
intermediates. The
branched carboxylates formed can be used as a feedstock to prepare branched
acyl
taurate, acyl isethionate, acyl sarcosinate or acyl N-methylglucamide
surfactants, etc.
W097/39091 A published 10/23/97 includes disclosure of a detergent surfactant
composition comprising at least 0.5 ( especially 5, more especially 10, most
especially
20) wt% of longer alkyl chain, MCB surfactant of formula (I). A-X-B (I)
wherein A is a
9-22 (especially 12-18) C MCB alkyl hydrophobe having: (i) a longest linear C
chain
attached to the X-B moiety of 8-21C atoms; (ii) 1-3C alkyl moiety(s) branching
from this
longest linear chain; (iii) at least one of the branching alkyl moieties
attached directly to a
C of the longest linear C chain at a position within the range of position 2
C, counting
from C 1 which is attached to the CHZB moiety, to the omega-2 carbon (the
terminal C
minus 2C); and (iv) the surfactant composition has an average total number of
C atoms in
the A-X moiety of 14.5-17.5 ( especially 15-17); and B is a hydrophilic
(surfactant head-
group) moiety preferably selected from sulfates, sulfonates, polyoxyalkylene (
especially
polyoxyethylene or polyoxypropylene), alkoxylated sulphates, polyhydroxy
moieties,
phosphate esters, glycerol sulphonates, polygluconates, polyphosphate esters,
phosphonates, sulphosuccinates, sulphosuccinates, polyalkoxylated
carboxylates,
glucamides, taurinates, sarcosinates, glycinates, isethionates, mono-/di-
alkanol-amides,
monoalkanolamide sulphates, diglycol-amide and their sulphates, glyceryl
esters and
their sulphates, glycerol ethers and their sulphates, polyglycerol ether and
their sulphates,
sorbitan esters, polyalkoxylated sorbitan esters, ammonio-alkane-sulphonates,
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49
amidopropyl betaines, alkylated quat., alkylated/poly-hydroxyalkylated
(oxypropyl) quat.,
imidazolines, 2-yl succinates, sulphonated alkyl esters and sulphonated fatty
acids; and
X- is -CHZ- or -C(O)-. W097/39091 A also discloses a laundry detergent or
other
cleaning composition comprising: (a) 0.001-99% of detergent surfactant (I);
and (b) 1 -
99.999% of adjunct ingredients.
W097/39089 A published 10/23/97 includes disclosure of liquid cleaning
compositions comprising: (a) as part of surfactant system 0.1-50 (especially 1-
40) wt
of a mid-chain branched surfactant of formula (I); (b) as the other part of
the surfactant
system 0.1-50 wt% of co-surfactant(s); (c) 1-99.7 wt% of a solvent; and (d)
0.1-75 wt%
of adjunct ingredients. Formula (I) is A-CHZ-B wherein A = 9-22 (especially 12-
18) C
MCB alkyl hydrophobe having: (i) a longest linear C chain attached to the X-B
moiety of
8-21C atoms; (ii) 1-3C alkyl moiety(s) branching from this longest linear
chain; (iii) at
least one of the branching alkyl moieties attached directly to a C of the
longest linear C
chain at a position within the range of position 2 C, counting from Carbon No.
1 which is
attached to the CH2B moiety, to the omega-2 carbon (the terminal C minus 2C);
and (iv)
the surfactant composition has an average total number of C atoms in the A-X
moiety of
14.5-17.5 ( especially 15-17); and B is a hydrophilic moiety selected from
sulphates,
polyoxyalkylene (especially polyoxyethylene and polyoxypropylene) and
alkoxylated
sulphates.
W097/39088 A published 10/23/97 includes disclosure of a surfactant
composition comprising 0.001-100% of MCB primary alkyl alkoxylated sulphates)
of
formula (I):
CH3CH2(CH)WCHR(CH2)XCHRI(CHZ)yCHR2(CH2)ZOS03M (I) wherein the total number
of C atoms in compound (I) including R, RI and R2, is preferably 14-20 and the
total
number of C atoms in the branched alkyl moieties preferably averages 14.5-17.5
(especially 15-17); R, Rl and RZ are selected from H and 1-3C alkyl (
especially Me)
provided R, Rl and RZ are not all H; when z = 1 at least R or Rl is not H; M
are canons
especially selected from Na, K, Ca, Mg, quaternary alkyl ammonium of formula
N+R3R4RSR6 (II); M is especially Na and/or K; R3, R4, R5, R6 are selected from
H, 1-22C
alkylene, 4-22C branched alkylene, 1-6C alkanol, 1-22C alkenylene, and/or 4-
22C
branched alkenylene; w, x, y = 0-13; z is at least l; w+x+y+z = 8-14.
W097/39088 A
also discloses (1) a surfactant composition comprising a mixture of branched
primary
alkyl sulphates of formula (I) as above. M is a water-soluble canon; When RZ
is 1-3C
alkyl, the ratio of surfactants having z = 1 to surfactants having z = 2 or
greater is
preferably at least 1:1 ( most especially 1:100); (2) a detergent composition
comprising:
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WO 00/46332 PCT/US00/02666
(a) 0.001-99% of MCB primary alkyl alkoxylated sulphate of formula (III)
and/or (IV).
CH3(CHZ)aCH(CH3)(CHZ)bCH20S03M (III)
CH3(CHZ)dCH(CH3)(CH2)eCH(CH3)CHZOS03M (IV) wherein a, b, d, and a are
integers,
preferably a+b = 10-16, d+e = 8-14 and when a+b = 10, a = 2-9 and b = 1-8;
when a+b =
11, a = 2-10 and b = 1-9; when a+b = 12, a = 2-11 and b = 1-10; when a+b = 13,
a = 2-12
and b = 1-1 l; when a+b = 14, a = 2-13 and b = 1-12; when a+B = 15, a = 2-14
and b = 1-
13; when a+b = 16, a = 2-14 and b = 1-14; when d+e = 8, d = 2-7 and a = 1-6;
when d+e
= 9, d = 2-8 and a = 1-7; when d+e = 10, d = 2-9 and a = 1-8; when d+e = 11, d
= 2-10
and a = 1-9; when d+e = 12, d = 2-11 and a = 1-10; when d+e = 13, d = 2-12 and
a = 1-
11; when d+e = 14, d = 2-13 and a = 1-12; and (b) 1-99.99 wt% of detergent
adjuncts; (3)
a mid-chain branched primary alkyl sulphate surfactant of formula(V):
CH3CH2(CHZ)XCHR~(CH2)yCHR2(CHZ)ZOS03M (V) wherein x, y = 0-12; z is at least
2;
x+y+z = 11-14; R' and RZ are not both H; when one of RI or R2 is H, and the
other is
Me, x + y +z is not 12 or 13; and when RI is H and RZ is Me, x + y is not 11
when z = 3
and x + y is not 9 when z = 5; (4) Alkyl sulphates of formula (III) in which a
and b are
integers and a = b = 12 or 13, a = 2-11, b = 1-10 and M is Na, K, and
optionally
substituted ammonium; (5) alkyl sulphates of formula (IV) in which d and a are
integers
and d = a is 10 or 11 and when d = a is 10, d = 2-9 and a = 1-8; when d = a =
11, d = 2-10
and a = 1-9 and m is Na, K, optionally substituted ammonium ( especially Na);
(6)
methyl branched primary alkyl sulphates selected from 3-, 4- 5-, 6-, 7-, 8-, 9-
, 10-, 11-,
12- or 13- methyl pentadecanol sulphate; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-,
12-, 13-, or 14-
methyl hexadecanol sulphate; 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 2,9-, 2,10-,
2,11-, 2,12-
methyl tetradecanol sulphate; 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 2,9-, 2,10-,
2,11-, 2,12-, or
2,13- methyl pentadecanol sulphate and/or mixtures of these compounds.
W097/39087 A published 10/23/97 includes disclosure of a surfactant
composition comprising 0.001-100% of mid-chain branched primary alkyl
alkoxylated
sulphates) of formula (I) wherein that total number of C atoms in compound (I)
including R, R' and R3, but not including C atoms of EO/PO alkoxy moieties is
14-20
and yhe total number of C atoms in branched alkyl moieties averages 14.5-17.5
(especially 15-17); R, R1 and R2 = H or 1-3C alkyl ( especially Me) and R, Rl
and RZ are
not all H; when z = 1 at least R or R' is not H; M = canons especially
selected from Na,
K, Ca, Mg, quaternary alkyl amines of formula (II) ( M is especially Na and/or
K) R3, R4,
R5, R6 = H, 1-22C alkylene, 4-22C branched alkylene, 1-6C alkanol, 1-22C
alkenylene,
and/or 4-22C branched alkenylene; w, x, y = 0-13; z is at least 1; w+x+y+z = 8-
14;
EO/PO are alkoxy moieties, especially ethoxy and/or propoxy; m is at least
0.01,
especially 0.1-30, more especially 0.5-10, most especially 1-5. Also disclosed
are: (1) a
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51
surfactant composition comprising a mixture of branched primary alkyl
alkoxylated
sulphates of formula (I) When R2 = 1-3C alkyl, the ratio of surfactants having
z = 2 or
greater to surfactant having z = 1 is at least l:l, especially 1.5:1, more
especially 3:1,
most especially 4:1; (2) a detergent composition comprising: (a) 0.001-99% of
mid-chain
branched primary alkyl alkoxylated sulphate of formula (III) and/or (IV) M is
as above; a,
b, d, and a are integers, a+b = 10-16, d+e = 8-14 and when a+b = 10, a = 2-9
and b = 1-8;
when a+b = 11, a = 2-10 and b = 1-9; when a+b = 12, a = 2-11 and b = 1-10;
when a+b =
13, a = 2-12 and b = 1-11; when a+b = 14, a = 2-13 and b = 1-12; when a+b =
15, a = 2-
14 and b = 1-13; when a+b = 16, a = 2-14 and b = 1-14; when d+e = 8, d = 2-7
and a = 1-
6; when d+e = 9, d = 2-8 and a = 1-7; when d+e = 10, d = 2-9 and a = 1-8; when
d+e =
11, d = 2-10 and a = 1-9; when d+e = 12, d = 2-11 and a = 1-10; when d+e = 13,
d = 2-12
and a = 1-11; when d+e = 14, d = 2-13 and a = 1-12; and (b) 1-99.99 wt% of
detergent
adjuncts; (3) a MCB primary alkyl alkoxylated sulphate surfactant of
formula(V) Rl, R2,
M, EO/PO, m as above; x,y = 0-12; z is at least 2; x+y+z = 11-14; (4) a mid-
chain
branched alkyl alkoxylated sulphate of formula (III) in which: a = 2-1 l; b =
1-10; a+b =
12 or 13; M, EO/PO and m are as above; (S) a mid-chain branched alkyl
alkoxylated
sulphate compound of formula (IV) in which: d+e = 10 or 11; when d+e = 10, d =
2-9
and a = 1-8 and when d+e = 11, d = 2-10 and a = 1-9; M is as above (
especially Na);
EO/PO and m are as above; and (6) methyl branched primary alkyl ethoxylated
sulphates
selected from 3-, 4- 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12- or 13- methyl
pentadecanol ethoxylated
sulphate; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, or 14- methyl
hexadecanol
ethoxylated sulphate; 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 2,9-, 2,10-, 2,11-,
2,12-methyl
tetradecanol ethoxylated sulphate; 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 2,9-,
2,10-, 2,11-, 2,12-
or 2,13- methyl pentadecanol ethoxylated sulphate and/or mixtures of these
compounds.
The compounds are ethoxylated with average degree of ethoxylation of 0.1-10.
W097/38972 A published 10/23/97 includes disclosure of a method for
manufacturing
longer chain alkyl sulphate surfactant mixture compositions comprising (a)
sulphating
with S03, preferably in a falling film reactor, a long chain aliphatic alcohol
mixture
having an average carbon chain length of at least 14.5-17.5, the alcohol
mixture
comprising at least 10%, preferably at least 25%, more preferably at least 50%
still more
preferably at least 75%, most preferably at least 95% of a MCB aliphatic
alcohol having
formula (I); where: R,R1,R2 = H or 1-3C alkyl, preferably methyl, provided R,
Rl and RZ
are not all H, and when z = 1, at least R or RI is not H; w,x,y = integers 0-
13; z = integer
of at least l; and w+x+y+z = 8-14; where the total number of carbon atoms in
the
branched primary, alkyl moiety of formula (I), including the R, Rl and RZ
branching, is
14-20, and where further for the alcohol mixture the average total number of
carbon
CA 02360657 2001-07-20
WO 00/46332 PCT/US00/02666
52
atoms in the branched primary alkyl moieties having formula (I) is > 14.5-
17.5,
preferably, >15-17; and (b) neutralising the alkyl sulphate acid produced by
step (a),
preferably using a base selected from KOH, NaOH, ammonia, monoethanolamine,
triethanolamine and mixtures of these. Also disclosed is a method for
manufacturing
longer chain alkyl alkoxylated sulphate surfactant mixture compositions,
comprising
alkoxylating the specified long chain aliphatic alcohol mixture; sulphating
the resulting
polyoxyalkylene alcohol with 503; and neutralising the resulting alkyl
alkoxylate
sulphate acid. Alternatively, the alkyl alkoxylated sulphates may be produced
directly
from the polyoxyalkylene alcohol by sulphating with S03 and neutralising.
WO 98/23566 A Shell, published 06/04/98 discloses branched primary alcohol
compositions having 8-36 C atoms and an average number of branches per mol of
0.7-3
and comprising ethyl and methyl branches. Also disclosed are: (1) a branched
primary
alkoxylate composition preparable by reacting a branched primary alcohol
composition
as above with an oxirane compound; (2) a branched primary alcohol sulphate
preparable
by sulphating a primary alcohol composition as above; (3) a branched
alkoxylated
primary alcohol sulphate preparable by alkoxylating and sulphating a branched
alcohol
composition as above; (4) a branched primary alcohol carboxylate preparable by
oxidising a branched primary alcohol composition as above; (5) a detergent
composition
comprising: (a) surfactants) selected from branched primary alcohol
alkoxylates as in
(1), branched primary alcohol sulphates as in (2), and branched alkoxylated
primary
alcohol sulphates as in (3); (b) a builder; and (c) optionally additives)
selected from
foam control agents, enzymes, bleaching agents, bleach activators, optical
brighteners,
co-builders, hydrotropes and stabilisers. The primary alcohol composition, and
the
sulphates, alkoxylates, alkoxy sulphates and carboxylates prepared from them
exhibit
good cold water detergency and biodegradability.
Biodegradably branched surfactants useful herein also include the modified
alkylaromatic, especially modified alkylbenzenesulfonate surfactants described
in
copending commonly assigned patent applications (P&G Case Nos. 7303P, 7304P).
In
more detail, these surfactants include (P&G Case 6766P) alkylarylsulfonate
surfactant
systems comprising from about 10% to about 100% by weight of said surfactant
system
of two or more crystallinity-disrupted alkylarylsulfonate surfactants of
formula (B-Ar-
D)a(Mq+)b wherein D is S03-, M is a canon or cation mixture, q is the valence
of said
canon, a and b are numbers selected such that said composition is
electroneutral; Ar is
selected from benzene, toluene, and combinations thereof; and B comprises the
sum of at
least one primary hydrocarbyl moiety containing from 5 to 20 carbon atoms and
one or
more crystallinity-disrupting moieties wherein said crystallinity-disrupting
moieties
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53
interrupt or branch from said hydrocarbyl moiety; and wherein said
alkylarylsulfonate
surfactant system has crystallinity disruption to the extent that its Sodium
Critical
Solubility Temperature, as measured by the CST Test, is no more than about
40°C and
wherein further said alkylarylsulfonate surfactant system has at least one of
the following
properties: percentage biodegradation, as measured by the modified SCAS test,
that
exceeds tetrapropylene benzene sulfonate; and weight ratio of nonquaternary to
quaternary carbon atoms in B of at least about 5:1.
Such compositions also include (P&G Case 7303P) surfactant mixtures
comprising (preferably, consisting essentially of): (a) from about 60% to
about 95% by
weight (preferably from about 65% to about 90%, more preferably from about 70%
to
about 85%) of a mixture of branched alkylbenzenesulfonates having formula (I):
O
R~ R2
\ L~
I
A [Mq~]b
S03
a
(I)
wherein L is an acyclic aliphatic moiety consisting of carbon and hydrogen and
having two methyl termini, and wherein said mixture of branched
alkylbenzenesulfonates
contains two or more (preferably at least three, optionally more) of said
compounds
differing in molecular weight of the anion of said formula (I) and wherein
said mixture of
branched alkylbenzenesulfonates is characterized by an average carbon content
of from
about 10.0 to about 14.0 carbon atoms (preferably from about 11.0 to about
13.0, more
preferably from about 11.5 to about 12.5), wherein said average carbon content
is based
on the sum of carbon atoms in R', L and R2, (preferably said sum of carbon
atoms in Rl,
L and RZ is from 9 to 15, more preferably, 10 to 14) and further, wherein L
has no
substituents other than A, R' and RZ; M is a cation or cation mixture
(preferably selected
from H, Na, K, Ca, Mg and mixtures thereof, more preferably selected from H,
Na, K
and mixtures thereof, more preferably still, selected from H, Na, and mixtures
thereof)
having a valence q (typically from 1 to 2, preferably 1 ); a and b are
integers selected such
that said compounds are electroneutral (a is typically from 1 to 2, preferably
1, b is 1); Rl
is Cl-C3 alkyl (preferably Cl-Cz alkyl, more preferably methyl); RZ is
selected from H
and C,-C3 alkyl (preferably H and CI-CZ alkyl, more preferably H and methyl,
more
preferably H and methyl provided that in at least about 0.5, more preferably
0.7, more
preferably 0.9 to 1.0 mole fraction of said branched alkylbenzenesulfonates RZ
is H); A is
a benzene moiety (typically A is the moiety -C6H4- , with the S03 moiety of
Formula (I)
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54
in para- position to the L moiety, though in some proportion, usually no more
than about
5%, preferably from 0 to 5% by weight, the S03 moiety is ortho- to L); and (b)
from
about 5% to about 60% by weight (preferably from about 10% to about 35%, more
preferably from about 1 S% to about 30%) of a mixture of nonbranched
alkylbenzenesulfonates having formula (II):
O
Y
I
[Mq~~b
3
a (II)
wherein a, b, M, A and q are as defined hereinbefore and Y is an unsubstituted
linear
aliphatic moiety consisting of carbon and hydrogen having two methyl termini,
and
wherein Y has an average carbon content of from about 10.0 to about 14.0
(preferably
from about 11.0 to about 13.0, more preferably 11.5 to 12.5 carbon atoms);
(preferably
said mixture of nonbranched alkylbenzenesulfonates is further characterized by
a sum of
carbon atoms in Y, of from 9 to 1 S, more preferably 10 to 14); and wherein
said
composition is further characterized by a 2/3-phenyl index of from about 350
to about
10,000 (preferably from about 400 to about 1200, more preferably from about
500 to
about 700) (and also preferably wherein said surfactant mixture has a 2-methyl-
2-phenyl
index of less than about 0.3, preferably less than
about 0.2, more preferably less than about 0.1, more preferably still, from 0
to 0.05).
Also encompassed by way of mid-chain branched surfactants of the alkylbenzene-
derived types are surfactant mixtures comprising the product of a process
comprising the
steps o~ alkylating benzene with an alkylating mixture; sulfonating the
product of (I);
and neutralizing the product of (II); wherein said alkylating mixture
comprises: (a) from
about 1 % to about 99.9%, by weight of branched C7-CZO monoolefins, said
branched
monoolefins having structures identical with those of the branched monoolefins
formed
by dehydrogenating branched parafins of formula R1LR2 wherein L is an acyclic
aliphatic
moiety consisting of carbon and hydrogen and containing two terminal methyls;
RI is C~
to C3 alkyl; and RZ is selected from H and C1 to C3 alkyl; and (b) from about
0.1% to
about 85%, by weight of C7-CZO linear aliphatic olefins; wherein said
alkylating mixture
contains said branched C7-CZO monoolefins having at least two different carbon
numbers
in said C7-CZO range, and has a mean carbon content of from about 9.5 to about
14.5
carbon atoms; and wherein said components (a) and (b) are at a weight ratio of
at least
about 15:85.
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SS
Bleaching-System - The laundry compositions of the present invention may
comprise a bleaching system. Bleaching systems typically comprise a "bleaching
agent"
(source of hydrogen peroxide) and an "initiator" or "catalyst". When present,
bleaching
agents will typically be at levels of from about 1%, preferably from about 5%
to about
30%, preferably to about 20% by weight of the composition. If present, the
amount of
bleach activator will typically be from about 0.1%, preferably from about 0.5%
to about
60%, preferably to about 40% by weight, of the bleaching composition
comprising the
bleaching agent-plus-bleach activator.
Bleaching Agents - Hydrogen peroxide sources are described in detail in the
herein incorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed
(1992,
John Wiley & Sons), Vol. 4, pp. 271-300 "Bleaching Agents (Survey)", and
include the
various forms of sodium perborate and sodium percarbonate, including various
coated
and modified forms.
The preferred source of hydrogen peroxide used herein can be any convenient
source, including hydrogen peroxide itself. For example, perborate, e.g.,
sodium
perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium
carbonate
peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate
peroxyhydrate,
urea peroxyhydrate, or sodium peroxide can be used herein. Also useful are
sources of
available oxygen such as persulfate bleach (e.g., OXONE, manufactured by
DuPont).
Sodium perborate monohydrate and sodium percarbonate are particularly
preferred.
Mixtures of any convenient hydrogen peroxide sources 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
micrometers, 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 a
silicate,
borate or water-soluble surfactants. Percarbonate is available from various
commercial
sources such as FMC, Solway and Tokai Denka.
Compositions of the present invention may also comprise as the bleaching agent
a
chlorine-type bleaching material. Such agents are well known in the art, and
include for
example sodium dichloroisocyanurate ("NaDCC"). However, chlorine-type bleaches
are
less preferred for compositions which comprise enzymes.
Via) Bleach Activators - Preferably, the peroxygen bleach component in the
composition is formulated with an activator (peracid precursor). The activator
is present
at levels of from about 0.01 %, preferably from about 0.5%, more preferably
from about
1% to about 15%, preferably to about 10%, more preferably to about 8%, by
weight of
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56
the composition. Preferred activators are selected from the group consisting
of
tetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL), 4-
nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam,
benzoyloxybenzenesulphonate
(BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz),
decanoyloxybenzenesulphonate (C10-OBS), benzoylvalerolactam (BZVL),
octanoyloxybenzenesulphonate (Cg-OBS), perhydrolyzable esters and mixtures
thereof,
most preferably benzoylcaprolactam and benzoylvalerolactam. Particularly
preferred
bleach activators in the pH range from about 8 to about 9.5 are those selected
having an
OBS or VL leaving group.
Preferred hydrophobic bleach activators include, but are not limited to,
nonanoyloxybenzenesulphonate (NOBS), 4-[N-(nonaoyl) amino hexanoyloxy]-benzene
sulfonate sodium salt (NACA-OBS) an example of which is described in U.S.
Patent No.
5,523,434, dodecanoyloxybenzenesulphonate (LOBS or C12-OBS), 10-
undecenoyloxybenzenesulfonate (UDOBS or C11-OBS with unsaturation in the 10
position), and decanoyloxybenzoic acid (DOBA).
Preferred bleach activators are those described in U.S. 5,698,504 Christie et
al.,
issued December 16, 1997; U.S. 5,695,679 Christie et al. issued December 9,
1997; U.S.
5,686,401 Willey et al., issued November 11, 1997; U.S. 5,686,014 Hartshorn et
al.,
issued November 11, 1997; U.S. 5,405,412 Willey et al., issued April 11, 1995;
U.S.
5,405,413 Willey et al., issued April 11, 1995; U.S. 5,130,045 Mitchel et al.,
issued July
14, 1992; and U.S. 4,412,934 Chung et al., issued November 1, 1983, and
copending
patent applications U. S. Serial Nos. 08/709,072, 08/064,564, all of which are
incorporated herein by reference.
The mole ratio of peroxygen bleaching compound (as Av0) to bleach activator in
the present invention generally ranges from at least 1:1, preferably from
about 20:1, more
preferably from about 10:1 to about 1:1, preferably to about 3:1.
Quaternary substituted bleach activators may also be included. The present
laundry compositions preferably comprise a quaternary substituted bleach
activator
(QSBA) or a quaternary substituted peracid (QSP); more preferably, the former.
Preferred QSBA structures are further described in U.S. 5,686,015 Willey et
al., issued
November 11, 1997; U.S. 5,654,421 Taylor et al., issued August 5, 1997; U.S.
5,460,747
Gosselink et al., issued October 24, 1995; U.S. 5,584,888 Miracle et al.,
issued
December 17, 1996; and U.S. 5,578,136 Taylor et al., issued November 26, 1996;
all of
which are incorporated herein by reference.
Highly preferred bleach activators useful herein are amide-substituted as
described in U.S. 5,698,504, U.S. 5,695,679, and U.S. 5,686,014 each of which
are
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WO 00/46332 PCT/US00/02666
57
cited herein above. Preferred examples of such bleach activators include: (6-
octanamidocaproyl)oxybenzenesulfonate,(6-nonanamidocaproyl)
oxybenzenesulfonate,
(6-decanamidocaproyl)oxybenzenesulfonate and mixtures thereof.
Other useful activators, disclosed in U.S. 5,698,504, U.S. 5,695,679, U.S.
5,686,014 each of which is cited herein above and U.S. 4,966,723Hodge et al.,
issued
October 30, 1990, include benzoxazin-type activators, such as a C6H4 ring to
which is
fused in the 1,2-positions a moiety --C(O)OC(Rl)=N-.
Depending on the activator and precise application, good bleaching results can
be obtained from bleaching systems having with in-use pH of from about 6 to
about 13,
preferably from about 9.0 to about 10.5. Typically, for example, activators
with
electron-withdrawing moieties are used for near-neutral or sub-neutral pH
ranges.
Alkalis and buffering agents can be used to secure such pH.
Acyl lactam activators, as described in U.S. 5,698,504, U.S. 5,695,679 and
U.S.
5,686,014, each of which is cited herein above, are very useful herein,
especially the acyl
caprolactams (see for example WO 94-28102 A) and acyl valerolactams (see U.S.
5,503,639 Willey et al., issued April 2, 1996 incorporated herein by
reference).
fib) Organic Peroxides, especially Diacyl Peroxides - These are extensively
illustrated in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John
Wiley
and Sons, 1982 at pages 27-90 and especially at pages 63-72, all incorporated
herein by
reference. If a diacyl peroxide is used, it will preferably be one which
exerts minimal
adverse impact on spotting/filming.
(c) Metal-containing Bleach Catalysts - The present invention compositions and
methods may utilize metal-containing bleach catalysts that are effective for
use in
bleaching compositions. Preferred are manganese and cobalt-containing bleach
catalysts.
One type of metal-containing bleach catalyst is a catalyst system comprising a
transition metal cation of defined bleach catalytic activity, such as copper,
iron, titanium,
ruthenium tungsten, molybdenum, or manganese canons, an auxiliary metal canon
having little or no bleach catalytic activity, such as zinc or aluminum
cations, and a
sequestrate having defined stability constants for the catalytic and auxiliary
metal cations,
particularly ethylenediaminetetraacetic acid, ethylenediaminetetra
(methylenephosphonic
acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S.
4,430,243
Bragg, issued February 2, 1982.
Manganese Metal Complexes - If desired, the compositions herein can be
catalyzed by means of a manganese compound. Such compounds and levels of use
are
well known in the art and include, for example, the manganese-based catalysts
disclosed
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WO 00/46332 PCT/US00/02666
58
in U.S. Patent Nos. 5,576,282; 5,246,621; 5,244,594; 5,194,416; and 5,114,606;
and
European Pat. App. Pub. Nos. 549,271 Al, 549,272 A1, 544,440 A2, and 544,490
Al;
Preferred examples of these catalysts include Mn~2(u-O)3(1,4,7-trimethyl-1,4,7-
triazacyclononane)2(PF6)2, MnEI2(u-O) 1 (u-OAc)2( 1,4,7-trimethyl-1,4,7-
triazacyclononane)2(C104)2, Mn~4(u-O)6(1,4,7-triazacyclononane)4(C104)4, MnEI-
Mn~4(u-O)1(u-OAc)2-(1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)3,
Mn~(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. Patent Nos. 4,430,243
and U.S.
5,114,611. The use of manganese with various complex ligands to enhance
bleaching is
also reported in the following: U.S. Patent Nos. 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.
Cobalt Metal Complexes - Cobalt bleach catalysts useful herein are known, and
are described, for example, in U.S. Patent Nos. 5,597,936; 5,595,967; and
5,703,030; and
M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inor~.
Bioino~
Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst useful herein
are cobalt
pentaamine acetate salts having the formula [Co(NH3)SOAc] Ty, wherein "OAc"
represents an acetate moiety and "Ty' is an anion, and especially cobalt
pentaamine
acetate chloride, [Co(NH3)SOAc]C12; as well as [Co(NH3)SOAc](OAc)2;
[Co(~3)SOAc](PF6)2~ [Co~3)SOAc](S04)~ [Co(~3)SOAc](BF4)2~ and
[Co(NH3)SOAc](N03)2 (herein "PAC").
These cobalt catalysts are readily prepared by known procedures, such as
taught
for example in U.S. Patent Nos. 5,597,936; 5,595,967; and 5,703,030; in the
Tobe article
and the references cited therein; and in U.S. Patent 4,810,410; J. Chem. Ed.
(1989), 66
(12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L.
Jolly
(Prentice-Hall; 1970), pp. 461-3; Inor~. Chem., 18, 1497-1502 (1979); Inor~.
Chem., 21,
2881-2885 (1982); Inor~. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-
176
(1960); and Journal of Physical Chemistry, 56, 22-25 (1952).
Transition Metal Complexes of Macropolycyclic Rigid Lig_ands - Compositions
herein may also suitably include as bleach catalyst a transition metal complex
of a
macropolycyclic rigid ligand. The phrase "macropolycyclic rigid ligand" is
sometimes
abbreviated as "MRL" in discussion below. The amount used is a catalytically
effective
amount, suitably about 1 ppb or more, for example up to about 99.9%, more
typically
about 0.001 ppm or more, preferably from about 0.05 ppm to about 500 ppm
(wherein
"ppb" denotes parts per billion by weight and "ppm" denotes parts per million
by weight).
Suitable transition metals e.g., Mn are illustrated hereinafter.
"Macropolycyclic"
means a MRL is both a macrocycle and is polycyclic. "Polycyclic" means at
least
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59
bicyclic. The term "rigid" as used herein herein includes "having a
superstructure" and
"cross-bridged". "Rigid" has been defined as the constrained converse of
flexibility: see
D.H. Busch., Chemical Reviews., (1993), 93, 847-860, incorporated by
reference. More
particularly, "rigid" as used herein means that the MRL must be determinably
more rigid
than a macrocycle ("parent macrocycle") which is otherwise identical (having
the same
ring size and type and number of atoms in the main ring) but lacking a
superstructure
(especially linking moieties or, preferably cross-bridging moieties) found in
the MRL's.
In determining the comparative rigidity of macrocycles with and without
superstructures,
the practitioner will use the free form (not the metal-bound form) of the
macrocycles.
Rigidity is well-known to be useful in comparing macrocycles; suitable tools
for
determining, measuring or comparing rigidity include computational methods
(see, for
example, Zimmer, Chemical Reviews, (1995), 95(38), 2629-2648 or Hancock et
al.,
Inorganica Chimica Acta, (1989), 164, 73-84.
Preferred MRL's herein are a special type of ultra-rigid ligand which is cross-
bridged. A "cross-bridge" is nonlimitingly illustrated in 1.11 hereinbelow. In
1.11, the
cross-bridge is a -CH2CH2- moiety. It bridges N1 and N8 in the illustrative
structure. By
comparison, a "same-side" bridge, for example if one were to be introduced
across N1
and N12 in 1.11, would not be sufficient to constitute a "cross-bridge" and
accordingly
would not be preferred.
Suitable metals in the rigid ligand complexes include Mn(II), Mn(III), Mn(IV),
Mn(V), Fe(II), Fe(III), Fe(N), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III),
Cu(I), Cu(II),
Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(N), V(V), Mo(IV),
Mo(V),
Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV). Preferred
transition-
metals in the instant transition-metal bleach catalyst include manganese, iron
and
chromium.
More generally, the MRL's (and the corresponding transition-metal catalysts)
herein suitably comprise:
(a) at least one macrocycle main ring comprising four or more heteroatoms; and
(b) a covalently connected non-metal superstructure capable of increasing the
rigidity of
the macrocycle, preferably selected from
(i) a bridging superstructure, such as a linking moiety;
(ii) a cross-bridging superstructure, such as a cross-bridging linking moiety;
and
(iii) combinations thereof.
The term "superstructure" is used herein as defined in the literature by Busch
et
al., see, for example, articles by Busch in "Chemical Reviews".
US 000002666
CA 02360657 2001-07-20
W
Transition Metal Complexes of Macronolvcvclic Rittid Liaands -
Compositions
herein may also suitably include as bleach catalyst a transition metal complex
of a
macropolycyclic rigid ligand. The phrase "macropolycyclic rigid ligand" is
sometimes abbreviated as "MRL" in discussion below. The amount used is a
catalytically effective amount, suitably about I ppb or more, for example up
to about
99.9gto, more typically about 0.001 ppm or more, preferably from about 0.05
ppm to
about 500 ppm (wherein "ppb" denotes parts per billion by weight and "ppm"
denotes parts per million by weight). '
Suitable transition metals e.g., Mn are illustrated hereinafter.
"Macropolycyciic" means a MRL is both a macrocycle and is polycyclic.
"Polycyclic" means at least bicyclic. The term "rigid" as used herein herein
includes
"having a superstructure" and "cross-bridged". "Rigid" has been defined as the
constrained converse of flexibility: see D.H. Busch., Chemical Reviews.. (
1993), 93,
847-860, incorporated by reference. More particularly, "rigid" as used herein
means
that the MRL must be determinably more rigid than a macrocycle ("parent .
macrocycle") which is otherwise identical (having the same ring size and type
and
number of atoms in the main ring) but lacking a superstructure (especially
linking
moieties or, preferably cross-bridging moieties) found in the MRL's. In
determining
the comparative rigidity of macrocycles with and without superstructures, the
practitioner will use the free form (not the metal-bound form) of the
macrocycles.
Rigidity is well-known to be useful in comparing macrocycles; suitable tools
for
determining, measuring or comparing rigidity include computational methods
(see,
for example, Zimmer, Chemical Reviews, (1995), 95(38), 2629-2648 or Hancock et
al., Inoreanica Chimica Acta. ( 1989), 164, 73-84.
Preferred MRL's herein are a special type of ultra-rigid ligand which is cross-
bridged. A "cross-bridge" is nonlimitingly illustrated in Fig. 3 hereinbelow.
In Fig.
3, the cross-bridge is a -CH2CH2- moiety. It bridges N 1 and N8 in the
illustrative
structure. By comparison, a "same-side" bridge, for example if one were to be
introduced across N 1 and N 1 ~ in Fig. 3, would not be sufficient to
constitute a
"cross-bridge" and accordingly would not be preferred.
Suitable metals in the rigid ligand complexes include Mn(II), Mn(I>I),
Mn(IV), Mn(V), Fe(II), Fe(In), Fe(IV), Co(n, Co(>I), Co(111), Ni(I), Ni(II),
Ni(Ill), 1
Cu(I), Cu(II), Cu(IIn, Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V()TI), V(IV),
V(V),
Mo(IV), Mo(V), Mo(VI). W(IV), W{V), W(VI), Pd(ll), Ru(In, Ru(III), and Ru(IV).
Preferred transition-metals in the instant transition-metal bleach catalyst
include
manganese, iron and chromium.
AMENDED SHEET
' 19-01-2001 CA 02360657 2001-07-20 US 000002666
!.J
61
More generally, the MRL's (and the corresponding transition-metal catalysts)
herein suitably comprise:
(a) at least one macrocycle main ring comprising four or more heteroatoms; and
(b) a covalently connected non-metal superstructure capable of increasing the
rigidity of the macrocycle, preferably selected from
(i) a bridging superstructure, such as a linking moiety;
(ii) a cross-bridging superstructure, such as a cross-bridging linking moiety;
and
(iii) combinations thereof.
The term "superstructure" is used herein as defined in the literature by Busch
et al., see, for example, articles by Busch in "Chemical Reviews".
Preferred superstructures herein not only enhance the rigidity of the parent
macrocycle, but also favor folding of the macrocycle so that it co-ordinates
to a
metal in a cleft. Suitable superstructures can be remarkably simple, for
example a
linking moiety such as any of those illustrated in Fig. 1 and Fig. 2 below,
can be
used.
'(CH
Fig. 1
wherein n is an integer, for example from 2 to 8, preferably less than 6,
typically 2 to
4, or
T
(CH2) ~(CHZ)n
Z
Fig. 2
wherein m and n are integers from about 1 to 8, more preferably from 1 to 3; Z
is N
or CH; and T is a compatible substituent, for example H, alkyl,
trialkylammonium,
halogen, nitro, sulfonate, or the like. The aromatic ring in Fig. 2 can be
replaced by a
saturated ring, in which the atom in Z connecting into the ring can contain N,
O, S or
C.
Suitable MItL's are further nonlimitingly illustrated by the following
compound:
AMENDED SHEET
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62
Also suitable as bleaching agents are preformed peracids, such as phthalimido-
peroxy-caproic acid ("PAP"). See for example U.S. Patent Nos. 5,487,818,
5,310,934,
5,246,620, 5,279,757 and 5,132,431.
Enzyme Stabilizers - Enzymes for use in detergents can be stabilized by
various
techniques. Enzyme stabilization techniques are disclosed and exemplified in
U.S.
3,600,319, EP 199,405 and EP 200,586. Enzyme stabilization systems are also
described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving
proteases, xylanases and cellulases, is described in WO 9401532. The enzymes
employed herein can be stabilized by the presence of water-soluble sources of
calcium
and/or magnesium ions in the finished compositions which provide such ions to
the
enzymes. Suitable enzyme stabilizers and levels of use are described in U.S.
Pat. Nos.
5,705,464, 5,710,115 and 5,576,282.
Builders - The detergent and laundry compositions described herein preferably
comprise one or more detergent builders or builder systems. When present, the
compositions will typically comprise at least about 1 % builder, preferably
from about
5%, more preferably from about 10% to about 80%, preferably to about 50%, more
preferably to about 30% by weight, of detergent builder. Lower or higher
levels of
builder, however, are not meant to be excluded.
Preferred builders for use in the detergent and laundry compositions,
particularly
dishwashing compositions, described herein include, but are not limited to,
water-soluble
builder compounds, (for example polycarboxylates) as described in U.S. Patent
Nos.
5,695,679, 5,705,464 and 5,710,115. Other suitable polycarboxylates are
disclosed in
U.S. Patent Nos. 4,144,226, 3,308,067 and 3,723,322. Preferred
polycarboxylates are
hydroxycarboxylates containing up to three carboxy groups per molecule, more
particularly titrates.
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 (see, for example, U.S. Patent Nos. 3,159,581; 3,213,030;
3,422,021;
3,400,148 and 3,422,137), 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.
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Suitable silicates include the water-soluble sodium silicates with an
SiO2:Na20
ratio of from about 1.0 to 2.8, with ratios of from about 1.6 to 2.4 being
preferred, and
about 2.0 ratio being most preferred. The silicates may be in the form of
either the
anhydrous salt or a hydrated salt. Sodium silicate with an SiO2:Na20 ratio of
2.0 is the
most preferred. Silicates, when present, are preferably present in the
detergent and
laundry compositions described herein at a level of from about 5% to about 50%
by
weight of the composition, more preferably from about 10% to about 40% by
weight.
Partially soluble or insoluble builder compounds, which are suitable for use
in
the detergent and laundry compositions, particularly granular detergent
compositions,
include, but are not limited to, crystalline layered silicates, preferably
crystalline layered
sodium silicates (partially water-soluble) as described in U.S. Patent No.
4,664,839, and
sodium aluminosilicates (water-insoluble). When present in detergent and
laundry
compositions, these builders are typically present at a level of from about 1
% to 80% by
weight, preferably from about 10% to 70% by weight, most preferably from about
20%
to 60% by weight of the composition.
Crystalline layered sodium silicates having the general formula
NaMSix02x+1'YH20 wherein M is sodium or hydrogen, x is a number from about 1.9
to about 4, preferably from about 2 to about 4, most preferably 2, and y is a
number from
about 0 to about 20, preferably 0 can be used in the compositions described
herein.
Crystalline layered sodium silicates of this type are disclosed in EP-A-
0164514 and
methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043.
The
most preferred material is delta-Na2Si05, available from Hoechst AG as NaSKS-6
(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. SKS-6 is a highly preferred layered
silicate for use
in the compositions described herein herein, but other such layered silicates,
such as
those having the general formula NaMSix02x+1'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 in the compositions described 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-Na2Si05 (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.
The crystalline layered sodium silicate material is preferably present in
granular
detergent compositions as a particulate in intimate admixture with a solid,
water-soluble
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ionizable material. The solid, water-soluble ionizable material is preferably
selected
from organic acids, organic and inorganic acid salts and mixtures thereof.
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 have the
empirical
formula:
[Mz(A102)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 15 to about 264. Preferably, the
aluminosilicate builder is an aluminosilicate zeolite having the unit cell
formula:
NaZ[(A102)Z(Si02)y] ~xH20
wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5
and x is at least
5, preferably 7.5 to 276, more preferably from 10 to 264. The aluminosilicate
builders
are preferably in hydrated form and are preferably crystalline, containing
from about
10% to about 28%, more preferably from about 18% to about 22% water in bound
form.
These aluminosilicate ion exchange materials 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.
3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange
materials useful
herein are available under the designations Zeolite A, Zeolite B, Zeolite P,
Zeolite X,
Zeolite MAP and Zeolite HS and mixtures thereof. In an especially preferred
embodiment, the crystalline aluminosilicate ion exchange material has the
formula:
Nal2[(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.
Zeolite X has the
formula:
Nag6[(A102)g6(Si02) 106]'276H20
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 granular compositions,
especially in
combination with zeolite and/or layered silicate builders. Oxydisuccinates are
also
especially useful in such compositions and combinations.
Also suitable in the detergent compositions described herein are the 3,3-dicar-
boxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S.
4,566,984.
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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,
myristylsuccinate,
palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate,
and the
like. Laurylsuccinates are the preferred builders of this group, and are
described in
European Patent Application 86200690.5/0,200,263, published November 5, 1986.
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.
Dispersants - One or more suitable polyalkyleneimine dispersants may be
incorporated into the laundry compositions of the present invention. Examples
of such
suitable dispersants can be found in European Patent Application Nos. 111,965,
111,984,
and 112,592; U.S. Patent Nos. 4,597,898, 4,548,744, and 5,565,145. However,
any
suitable clay/soil dispersent or anti-redepostion agent can be used in the
laundry
compositions of the present invention.
In addition, polymeric dispersing agents which include polymeric
polycarboxylates and polyethylene glycols, are suitable for use in the present
invention.
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.
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
U.S. 3,308,067.
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
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66
ratio of acrylate to maleate segments in such copolymers will generally range
from about
30:1 to about l:l, 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
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.
Polyaspartate and polyglutamate dispersing agents may also be used, especially
in
conjunction with zeolite builders. Dispersing agents such as polyaspartate
preferably
have a molecular weight (avg.) of about 10,000.
Soil Release Agents - The compositions according to the present invention may
optionally comprise one or more soil release agents. If utilized, soil release
agents will
generally comprise from about 0.01 %, preferably from about 0.1 %, more
preferably from
about 0.2% to about 10%, preferably to about 5%, more preferably to about 3%
by
weight, of the composition. Nonlimiting examples of suitable soil release
polymers are
disclosed in: U.S. Patent Nos. 5,728,671; 5,691,298; 5,599,782; 5,415,807;
5,182,043;
4,956,447; 4,976,879; 4,968,451; 4,925,577; 4,861,512; 4,877,896; 4,771,730;
4,711,730; 4,721,580; 4,000,093; 3,959,230; and 3,893,929; and European Patent
Application 0 219 048.
Further suitable soil release agents are described in U.S. Patent Nos.
4,201,824;
4,240,918; 4,525,524; 4,579,681; 4,220,918; and 4,787,989; EP 279,134 A; EP
457,205
A; and DE 2,335,044.
Chelating A ents - The compositions of the present invention herein may also
optionally contain a chelating agent which serves to chelate metal ions and
metal
impurities which would otherwise tend to deactivate the bleaching agent(s).
Useful
chelating agents can include amino carboxylates, phosphonates, amino
phosphonates,
polyfunctionally-substituted aromatic chelating agents and mixtures thereof.
Further
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examples of suitable chelating agents and levels of use are described in U.S.
Pat. Nos.
5,705,464, 5,710,115, 5,728,671 and 5,576,282.
The compositions herein may also contain water-soluble methyl glycine diacetic
acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for
example,
insoluble builders such as zeolites, layered silicates and the like.
If utilized, these chelating agents will generally comprise from about 0.1 %
to
about 15%, more preferably from about 0.1% to about 3.0% by weight of the
detergent
compositions herein.
Suds su~pressor - Another optional ingredient is a suds suppressor,
exemplified
by silicones, and silica-silicone mixtures. Examples of suitable suds
suppressors are
disclosed in U.S. Patent Nos. 5,707,950 and 5,728,671. These suds suppressors
are
normally employed at levels of from 0.001% to 2% by weight of the composition,
preferably from 0.01 % to 1 % by weight.
Softenin a ents - Fabric softening agents can also be incorporated into
laundry
detergent compositions in accordance with the present invention. Inorganic
softening
agents are exemplified by the smectite clays disclosed in GB-A-1 400 898 and
in U.S.
5,019,292. Organic softening agents include the water insoluble tertiary
amines as
disclosed in GB-A-1 514 276 and EP-B-Ol l 340 and their combination with mono
C12-
C 14 quaternary ammonium salts are disclosed in EP-B-026 527 and EP-B-026 528
and
di-long-chain amides as disclosed in EP-B-0 242 919. Other useful organic
ingredients of
fabric softening systems include high molecular weight polyethylene oxide
materials as
disclosed in EP-A-0 299 575 and 0 313 146.
Particularly suitable fabric softening agents are disclosed in U.S. Patent
Nos.
5,707,950 and 5,728,673.
Levels of smectite clay are normally in the range from 2% to 20%, more
preferably from 5% to 15% by weight, with the material being added as a dry
mixed
component to the remainder of the formulation. Organic fabric softening agents
such as
the water-insoluble tertiary amines or dilong chain amide materials are
incorporated at
levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight whilst
the high
molecular weight polyethylene oxide materials and the water soluble cationic
materials
are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight.
These
materials are normally added to the spray dried portion of the composition,
although in
some instances it may be more convenient to add them as a dry mixed
particulate, or
spray them as molten liquid on to other solid components of the composition.
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Biodegradable quaternary ammonium compounds as described in EP-A-040 562
and EP-A-239 910 have been presented as alternatives to the traditionally used
di-long
alkyl chain ammonium chlorides and methyl sulfates.
Non-limiting examples of softener-compatible anions for the quaternary
ammonium compounds and amine precursors include chloride or methyl sulfate.
Dye transfer inhibition - The detergent compositions of the present invention
can
also include compounds for inhibiting dye transfer from one fabric to another
of
solubilized and suspended dyes encountered during fabric laundering and
conditioning
operations involving colored fabrics.
i. Polymeric dye transfer inhibiting agents
The detergent compositions according to the present invention can also
comprise
from 0.001 % to 10 %, preferably from 0.01 % to 2%, more preferably from 0.05
% to 1
by weight of polymeric dye transfer inhibiting agents. Said polymeric dye
transfer
inhibiting agents are normally incorporated into detergent compositions in
order to inhibit
the transfer of dyes from colored fabrics onto fabrics washed therewith. These
polymers
have the ability to complex or adsorb the fugitive dyes washed out of dyed
fabrics before
the dyes have the opportunity to become attached to other articles in the
wash.
Especially suitable polymeric dye transfer inhibiting agents are polyamine N-
oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles
or
mixtures thereof. Examples of such dye transfer inhibiting agents are
disclosed in U.S.
Patent Nos. 5,707,950 and 5,707,951.
Additional suitable dye transfer inhibiting agents include, but are not
limited to,
cross-linked polymers. Cross-linked polymers are polymers whose backbone are
interconnected to a certain degree; these links can be of chemical or physical
nature,
possibly with active groups n the backbone or on branches; cross-linked
polymers have
been described in the Journal of Polymer Science, volume 22, pages 1035-1039.
In one embodiment, the cross-linked polymers are made in such a way that they
form a three-dimensional rigid structure, which can entrap dyes in the pores
formed by
the three-dimensional structure. In another embodiment, the cross-linked
polymers entrap
the dyes by swelling. Such cross-linked polymers are described in the co-
pending
European patent application 94870213.9.
Addition of such polymers also enhances the performance of the enzymes
according the invention.
pH and Buffering Variation - Many of the detergent and laundry compositions
described herein will be buffered, i.e., they are relatively resistant to pH
drop in the
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presence of acidic soils. However, other compositions herein may have
exceptionally low
buffering capacity, or may be substantially unbuffered. Techniques for
controlling or
varying pH at recommended usage levels more generally include the use of not
only
buffers, but also additional alkalis, acids, pH jump systems, dual compartment
containers, etc., and are well known to those skilled in the art.
Other Materials - Detersive ingredients or adjuncts optionally included in the
instant compositions can include one or more materials for assisting or
enhancing
laundry performance, treatment of the substrate to be cleaned, or designed to
improve the
aesthetics of the compositions. Adjuncts which can also be included in
compositions of
the present invention, at their conventional art-established levels for use
(generally,
adjunct materials comprise, in total, from about 30% to about 99.9%,
preferably from
about 70% to about 95%, by weight of the compositions), include other active
ingredients such as non-phosphate builders, color speckles, silvercare, anti-
tarnish and/or
anti-corrosion agents, dyes, fillers, germicides, alkalinity sources,
hydrotropes, anti-
oxidants, perfumes, solubilizing agents, Garners, processing aids, pigments,
and pH
control agents as described in U.S. Patent Nos. 5,705,464, 5,710,115,
5,698,504,
5,695,679, 5,686,014 and 5,646,101.
Methods of Laundry - In addition to the methods for laundry fabrics described
herein, the invention herein also encompasses a laundering pretreatment
process for
fabrics which have been soiled or stained comprising directly contacting said
stains
and/or soils with a highly concentrated form of the laundry composition set
forth above
prior to washing such fabrics using conventional aqueous washing solutions.
Preferably,
the laundry composition remains in contact with the soil/stain for a period of
from about
30 seconds to 24 hours prior to washing the pretreated soiled/stained
substrate in
conventional manner. More preferably, pretreatment times will range from about
1 to 180
minutes.
PRODUCT WITH INSTRUCTIONS FOR USE
The present invention also encompasses the inclusion of instructions on the
use of
the enzyme granulate containing compositions of the present invention with the
packages
containing the compositions herein or with other forms of advertising
associated with the
sale or use of the compositions. The instructions may be included in any
manner
typically used by consumer product manufacturing or supply companies. Examples
include providing instructions on a label attached to the container holding
the
composition; on a sheet either attached to the container or accompanying it
when
purchased; or in advertisements, demonstrations, and/or other written or oral
instructions
which may be connected to the purchase or use of the compositions.
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Specifically the instructions will include a description of the use of the
composition, for instance, the recommended amount of composition to use in a
washing
machine to clean the fabric; the recommended amount of composition to apply to
the
fabric; if soaking or rubbing is appropriate .
The compositions of the present invention are preferably included in a
product.
The product preferably comprises a composition comprising one or more enzyme
granulates of the present invention, and optionally one or more cleaning
adjunct
materials, and further comprises instructions for using the product to launder
fabrics by
contacting a fabric in need of cleaning with an effective amount of the
composition such
that the composition cleans the fabric.
While particular embodiments of the subject invention have been described, it
will be obvious to those skilled in the art that various changes and
modifications of the
subject invention can be made without departing from the spirit and scope of
the
invention. It is intended to cover, in the appended claims, all such
modifications that are
within the scope of the invention.
The compositions of the present invention can be suitably prepared by any
process chosen by the formulator, non-limiting examples of which are described
in U.S.
5,691,297 Nassano et al., issued November 11, 1997; U.S. 5,574,005 Welch et
al., issued
November 12, 1996; U.S. 5,569,645 Dinniwell et al., issued October 29, 1996;
U.S.
5,565,422 Del Greco et al., issued October 15, 1996; U.S. 5,516,448 Capeci et
al., issued
May 14, 1996; U.S. 5,489,392 Capeci et al., issued February 6, 1996; U.S.
5,486,303
Capeci et al., issued January 23, 1996 all of which are incorporated herein by
reference.
In addition to the above examples, the compositions of the present invention
can
be formulated into any suitable laundry detergent composition, non-limiting
examples of
which are described in U.S. 5,679,630 Baeck et al., issued October 21, 1997;
U.S.
5,565,145 Watson et al., issued October 15, 1996; U.S. 5,478,489 Fredj et al.,
issued
December 26, 1995; U.S. 5,470,507 Fredj et al., issued November 28, 1995; U.S.
5,466,802 Panandiker et al., issued November 14, 1995; U.S. 5,460,752 Fredj et
al.,
issued October 24, 1995; U.S. 5,458,810 Fredj et al., issued October 17, 1995;
U.S.
5,458,809 Fredj et al., issued October 17, 1995; U.S. 5,288,431 Huber et al.,
issued
February 22, 1994 all of which are incorporated herein by reference.
Having described the invention in detail with reference to preferred
embodiments
and the examples, it will be clear to those skilled in the art that various
changes and
modifications may be made without departing from the scope of the invention
and the
invention is not to be considered limited to what is described in the
specification.
