Note: Descriptions are shown in the official language in which they were submitted.
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LAUNDRY DETERGENT AND/OR FABRIC CARE
COMPOSITIONS COMPRISING A TRANSFERASE
Field of the Invention
The present invention relates to laundry detergent and/or fabric care
compositions
comprising a transferase.
Background of the invention
Laundry detergent and/or fabric care compositions are well-known in the art
and
extensively represented in the market place.
Laundry detergent compositions include nowadays a complex combination of
active ingredients which fulfil certain specific needs : a surfactant system,
enzymes
providing cleaning and fabric care benefits, bleaching agents, a builder
system, suds
suppressors, soil-suspending agents, soil-release agents, optical brighteners,
softening
agents, dispersants, dye transfer inhibition compounds, abrasives,
bactericides, perfumes,
and their overall performance has indeed improved over the years.
However, the complex nature of everyday "body" soils typically found on pillow
cases, T-shirts, collars and socks, provides a continuous thorough cleaning
challenge for
detergents. These soils are difficult to remove completely and often residues
build up on
fabric leading to dinginess and yellowing. In addition, removal by detergents
of stains
stemming from plants, wood, mud-clay based soil and fruits is one of the
toughest
cleaning challenges, in particular with the tendency to move to low wash
temperatures
and shorter washing cycles. These stains typically contain complex mixtures of
fibrous
material, based mainly on carbohydrates and their derivatives, fibre and cell
wall
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2
components. Such stains are generally accompanied by amylose, sugars and their
derivatives.
In recent years, consumer desirability for fabric conditioning compositions
has
risen. Fabric softening compositions impart several desirable properties to
treated
garments including softness and static control. Fabric softness of laundered
garments is
typically achieved by delivering a quaternary ammonium compound to the surface
of the
fabric.
Consumer desirability for durable press fabric garments, particularly cotton
fabric
garments, has also risen. Durable press garments include those garments which
resist
wrinkling of the fabric both during wear and during the laundering process.
Durable press
garments can greatly decrease the hand work associated with laundering by
eliminating
ironing or reducing ironing time sometimes necessary to prevent wrinkling of
the
garment. However, in most commercially available durable press fabrics, the
fabric's
ability to resist wrinkling is reduced over time as the garment is repeatedly
worn and
laundered.
Furthermore, coloured garments have a tendency to wear and show appearance
losses. A portion of this colour loss may be attributed to abrasion in the
laundering
process, particularly in automatic washing machines and automatic laundry
dryers.
Moreover, tensile strength loss of fabric appears as an unavoidable result of
mechanical / chemical action due to use / wearing or washing.
As indicated above, there is a continuous need for a laundry detergent
composition
which provides excellent fabric cleaning and/or fabric stain removal,
especially on body
soils and plant based stains and/or fabric whiteness maintenance and/or fabric
color
appearance and/or dye transfer inhibition.
In addition, there is a continuous need for a laundry detergent composition
and/or
fabric care composition, which can provide, refurbish or restore tensile
strength, anti-
wrinkle, anti-bobbling and anti-shrinkage properties to fabrics, as well as
provide static
control, fabric softness, colour appearance and fabric anti-wear properties
and benefits.
The above objectives have been met by formulating laundry detergent and/or
fabric care compositions comprising a transferase.
It is a further object of the present invention to provide detergent
composition
and/or fabric care composition comprising transferase enzyme, which can
provide,
refurbish or restore improved tensile strength, enhanced anti-wrinkle, anti-
bobbling and
anti-shrinkage properties to fabrics, as well as provide better static
control, fabric softness,
colour appearance and fabric anti-wear properties and benefits, while
providing improved
cleaning benefits.
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The above objective has been met by formulating laundry detergent and/or
fabric
care compositions fiuther comprising a surfactant selected from nonionic
and/or anionic
and/or cationic and/or mixtures thereof, a detergent enzyme, a bleaching
agent, a dye
transfer inhibiting polymer, a dispersant and/or a smectite clay.
Transferase enzymes have been described in the art
A process for producing saccharides of a definite chain length such as maltose
and
maltooligosaccharides in an isolated and highly pure form using a saccharide
chain
transferase such as cyclodextrin glycosyltransferase or a-amylase, has been
disclosed in
EP 560 982. These so-produced saccharides are used in the pharmaceutical
field.
US 5,516,689 describes an enzyme composition and a means of reducing the
stickiness of honeydew contaminated cotton. TransgIucosidases and/or
pectinases are
used to hydrolyse and/or reduce honeydew on cotton fiber for reducing the
stickiness of
such fiber and avoid severe problems during the milling of cotton.
Microbial transglutaminases, their production and their use in a variety of
industrial purposes, including gelling of proteins, improvement of baking
quality of flour,
producing paste type food material from protein, fat and water, preparation of
cheese from
milk concentrate, binding of chopped meat, improvement of taste and texture of
food
proteins, casein finishing in leather processing, shoe shine, etc. have been
described in
W096/06931.
JP 7-107971 relates to a micro-organism belonging to the genus Bacillus and
having the capacity to produce an alkali resistant cyclodextrin
glucanotransferase. Said
enzyme can be used in dishwashing applications wherein it demonstrates
decomposition
and removal of food soils and the produced cyclodextrin plays as a masking, de-
odorizing
agent. Moreover said alkali resistant cyclodextrin glucanotransferase improves
the
cleaning capabilities of said compositions by improving the sudsing properties
and
stimulating the emulsification of the soiling.
Dishwashing detergent compositions containing cyclodextrin glucanotransferase
with cleaning benefits and deodorising effect are described in JP 7-109488.
WO 97/23683 relates to the use of xyloglucan endotransglycosylase (XET) to
provide strength and/or shape-retention and/or anti-wrinkling properties to
cellulosic
material.
Nevertheless, none of these documents teaches the cleaning or fabric care
benefits obtained by transferase enzymatic activity from transferases nor
xyloglucan
transferases that exhibit greater transferase activity than hydrolytic
activity and/or
xyloglucan transferases that exhibit higher reaction rates for donor
substrates with
higher molecular weight than for donor substrates with lower molecular weight,
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when used in the laundry and/or fabric care process.
Summary of the invention
The present invention relates to laundry detergent and/or fabric care
compositions
comprising a transferase for fabric care and/or cleaning benefits.
Detailed description of the invention
The Transferase Enzymes and their Substrates
An essential component of the laundry detergent and/or fabric care
compositions
of the present invention is a transferase enzyme.
Transferase enzymes catalyse the transfer of functional compounds to a range
of
substrates. Particularly, the transferase of the invention have the potential
to transfer a
chemical moiety, for example a methyl group or a glycosyl group, from a small
substrate
to form oligomeric molecules or elongate polymeric compounds. Using small
substrates,
the enzyme improves the properties of garments by binding functional groups
like methyl,
hydroxymethyl, formyl, carboxyl, aldehyde, ketone, acyl, amino and phosphorous
functional groups and/or transferring glycosyl residues to the garment
surface. The
improved garments properties include tensile strength, anti-wrinkle, anti-
bobbling and
anti-shrinkage properties to fabrics, static control, fabric softness, colour
appearance and
fabric anti-wear properties and benefits. When the transferase level is high
and the
substrate concentration is low, the functional groups are transferred to water
molecules
providing cleaning benefits.
Suitable transferases for the present invention are represented by the EC 2.1
Transferring one-carbon groups enzymes, EC 2.2 Transferring aldehyde or ketone
residues enzymes, EC 2.3 Acyltransferases, EC 2.4 Glycosyltransferase, EC 2.5
Transferring alkyl or aryl groups other than methyl groups enzymes, EC 2.6
Transferring
nitrogenous groups enzymes and EC 2.7 Transfernng phosphorus-containing groups
enzymes.
Examples of suitable transferases are
EC 2.1.1.15 Fatty acid O-methyltransferase
EC 2.1.1.18 Polysaccharide O-methyltransferase
EC 2.1.2.1 Glycine hydroxymethyltransferase
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EC 2.1.2.4 Glycine formiminotransferase
EC 2.2.1.3 Formaldehyde transketolase
EC 2.3.1.3 Glucosamine N-acetyltransferase
EC 2.3.1.18 Galactoside acetyl transferase
EC 2.3.1.57 Diamine N-acetyltransferase
EC 2.3.1.75 Long-chain-alcohol O-fatty-acyltransferase
EC 2.3.1.79 Maltose O-acetyltransferase
EC 2.3. i .84 Alcohol O-fatty acetyltransferase
EC 2.3.1.88 Peptide a-N-acetyltransferase
EC 2.3.1.96 Glycoprotein N-palmitoyltransferase
EC 2.3.1.142 Glycoprotein O-fatty-acyltransferase
EC 2.5.1.10 Geranyltranstransferase
EC 2.5.1.20 Rubber cis-polypremylcistransferase
EC 2.6.1 Aminotransferase
For specific applications, preferred transferases demonstrate some / most of
their
activity in the alkaline conditions, i.e., enzymes having an enzymatic
activity of at least
10%, preferably at least 25%, more preferably at least 40% of its maximum
activity at a
pH ranging from 7 to I2. More preferred transferases are enzymes having their
maximum
activity at a pH ranging from 7 to 12. Other preferred transferase is a
transferase having at
least 50% of its maximum activity between 10°C and 50°C.
Preferred transferases for the laundry detergent and/or fabric care
compositions of
the present invention are included in the acyltransferases (EC 2.3) and
glycosyltransferases classes ( EC 2.4).
Of particular interest is the group of acyltransferases, especially the
aminoacyl
transferases (EC 2.3.2). These are enzymes transferring amino groups from a
donor,
generally an amino acid, to an acceptor. Even more preferred is the protein-
glutamine y-
glutamyltransferase (EC 2.3.2.13), also available under the name
transglutaminase.
Without wishing to be bound by theory, it is believed that enzymatic
cmsslinking of
amino acids, di/tri/poly-peptides and/or proteins will occur on the fabric,
resulting in
increased tensile strength and improved appearance. Moreover, hydrolysis by an
aminoacyl transferase of said substrates present in the soils/stains, will
pmvide cleaning
benefits.
Of particular interest is also the group of glycosyltransferases. The general
properties of these enzymes is to transfer a sugar from oligosaccharides to
another
carbohydrate as acceptor. Both hexosyltransferases and pentosyltransferases
can be used
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in the invention. Glycosyltransferases catalyse both hydrolytic and transfer
reactions in
incubation with oligosaccharides. As a result of the enzymatic activity,
oligosaccharides
are converted into a new class of polysaccharides. It has been surprisingly
found that
glycosyltransferases improve the tensile strength and appearance of fabrics,
e.g. reduce
fabric wrinkles. Without wishing to be limited by any theory, it is indeed
believed that
due to the glycosyltransferase activity, oligosaccharides are bound to the
cellulose
polymers of cotton fabrics resulting in improved tensile strength and
demonstrating
appearance benefits especially after multiple wash cycles.
Without wishing to be bound by theory, the glycosyltransferase activity is
believed to have four potential modes of action providing fabric care benefits
- Enzymatic stitching wherein the enzyme is thought to bind
oligosaccharides to cellulose fibers with reduced tensile strength;
- Enzymatic cross-linking wherein the glycosyltransferase is thought to
bind cellulose fibers with reduced tensile strength together; and
- Enzymatic polymer linking wherein polymers are linked to cellulose
fibers with reduced tensile strength.
In addition, in presence of a low level of substrate and a high level of
glycosyltransferase, the glycosyl groups are transferred to water molecules
providing
cleaning benefits.
For example, transglucosidase is an enzyme that catalyses both hydrolytic and
transfer reactions in solutions containing a-D- gluco-oligosaccharides. As a
result of the
transglucosidase enzymatic reactions, the malto-oligosaccharides are converted
to
isomalto-oligosaccharides providing a new class of polysaccharides
characterised by a
higher proportion of saccharides linked by a-D-1,6 linkages from the non-
reducing end.
These transglucos~dase reactions have been found to provide fabric care
performance. It is believed that the improved tensile strength, the reduced
wrinkling and
better appearance are due to oligosaccharides bound to the cellulose polymers
fibers of
cotton.
Examples of suitable glycosyltransferases are galactosyl transferases and
fructosyltransferases, such as 1,4-(3-galactosyltransferase; 1,3-a-
fructosyltransferase; 2,3-sialyl
transferase; cyclodextrin glycosyltransferase; N-acetylgluco- or -
galactosaminyltransferase; and
EC 2.4.1.2 1,4-a-D-glucan:l,6-a-D-glucan 6-a-D-glucosyltransferase
EC 2.4.1.4 Sucrose:l,4-a-D-glucan 4-a-D-glucosyltransferase
EC 2.4.1.5 Sucrose:l,6-a-D-glucan 6-a-D-glucosyltransferase
EC 2.4.1.9 Sucrose:2,1-(3-D-fructan 1-~i-D-fructosyltransferase
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EC 2.4.1.10Sucrose:2,6-(3-D-fructan 6-j3-D-fructosyltransferase
EC 2.4.1.11UDP glucose:glycogen 4-a-D-glucosyltransferase
EC 2.4.1.12UDPglucose : 1,4-(3-D-glucan 4-(3-D-glucosyl
transferase
EC 2.4.1.13UDPglucose:D-fntctose 2-a-D-glucosyltransferase
EC 2.4.1.16UDP-N-acetylglucosamine : chitin 4-~i-N-acetylglucosaminyl
transferase
EC 2.4.1.181,4-a-D-glucan:l,4-a-D-glucan 6-a-D-{1,4-a-D-glucano)-transferase
EC 2.4.1.191,4-a,-D-glucan 4-a-D-(1,4-a-D-giucano)-transferase
(cyclizing)
EC 2.4.1.21ADPglucose:l,4-a-D-glucan 4-a-Dglucosyltransferase
EC 2.4.1.241,4-a-D-glucan : 1,4-a-D-glucan(D-glucose) 6-a-D-
glucosyltransferase
EC 2.4.1.251,4-a-D-glucan : 1,4-a-D-glucan 4-a-D-glycosyl
transferase
EC 2.4.1.29GDPglucose:l,4-(3-D-glucan 4-~3-D-glucosyl transferase
EC 2.4.1.341,3-(3-glucan synthetase
EC 2.4.1.35UDPglucose:phenol (3-D-glucosyltransferase
EC 2.4.1.491,4-(3-D-oligo-D-glucan:orthophosphate a-d-glucosyltransferase
EC 2.4.1.67I-a-D-galactosyl-myo-inositol:raffnosegalactosyl
sansferase
EC 2.4.1.71UPDglucose:arylamine N-D-glucosyltransferase
EC 2.4.1.75UDPgaIacturonate (3-D-galacturonosyl transferase
EC 2.4.1.821-a-D-galactosyl-myo-inositolaucrose 6-a-D- galactosyltransferase
EC 2.4.1.90UDPgalactose:N-acetyl-D-glucosamine 4-~i-
galactosyltransferase
EC 2.4.1.93Inulin D-fructosyl-D-fructosyltransferase
EC 2.4.1.99Sucrose : 1 F-fructosyltransferase
EC 2.4.1.1001,2-~i-D-fructan : I ,2-~i-D-fructan 1-/3-D-fructosyltransferase
EC 2.4.1.113ADPglucose:protein 4-a-D-glucosyltransferase
EC 2.4.1.121UDPglucose:indole-3-acetate (3-D-glucosyltransferase
EC 2.4.1.125Sucrose : 1,6-a-D-glucan 3(6)-a-D-glucosyl
transferase
EC 2.4.1.140Sucrose : 1,6(1,3}-a-D-glucan 6(3)-a-D-glucosyl
transferase
EC 2.4.1.1611,4-a,-D-glucan:l,4-a-D-glucan 4-a-D-glucosyltransferase
EC 2.4.1.168UDPglucose : xylaglucan 1,4-/3-D-glucosyl
transferase
EC 2.4.1.169UDP-D-xylose : xyloglucan 1,6-~-D-xylosyl
transferase
EC 2.4.1.183UDPglucose:a-D-(1,3)-glucan 3-a-D-glucosyltransferase
Of particular interest is EC 2.4.1.24 1,4-a-D-glucan : 1,4-a-D-glucan(D-
glucose)
6-a-D-glucosyl transferase. A particulate member of this enzyme is
commercially
available under the name Transglucosidase L-500.
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In addition to the glycosyitransferases discussed above, it has been found
that
mutant glycosyltransferases and/or mutant glycosidases, examples of which are
described
in PCT Application Publication No. WO 97/21822, its Canadian equivalent
Canadian
Patent No. 2,165,041, and its U.S. equivalent U.S. Patent No. 5,716,812, all
to S.G.
Withers et al., improve the tensile strength and appearance of fabrics, e.g.,
reduce fabric
wrinkles, enhance shape retention and reduce shrinkage. The mutant forms of
glycosyltransferases and/or glycosidases provide enzymatic stitching,
enzymatic cross-
linking and enzymatic polymer linking, as discussed above in greater detail.
The mutant glycosyltransferases and/or mutant glycosidases only have one
nucleophilic amino acid on the active site of the enzyme, rather than two,
like non-
mutated glycosyltransferases andlor non-mutated glycosidases, respectively. In
other
words, the mutant glycosyltransferases and/or mutant glycosidases are formed
in which
one of the normal nucleophilic amino acids within the active site has been
changed to a
non-nucleophilic amino acid. As a result, the mutant glycosyltransferases
and/or mutant
glycosidases only exhibit transferase activity; no hydrolytic activity is
exhibited by the
mutant glycosyltransferases nor the mutant glycosidases. Accordingly, unlike
non-
mutated glycosyltransferases and/or non-mutated glycosidases, the mutant
glycosyltransferases and/or mutant glycosidases convert oligosaccharides into
a new
class of polysaccharides without the detrimental hydrolyzation of the new
class of
polysaccharides back into oligosaccharides or without water acting as acceptor
for the
transfer reaction.
These mutant glycosyltransferases and/or mutant glycosidases can be extracted
from plant, yeast, bacteria or other organisms. The DNA of the mutant
glycosyltransferases and/or mutant glycosidases can be cloned and expressed in
bacteria,
yeast or fungi and obtained in this way.
These mutant glycosyltransferases and/or mutant glycosidases can be
incorporated
into heavy duty liquid detergents, heavy duty granular detergents, fabric care
compositions, and the like.
In addition to the usefulness of mutant glycosyltransferases and/or mutant
glycosidases in laundry detergents and fabric care compositions, they can also
be used in
solutions for the treatment of fabrics in the textile process industry, and
the treatment of
paper and paper pulp.
The novel characteristics and properties of the mutated glycosyltransferases
and/or
the mutated glycosidases make them highly suitable for use in laundry
detergent and
fabric care compositions because the absence of hydrolytic activity implies no
loss in
tensile strength of fabrics, even in the absence of donors in the transferase
reaction.
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When mutant glycosyltransferases and/or mutant glycosidases are present in the
compositions of the present invention, it is desirable that the saccharide
concentration in
the compositions is in the range of from about 0.01 % to 30% by weight of the
total
composition, more preferably, 1 % to 10% by weight of the total composition.
Furthermore, the compositions of the present invention can have saccharides of
high
molecular weight added to the compositions to obtain the benefits discussed
above.
Another class of enzymes that is of particular interest is xyloglucan
transferases.
A preferred xyloglucan transferase is endoxyloglucan transferase ("EXT"),
which is
described in J. Plant Res. 108, 137-148, 1995 by Nishitani, Kagoma University,
and now
called "EXGT" in Int. Review of Cytology, Vol. 173, p. 157, 1997 by Nishitani,
Kagoma
University. EXT is also described in J. Biol. Chem. 267, 21058-21064, 1992 by
Nishitani
et al.
Like the mutant glycosyltransferases discussed above, this endoxyloglucan
transferase improves the tensile strength and appearance of fabrics, e.g.,
reduce fabric
wrinkles, enhance shape retention and reduce shrinkage. The endoxyloglucan
transferase
stitch cellulose fibrils. These stitching properties of the enzyme on
cellulose fibrils
delivers the above mentioned benefits.
Endoxyloglucan transferase is responsible for rejoining intermicrofibrillar
xyloglucan chains, the xyloglucan chains between cellulosic microfibrils
during the
formation of plant cell walls. By rejoining the cellulosic microfibrils
through xyloglucan
linkages, the cellulose structure acquires improved strength of the fibers.
Since the
structure of fabrics is of cellulosic nature, the enzyme has a stitching
activity on the
microfibrils. Also shape retention, anti-shrinkage and anti-wrinkle benefits
can be
explained by the stitching properties of the enzyme.
Endoxyloglucan transferase differs in activity from xyloglucan
endotransglycosylase ("XET transferase"), which is described in WO 97/23683 to
Novo
Nordisk A/S, in Biochem. J. (1992) 282, 821-828 by Fry et al. and in Plant J.
(1993) 3(5),
691-700. The difference being that the xyloglucan endotransglycosylase shows
both
transferase activity and hydrolase ("hydrolytic") activity. In contrast,
endoxyloglucan
transferase only shows transferase activity. No hydrolase activity is shown by
endoxyloglucan transferase. Accordingly, unlike xyloglucan
endotransglycosylase, the
endoxyloglucan transferase converts oligosaccharides into a new class of
polysaccharides
without the detrimental hydrolyzation of the new class of polysaccharides back
into
oligosaccharides.
Furthermore, the endoxyloglucan transferase exhibits strict donor specificity
for
high molecular weight xyloglucan polymers and does not act on lower molecular
weight
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xyloglucan oligomers. Preferably, endoxyloglucan transferase exhibits strict
donor
specificity for xyloglucan polymers having molecular weights of at least
10,000.
The novel characteristics and properties of endoxyloglucan transferase make it
highly suitable for use in laundry detergent and fabric care compositions
because the
absence of hydrolytic activity implies no loss in tensile strength of fabrics,
even in the
absence of donors in the transferase reaction. Furthermore, lower levels of
substrate
donor can be used. Without desiring to be limited, it is believed that high
benefits can be
obtained even in the absence of a donor substrate if the endoxyloglucan
transferase uses
xyloglucans of the primary wall of the cotton fiber within fabrics.
Endoxyloglucan transferase can be extracted from plants and other organisms.
Endoxyloglucan transferase can be obtained from a large number of plants
including, but
not limited to, A. thaliana and V. angularis. Alternatively, the DNA of the
enzyme can
be cloned and expressed in bacteria, yeast or fungi and obtained in this way.
The endoxyloglucan transferase can be incorporated into heavy duty liquid
detergents, heavy duty granular detergents, fabric care compositions, and the
like.
In addition to its usefulness in laundry detergent and fabric care
compositions,
endoxyloglucan transferase can also be used in solutions for the treatment of
fabrics in the
textile process industry, and for the treatment of paper and paper pulp.
When endoxyloglucan transferase is present in the compositions of the present
invention, it is desirable that the xyloglucan concentration in the
compositions is in the
range of from about 0.01 % to 30% by weight of the total composition, more
preferably,
1 % to 10% by weight of the total composition. Furthermore, the compositions
of the
present invention can have xyloglucan polymers of high molecular weight added
to the
compositions to obtain the benefits discussed above.
Accordingly, when the transferase is a xyloglucan transferase, such as
endoxyloglucan transferase, the xyloglucan transferase preferably exhibits
greater
transferase activity than hydrolase (hydrolytic) activity and/or the
xyloglucan transferase
preferably exhibits strict donor specificity for high molecular weight
xyloglucan polymers
and does not act on lower molecular weight xyloglucan oligomers, more
preferably the
xyloglucan transferase exhibits strict donor specificity for xyloglucan
polymers having
molecular weights of at least 10,000.
Yet another enzyme that is of particular interest is cyclomaltodextrin
glucanotransferase ("CGT-ase") (EC 2.4.1.19), which is commercially available
from
Amano and Novo Nordisk A/S.
Covalent linking of carbohydrates, oligo and polysaccharides to cotton
surfaces,
such as fabrics, with a transferase delivers benefits such as anti-wrinkling,
color
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11
maintenance, dye fixation and soil repulsion. Covalent linkage of glucose
units to the
cellulose surface versus a physical absorption of polymers, which are produced
by the
transferase in situ (or others), make the observed benefits durable.
Cyclomaltodextrin glucanotransferase is a transferase that exhibits several
different actions on starch. It produces from starch a, ~3, and y
cyclodextrins, hydrolyzes
starch and cross links starch. In these types of reactions, a sugars are both
donor and
acceptor for the transferase reaction. Up to now, it was not clear if these
transferase
enzymes could covalently link sugar units to cotton.
Surprisingly, it has been found that cyclomaltodextrin glucanotransferase can
covalently link glucose units from a-cyclodextrine to the cotton surfaces of
fabrics at the
non-reducing end of the cellulose polymers. Accordingly, cyclomaltodextrin
glucanotransferase has the ability to make the benefits discussed above more
durable.
As discussed above, it is known that covalently linking cellulose polymers
with
cross-linking agents delivers benefits to fabrics, such as anti-wrinkle
benefits, but anti-
wrinkle benefits can also be obtained by a physical absorption of polymers on
the cotton
surface. This physical absorption of polymers on the cotton surface can now be
made
more durable since one of the polymer units is covalently linked to the cotton
surface by
the action of cyclomaltodextrin glucanotransferase. Since these more durable
benefits
are produced enzymatically, the covalent linking occurs at a much lower
temperature,
thus, much lower temperatures as compared to conventional wash cycles are
feasible in
the wash cycle. In addition, conventional cross-linking chemicals (some of
them are
potentially toxic), which are used in the textile industry, are not applicable
at the lower
temperatures in the wash cycle.
Other benefits, such as dye fixation and improved soil release, are obtained
through the covalent incorporation of cationic or anionic glucose units to the
cotton
surface.
Accordingly, the use of cyclomaltodextrin glucanotransferase in laundry
detergent
and fabric care compositions provides improved anti-wrinkle, shape retention,
anti-
shrinkage, dye fixation, soil repulsion and tensile strength benefits for
fabrics.
The cyclomaltodextrin glucanotransferase can be incorporated into heavy duty
liquid detergents, heavy duty granular detergents, fabric care compositions,
and the like.
In addition to its usefulness in laundry detergent and fabric care
compositions,
cyclomaltodextrin glucanotransferase can also be used in solutions for the
treatment of
fabrics in the textile process industry, and for the treatment of paper and
paper pulp.
When cyclomaltodextrin glucanotransferase is present in the compositions of
the
present invention, it is desirable that the starch concentration in the
compositions is in the
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I2
range of from about 0.01% to 30% by weight of the total composition; more
preferably,
1 % to I 0% by weight of the total composition. Furthermore, the compositions
of the
present invention can have cyclodextrins or types of starch and sucrose added
to the
compositions to obtain the benefits discussed above.
Still yet another group of enzymes that is of particular interest is
glucansucrases,
of which dextransucrase (EC 2.4.1.5), a glycosyltransferase, is one example.
Other
glucansucrases that are suitable for use in the compositions described herein
include, but
are not limited to, various dextransucrases and alternansucrases.
Alternatively,
levansucrase, which is commercially available from Genencor, can be used.
Dextransucrase enzymes can be obtained from any suitable source known in the
art, and are used in conjunction with appropriate substrates (sucrose +/-
maltose).
Dextransucrase catalyzes transfer reactions of glycosyl residues from one
polysaccharide
to another. As a result of dextransucrase reactions, high molecular weight
dextrans are
produced on fabric surfaces. In dextrans, glucose residues are linked by 1-6-a
linkages.
Modification of cotton fiber with carbohydrates, oligo and polysaccharides,
delivers
benefits such as anti-wrinkling, color maintenance, dye fixation and soil
repulsion. The
durability of these benefits may require covalent linkage of the
oligosaccharides.
It has been found that dextransucrase can be bound to oligosaccharides to
cellulose polymers in cotton. As a result of this binding via the transfer
reactions
catalyzed by the dextransucrase provided improved fabric appearance benefits
i.e.,
improved anti-wrinkling, shape retention, anti-shrinkage, dye fixation, soil
repulsion and
tensile strength benefits. When the reaction products are bound (may or may
not be a
covalent linkage) to cotton, they modify the cotton surface and fibrils, which
in turn
delivers the fabric care benefits discussed above. Dextransucrase with sucrose
also
provided improved whiteness benefits (dyes from other color garments are not
deposited
on white fabrics). The dextransucrase/sucrose combination forms high molecular
weight
dextran (and smaller oligomers when other saccharides such as maltose,
cellobiose, etc.,
are present).
Furthermore, it has been found that the deposition e~ciency of reaction
products
on the fabrics is high, and that the reaction products are all not washed off
in the
following wash cycle.
The glucansucrases can be incorporated into heavy duty liquid detergents,
heavy
duty granular detergents, fabric care compositions, and the like.
In addition to their usefulness in laundry detergent and fabric care
compositions,
glucansucrases can also be used in solutions for the treatment of fabrics in
the textile
process industry, and for the treatment of paper and paper pulp.
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WO 99/55817 PCTNS98/08629
3.3
When glucansucrase is present in the compositions of the present invention, it
is
desirable that the substrate (typically sucrose or other disaccharides)
concentration in the
compositions is in the range of from about 0.01 % to 30% by weight of the
total
composition, more preferably, 1 % to 10% by weight of the total composition.
Furthermore, the compositions of the present invention can have smaller
polysaccharides
such as sucrose, maltose, maltdextrins, cellosaccharides, and types of starch
added to the
compositions to obtain the benefits discussed above.
These transferases are preferably incorporated into the compositions in
accordance
with the invention at a level of from 0.0001 % to 10%, more preferably from
0.0005% to 5
%, most preferred from 0.001 % to 1 % pure enzyme by weight of the total
composition.
The fabric care and/or cleaning benefits can be obtained by the laundry and/or
fabric care compositions of the present invention in presence or absence of
the
corresponding natural substrate. In general, the first part of the enzyme name
indicates
the substrate for the enzyme reaction and the second part is the acceptor to
which the
group is transferred. The substrate of the transferase enzyme can be the
fabric itself,
stains and/or soils, added in any treatment including pre- or post-treatment
from the
textile industry and/or from any washing and/or fabric care process, and/or
added together
with the transferase-containing composition.
Examples of substrates for some of the transferases listed above are : S-
adenosyl-
L-methionine, 5,10-methylenetetrahydrofolate or formiminotetra-hydrofolate
(hydroxymethyl or formyl group transfer to glycine), formaldehyde, acetyl Co
A, methyl-
a,w-diamine, palmityl Co A, geranoyl di phosphate.
In particular, the substrate for the aminoacyl transferases is an amino
containing
compound such as an amino acid, a di/tri/polypeptide and/or a protein.
Among the glycosyltransferases, though the transferring group is a glycosyl
residue, the specifics of the substrate for each enzyme is derived from the
first part of the
name. Especially for the glycosyltransferases, the natural substrate could be
any alpha-
glucosyl saccharide chosen from amylaceous substances in a dimer, oligomer
and/or
polymer. The examples are preferably different forms of starch (gelatinized,
liquefied,
solubilized), partial starch hydrolysate, more preferably malto-
oligosaccharides, and
most preferably maltose. Of interest are also substituted starch/sugar
substrates,
containing methylation and carboxylation substitution. Alternatively, the
following
substrates could be used for the mentioned glycosyltransferases: dextrins,
sucrose,
raffinose, fructosyl polymers, UDP glucose, xyloglucan, GDP glucose,
arylamine, UDP
galacturonate, ADP glucose, indole-3-acetate, a-D-glucans, UDP-xylan.
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14
The transferase-substrates are preferably incorporated into the compositions
in
accordance with the invention at a level of from 0.01% to 30%, more preferably
from
0.1 % to 20%, most preferably from 1 % to 10% by weight of the total
composition.
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 optimise their performance efficiency in
the cleaning
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
and/or chelant stability, catalytic activity and the like, of the enzyme
variant is tailored to
suit the particular fabric conditioning and/or cleaning 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.
Surfactants
Preferably, the detergent compositions according to the present invention
comprise a surfactant or surfactant system wherein the surfactant can be
selected from
nonionic and/or anionic andlor cationic and/or ampholytic and/or zwitterionic
andlor
semi-polar nonionic surfactants.
The surfactant is typically present at a level of from 0.1% to 60% by weight.
More
preferred levels of incorporation are 1% to 35% by weight, most preferably
from 1% to
30% by weight of detergent compositions in accord with the invention.
The surfactant is preferably formulated to be compatible with enzyme
components
present in the composition. In liquid or gel compositions the surfactant is
most preferably
formulated such that it promotes, or at least does not degrade, the stability
of any enzyme
in these compositions.
Examples of suitable nonionic, anionic, cationic, ampholytic, zwitterionic and
semi-polar nonionic surfactants are disclosed in U.S. Patent Nos. 5,707,950
and
5,576,282.
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WO 99/55817 PCT/US98/08629
Highly preferred nonionic surfactants are polyhydroxy fatty acid amide
surfactants
of the formula:
R2 C(O} N(R ) Z
wherein RI is H, or R1 is C1_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl
or a
mixture thereof, R2 is CS_31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl
having a
linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the
chain, or an
alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight C11-
15 ~kYl or
C16-18 ~kYl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z
is derived
from a reducing sugar such as glucose, fructose, maltose, lactose, in a
reductive amination
reaction.
Highly preferred anionic surfactants include alkyl alkoxylated sulfate
surfactants
hereof are water soluble salts or acids of the formula RO(A)mS03M wherein R is
an
unsubstituted C 10-C24 alkyl or hydroxyalkyl group having a C 10-C24 alkyl
component,
preferably a C 12-C20 alkyl or hydroxyalkyl, more preferably C 12-C 1 g alkyl
or
hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero,
typically between
about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is
H or a
cation which can be, for example, a metal cation (e.g., sodium, potassium,
lithium,
calcium, magnesium, etc.}, ammonium or substituted-ammonium cation. Alkyl
ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated
herein.
When included therein, the laundry detergent compositions of the present
invention typically comprise from about 1% to about 40%, preferably from about
3% to
about 20% by weight of such anionic surfactants.
Highly preferred cationic surfactants are the water-soluble quaternary
ammonium
compounds useful in the present composition having the formula
R1R2R3R4N+X_
wherein R 1 is C g-C 16 alkyl, each of R2, R3 and R4 is independently C 1-C4
alkyl, C 1-C4
hydroxy alkyl, benzyl, and -(C2H40)xH where x has a value from 2 to 5, and X
is an
anion. Not more than one of R2, R3 or R4 should be benzyl.
When included therein, the detergent compositions of the present invention
typically comprise from 0.2% to about 25%, preferably from about 1% to about
8% by
weight of such cationic surfactants.
When included therein, the detergent compositions of the present invention
typically comprise from 0.2% to about 15%, preferably from about 1 % to about
Z 0% by
weight of such ampholytic surfactants.
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16
When included therein, the detergent compositions of the present invention
typically comprise from 0.2% to about 15%, preferably from about 1% to about
10% by
weight of such zwitterionic surfactants.
When included therein, the detergent compositions of the present invention
typically comprise from 0.2% to about 15%, preferably from about 1% to about
10% by
weight of such semi-polar nonionic surfactants.
T'he detergent composition of the present invention may further comprise a
cosurfactant selected from the group of primary or tertiary amines.
Suitable primary amines for use herein include amines according to the formula
R1NH2 wherein R1 is a C6-C12~ preferably C6-Clp alkyl chain or R4X(CH2)n, X is
-
O-, -C(O)NH- or -NH-~ R4 is a C6-C12 alkyl chain n is between 1 to S,
preferably 3. Rl
alkyl chains may be straight or branched and may be interrupted with up to 12,
preferably
less than S ethylene oxide moieties.
Preferred amines according to the formula herein above are n-alkyl amines.
Suitable amines for use herein may be selected from 1-hexylamine, 1-
octylamine, 1-
decylamine and laurylamine. Other preferred primary amines include C8-C 10
oxypropylamine, octyloxypropylamine, 2-ethylhexyl-oxypropylamine, lauryl amido
propylamine and amido propylamine.
Suitable tertiary amines for use herein include tertiary amines having the
formula
R1R2R3N wherein R1 and R2 are Cl-Cg alkylchains or
Rs
-{CHZ-CH-O~H
R3 is either a C6-C 12~ preferably C6-C l0 alkyl chain, or R3 is R4X(CH2)n,
whereby X is
-O-, -C(O)NH- or -NH-~R4 is a C4-C12~ n is between i to 5, preferably 2-3. RS
is H or
Cl-C2 alkyl and x is between 1 to 6 .
R3 and R4 may be linear or branched ; R3 alkyl chains may be interrupted with
up
to 12, preferably less than 5, ethylene oxide moieties.
Preferred tertiary amines are R1R2R3N where Rl is a C6-C12 alkyl chain, R2 and
R3 are C 1-C3 alkyl or
Rs
I
-C CHZ-CH-O ~H
where RS is H or CH3 and x = 1-2.
Also preferred are the amidoamines of the formula:
O
Ri-C-NH-( CH2 n N-( R2 2
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17
wherein R1 is C6-C12 alkyl; n is 2-4,
preferably n is 3; R2 and R3 is C1-C4
Most preferred amines of the present invention include 1-octylamine, 1-
hexylamine, 1-decylamine, 1-dodecylamine,CB-l0oxypropylamine, N coco 1-
3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl
bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2 moles
propoxylated, octyl amine 2 moles propoxylated, lauryl
amidopropyldimethylamine, C8-
amidopropyldimethylamine and C 10 amidopropyldimethylamine.
The most preferred amines for use in the compositions herein are 1-hexylamine,
1-
octylamine, 1-decylamine, 1-dodecylamine. Especially desirable are n-
dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7
times
ethoxylated, lauryl amido propylamine and cocoamido propylamine.
The surfactant and surfactant system of the present invention is preferably
formulated to be compatible with enzyme components present in the composition.
In
liquid or gel compositions the surfactant is most preferably formulated such
that it
promotes, or at least does rat degrade, the stability of any enzyme in these
compositions.
Builders
The compositions according to the present invention may further comprise a
builder or builder system. Any conventional builder system is suitable for use
herein
including aluminosilicate materials, silicates, polycarboxylates, alkyl- or
alkenyl-succinic
acid and fatty acids, materials such as ethylenediamine tetraacetate,
diethylene triamine
pentamethyleneacetate, metal ion sequestrants such as aminopolyphosphonates,
particularly ethylenediamine tetramethylene phosphoric acid and diethylene
triamine
pentamethylenephosphonic acid. Phosphate builders can also be used herein.
The present invention may include a suitable builder or detergency salt. The
level
of detergent salt/builder can vary widely depending upon the end use of the
composition
and its desired physical form. When present, the compositions will typically
comprise at
least about 1 % builder and more typically from about 10% to about 80%, even
more
typically from about 15% to about SO% by weight, of the builder. Lower or
higher levels,
however, are not meant to be excluded.
Inorganic or P-containing detergent salts include, but are not limited to, the
alkali
metal, ammonium and alkanolammonium salts of polyphosphates {exemplified by
the
tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates),
phosphonates, phytic acid, silicates, carbonates (including bicarbonates and
sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate
salts are
required in some locales. Importantly, the compositions herein function
surprisingly well
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18
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.
Organic detergent builders suitable for the purposes of the present invention
include, but are not restricted to, a wide variety of polycarboxylate
compounds. As used
herein, "polycarboxylate" refers to compounds having a plurality of
carboxylate groups,
preferably at least 3 carboxylates. Polycarboxylate builder can generally be
added to the
composition in acid form, but can also be added in the form of a neutralized
salt. When
utilized in salt form, alkali metals, such as sodium, potassium, and lithium,
or
alkanolammonium salts are preferred.
Examples of suitable silicate builders, carbonate salts, aluminosilicate
builders,
polycarboxylate builders, citrate builders, 3,3-dicarboxy-4-oxa-1,6-
hexanedioate builders
and related compounds disclosed in U.S. Patent No. 4,566,984, to Bush,
succinic acid
builders, phosphorous-based builders and fatty acids, are disclosed in U.S.
Patent Nos.
5,576,282, 5,728,671 and 5,707,950.
Additional suitable builders can be an inorganic ion exchange material,
commonly
an inorganic hydrated aluminosilicate material, more particularly a hydrated
synthetic
zeolite such as hydrated zeolite A, X, B, HS or MAP.
Specific polycarboxylates suitable for the present invention are
polycarboxylates
containing one carboxy group include lactic acid, glycolic acid and ether
derivatives
thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370.
Polycarboxylates containing two carboxy groups include the water-soluble salts
of
succinic acid, malonic acid, (ethylenedioxy) diacetic acid, malefic acid,
diglycollic acid,
tartaric acid, tartronic acid and fumaric acid, as well as the ether
carboxylates described in
German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No.
3,935,257 and
the sulfmyl carboxylates described in Belgian Patent No. 840,623.
Polycarboxylates
containing three carboxy groups include, in particular, water-soluble
citrates, aconitrates
and citraconates as well as succinate derivatives such as the
carboxymethyloxysuccinates
described in British Patent No. 1,379,241, lactoxysuccinates described in
Netherlands
Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-
propane
tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates,
1,1,3,3-
propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
Polycarboxylates
containing sulfo substituents include the sulfosuccinate derivatives disclosed
in British
Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the
sulfonated
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19
pyroiysed citrates described in British Patent No. 1,082,179, while
polycarboxyiates
containing phosphone substituents are disclosed in British Patent No.
1,439,000.
Alicyclic and heterocyclic polycarboxylates include cyciopentane-cis,cis,cis-
tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydro-
furan - cis, cis,
cis-tetracarboxylates, 2,5-tetrahydro-furan -cis - dicarboxylates, 2,2,5,5-
tetrahydrofiu~an -
tetracarboxylates, 1,2,3,4,5,6-hexane -hexacar-boxylates and carboxymethyl
derivatives
of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic poly-
carboxylates
include mellitic acid, pyromellitic acid and the phthalic acid derivatives
disclosed in
British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates
containing
up to three carboxy groups per molecule, more particularly citrates.
Preferred builder systems for use in the present compositions include a
mixture of
a water-insoluble aiuminosilicate builder such as zeolite A or of a layered
silicate (SKS-
6), and a water-soluble carboxylate chelating agent such as citric acid.
Preferred builder systems include a mixture of a water-insoluble
aluminosilicate
builder such as zeolite A, and a watersoluble carboxyiate chelating agent such
as citric
acid. Preferred builder systems for use in liquid detergent compositions of
the present
invention are soaps and polycarboxylates.
Other suitable water-soluble organic salts are the homo- or co-polymeric acids
or
their salts, in which the polycarboxylic acid comprises at least two carboxyl
radicals
separated from each other by not more than two carbon atoms. Polymers of this
type are
disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MW
2000-
5000 and their copolymers with malefic anhydride, such copolymers having a
molecular
weight of from 20,000 to 70,000, especially about 40,000.
Detergency builder salts are normally included in amounts of from 5% to 80% by
weight of the composition preferably from 10% to 70% and most usually from 30%
to
60% by weight.
Bleaching~a
Additional optional detergent ingredients that can be included in the
detergent
compositions of the present invention include bleaching agents such as
hydrogen
peroxide, PB1, PB4 and percarbonate with a particle size of 400-800 microns.
These
bleaching agent components can include one or more oxygen bleaching agents
and,
depending upon the bleaching agent chosen, one or more bleach activators. When
present
oxygen bleaching compounds will typically be present at levels of from about 1
% to
about 25%.
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WO 99/55817 PCT/US98/08629
The bleaching agent component for use herein can be any of the bleaching
agents
useful for detergent compositions including oxygen bleaches as well as others
known in
the art. The bleaching agent suitable for the present invention can be an
activated or non-
activated bleaching agent.
Examples of suitable bleaching agents are disclosed in U.S. Patent Nos.
5,707,950
and 5,576,282.
The hydrogen peroxide releasing agents can be used in combination with, for
example, the bleach activators disclosed in U.S. Patent No. 5,707,950 or
Phenolsulfonate
ester of N-nonanoyl-6-aminocaproic acid (NACA-OBS, described in W094/28106),
which are perhydrolyzed to form a peracid as the active bleaching species,
leading to
improved bleaching effect. Also suitable activators are acylated citrate
esters.
Useful bleaching agents, including peroxyacids and bleaching systems
comprising
bleach activators and peroxygen bleaching compounds for use in detergent
compositions
according to the invention are described in W095/27772, W095/27773,
W095/27774,
W095/27775 and U.S. Patent No. 5,707,950.
Metal-containing catalysts for use in bleach compositions, include cobalt-
containing catalysts such as Pentaamine acetate cobalt(III) salts and
manganese-
containing catalysts such as those described in EPA 549 271; EPA 549 272; EPA
458
397; US 5,246,621; EPA 458 398; US 5,194,416 and US 5,114,611. Bleaching
composition comprising a peroxy compound, a manganese-containing bleach
catalyst and
a chelating agent is described in the patent application No 94870206.3.
Dve 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.
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 poiyamine N-
oxide
polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidone
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21
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.
Dispersants
The detergent composition of the present invention can also contain
dispersants.
Suitable water-soluble organic salts are the homo- or co-polymeric acids or
their salts, in
which the polycarboxylic acid comprises at least two carboxyl radicals
separated from
each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts
are polyacrylates of MW 2000-5000 and their copolymers with malefic anhydride,
such
copolymers having a molecular weight of from 1,000 to 100,000.
Especially, copolymer of acrylate and methylacrylate such as the 480N having a
molecular weight of 4000, at a level from 0.5-20% by weight of composition can
be
added in the detergentcompositions of the present invention.
The compositions of the invention may contain a lime soap peptiser compound,
which has a lime soap dispersing power (LSDP), as defined hereinafter of no
more than 8,
preferably no more than 7, most preferably no more than 6. The lime soap
peptiser
compound is preferably present at a level from 0% to 20% by weight.
A numerical measure of the effectiveness of a lime soap peptiser is given by
the
lime soap dispersant power (LSDP) which is determined using the lime soap
dispersant
test as described in an article by H.C. Borghetty and C.A. Bergman, J. Am.
Oil. Chem.
Soc., volume 27, pages 88-90, (1950). This lime soap dispersion test method is
widely
used by practitioners in this art field being referred to, for example, in the
following
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22
review articles; W.N. Linfield, Surfactant science Series, Volume 7, page 3;
W.N.
Linfield, Tenside surf..det., volume 27, pages 159-163, (1990); and M,K.
Nagarajan, W.F.
Masler, Cosmetics and Toiletries, volume i 04, pages 71-73, ( 1989). The LSDP
is the
weight ratio of dispersing agent to sodium oleate required to disperse the
lime soap
deposits formed by 0.025g of sodium oleate in 30m1 of water of 333ppm CaCo3
(Ca:Mg=3:2) equivalent hardness.
Surfactants having good lime soap peptiser capability will include certain
amine
oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated
alcohols.
Exemplary surfactants having a LSDP of no more than 8 for use in accord with
the
present invention include C 16-C 1 g dimethyl amine oxide, C 12-C 1 g alkyl
ethoxysulfates
with an average degree of ethoxylation of from 1-S, particularly C 12-C 15
alkyl
ethoxysulfate surfactant with a degree of ethoxylation of amount 3 (LSDP=4),
and the
C 14-C 15 e~oxylated alcohols with an average degree of ethoxylation of either
12
(LSDP=6) or 30, sold under the tradenames Lutensol A012 and Lutensol A030
respectively, by BASF GmbH.
Polymeric lime soap peptisers suitable for use herein are described in the
article by
M.K. Nagarajan, W.F. Masler, to be found in Cosmetics and Toiletries, volume
104,
pages 71-73, ( 1989).
Hydrophobic bleaches such as 4-(N-octanoyl-6-aminohexanoyl]benzene sulfonate,
4-[N-nonanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-decanoyl-6-
aminohexanoyl]benzene sulfonate and mixtures thereof; and nonanoyloxy benzene
sulfonate together with hydrophilic / hydrophobic bleach formulations can also
be used as
lime soap peptisers compounds.
Examples of other suitable dispersing agents are disclosed in U.S. .Patent
Nos.
5,576,282 and 5,728,671.
Conventional detergent enzymes
It has also been surprisingly found that the combination of a transferase with
a
detergent enzyme - especially a protease, cellulase, lipase andlor amylase -
provides,
refurbishes or restores improved tensile strength, enhanced anti-wrinkle, anti-
shrinkage,
anti-bobbling properties to fabrics, as well as provide better static control,
fabric softness,
colour appearance and fabric anti-wear properties and benefits. In addition,
improved
cleaning benefits are achieved with said combinations.
Said enzymes include enzymes selected from hemicellulases, cellulase,
peroxidases, gluco-amylases, amylases, xylanases, lipases, phospholipases,
esterases,
cutinases, pectinases, keratinases, reductases, oxidases, phenoloxidases,
lipoxygenases,
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23
ligninases, pullulanases, tannases, pentosanases, malanases,13-glucanases,
arabinosidases,
hyaluronidase, chondroitinase, laccase or mixtures thereof.
A preferred combination is a laundry detergent and/or fabric care composition
having cocktail of conventional applicable enzymes like protease, amylase,
lipase,
cutinase and/or cellulase in conjunction with one or more plant cell wall
degrading
enzymes.
Examples of suitable enzymes are disclosed in U.S. Patent Nos. 5,576,282,
5,728,671 and 5,707,950
A preferred combination is a detergent composition having cocktail of
conventional applicable enzymes like protease, lipase, cutinase and/or
cellulase in
conjunction with the hexosaminidase.
Particularly useful proteases are described in PCT publications: WO 95/30010
published November 9, 1995 by The Procter & Gamble Company; WO 95/30011
published November 9, 1995 by The Procter & Gamble Company; and WO 95/29979
published November 9, 1995 by The Procter & Gamble Company.
In addition to the peroxidase enzymes disclosed in U.S. Patent Nos. 5,576,282,
5,728,671 and 5,707,950, other suitable peroxidase enzymes are disclosed in
European
Patent application EP No. 96870013.8, filed February 20, 1996. Also suitable
is the
laccase enzyme.
Preferred enhancers are substituted phenthiazine and phenoxasine 10-
Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid
(EPC), 10-
phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO
94/1262i) and substitued syringates (C3-C5 substitued alkyl syringates) and
phenols.
Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
Said peroxidases are normally incorporated in the detergent composition at
levels
from 0.0001 % to 2% of active enzyme by weight of the detergent composition.
Other preferred enzymes that can be included in the detergent 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;
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Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth
Co.,
The Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable
lipases are
lipases such as M1 LipaseR ~d LipomaxR (Gist-Brocades) and LipolaseR and
Lipoiase
UltraR{Novo) which have found to be very effective when used in combination
with the
compositions of the present invention.
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 detergent compositions have been described in e.g. WO 88/09367
(Genencor).
The lipases and/or cutinases are normally incorporated in the detergent
composition at levels from 0.0001 % to 2% of active enzyme by weight of the
detergent
composition.
Known amylases (a and/or 13) can be included for removal of carbohydrate-based
stains. WO 94/02597, Novo Nordisk A/S published February 03, 1994, describes
cleaning
compositions which incorporate mutant amylases. See also W094/18314, Genencor,
published August 18, 1994 and W095/10603, Novo Nordisk A/S, published April
20,
i 995. Other amylases known for use in detergent compositions include both a-
and ~i-
amylases. a-Amylases are known in the art and include those disclosed in US
Pat.
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
amylase
are stability-enhanced amylases including Purafact Ox AmR described in WO
94/18314,
published August 18, 1994 and W096/05295, Genencor, published February 22,
1996
and amylase variants from Novo Nordisk A/S, disclosed in WO 95/10603,
published
April 95.
Examples of commercial a-amylases products are 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
specif c 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. 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. Purified or non-purified forms of
these
enzymes may be used. Also included by definition, are mutants of native
enzymes.
Mutants can be obtained e.g. by protein and/or genetic engineering, chemical
and/or
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physical modifications of native enzymes. Common practice as well is the
expression of
the enzyme via host organisms in which the genetic material responsible for
the
production of the enzyme has been cloned.
Said enzymes are normally incorporated in the detergent composition at levels
from 0.0001 % to 2% of active enzyme by weight of the detergent composition.
The
enzymes can be added as separate single ingredients (grills, granulates,
stabilized liquids,
etc. containing one enzyme ) or as mixtures of two or more enzymes ( e.g.
cogranulates).
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 and means for their incorporation into synthetic
detergent compositions is also disclosed in WO 9307263 and WO 9307260 to
Genencor
International, WO 8908694 to Novo, and U.S. 3,553,139, January 5, 1971 to
McCarty et
al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18,
1978, and in
U.S. 4,507,2 / 9, Hughes, March 26, 1985. Enzyme materials useful for liquid
detergent
formulations, and their incorporation into such formulations, are disclosed in
U.S.
4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be
stabilized by
various techniques. Enzyme stabilisation techniques are disclosed and
exemplified in
U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586,
October 29,
1986, Venegas. Enzyme stabilisation systems are also described, for example,
in U.S.
3,519,570. A useful Bacillus, sp. AC 13 giving proteases, xylanases and
cellulases, is
described in WO 9401532 to Novo.
Chelatina Agents
The detergent compositions herein may also optionally contain one or more iron
and/or manganese chelating agents. Such chelating agents can be selected from
the group
consisting of amino carboxylates, amino phosphonates, polyfunctionally-
substituted aro-
matic chelating agents and mixtures therein, all as hereinafter defined.
Without intending
to be bound by theory, it is believed that the benefit of these materials is
due in part to
their exceptional ability to remove iron and manganese ions from washing
solutions by
formation of soluble chelates.
Examples of suitable chelating agents are disclosed in U.S. Patent No.
5,728,671.
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% by weight of the detergent compositions herein. More preferably, if
utilized,
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26
the chelating agents will comprise from about 0.1 % to about 3.0% by weight of
such
compositions.
Suds suppressor
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~~ agents
Fabric softening agents can also be incorporated into laundry detergent
compositions in accordance with the present invention. These agents may be
inorganic or
organic in type. Inorganic softening agents are exemplified by the smectite
clays
disclosed in GB-A-1 400 898 and in USP 5,019,292. Organic fabric softening
agents
include the water insoluble tertiary amines as disclosed in GB-A1 SI4 276 and
EP-BO 011
340 and their combination with mono C 12-C 14 quaternary ammonium salts are
disclosed
in EP-B-0 026 527 and EP-B-0 026 528 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.
Typical cationic fabric softening components include the water-insoluble
quaternary-ammonium fabric softening actives, the most commonly used having
been di-
long alkyl chain ammonium chloride or methyl sulfate.
Preferred cationic softeners among these include the following:
1 ) ditallow dimethylammonium chloride (DTDMAC);
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27
2) dihydrogenated tallow dimeihylammonium chloride;
3) dihydrogenated tallow dimethylammonium methylsulfate;
4) distearyl dimethylammonium chloride;
5) dioleyl dimethylammonium chloride;
6) dipalmityl hydroxyethyl methylammonium chloride;
7) stearyl benzyl dimethylammonium chloride;
8) tallow trimethylammonium chloride;
9) hydrogenated tallow trimethylammonium chloride;
10) 012-14 ~kYl hydroxyethyl dimethylammonium chloride;
11 ) C 12-18 ~k3'1 dihydroxyethyl methylammonium chloride;
12) di(stearoyloxyethyl) dimethylammonium chloride (DSOEDMAC);
13) di(tallowoyloxyethyl) dimethylammonium chloride;
14) ditallow imidazolinium methylsulfate;
15) 1-{2-tallowylamidoethyl)-2-tallowyl imidazolinium methylsulfate.
Biodegradable quaternary ammonium compounds have been presented as
alternatives to the traditionally used di-long alkyl chain ammonium chlorides
and methyl
sulfates. Such quaternary ammonium compounds contain long chain alk(en)yl
groups
interrupted by functional groups such as carboxy groups. Said materials and
fabric
softening compositions containing them are disclosed in numerous publications
such as
EP-A-0,040,562, and EP-A-0,239,910.
Non-limiting examples of softener-compatible anions for the quaternary
ammonium compounds and amine precursors include chloride or methyl sulfate.
Preservatives
The laundry detergent and/or fabric care compositions herein may also
optionally
contain one or more preservatives. The function of the preservatives is to
prevent
organisms/micro-organisms from breeding and growing on the fabrics treated
with the
laundry detergent and/or fabric care compositions herein. In the absence of
such
preservatives, organisms/micro-organisms could grow on the fabrics treated
with the
laundry detergent and/or fabric care compositions herein because a significant
amount of
carbohydrates/sugar could remain on the fabrics after treatment.
Sanitization of fabrics can be achieved by the compositions of the present
invention containing antimicrobial materials, e.g., antibacterial halogenated
compounds,
quaternary compounds, and phenolic compounds.
Suitable preservatives for use with the present invention include, but are not
limited to, the following.
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28
It is preferable to use a broad spectrum preservative, e.g., one that is
effective on
both bacteria (both gram positive and gram negative) and fungi. A limited
spectrum
preservative, e.g., one that is only effective on a single group of
microorganisms, e.g.,
fungi, can be used in combination with a broad spectrum preservative or other
limited
spectrum preservatives with complimentary and/or supplementary activity. A
mixture of
broad spectrum preservatives can also be used. In some cases where a specific
group of
microbial contaminants is problematic (such as Gram negatives),
aminocarboxylate
chelators may be used alone or as potentiators in conjunction with other
preservatives.
These chelators which include, e.g., ethylenediaminetetraacetic acid (EDTA),
hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and
other
aminocarboxylate chelators, and mixtures thereof, and their salts, and
mixtures thereof,
can increase preservative effectiveness against Gram-negative bacteria,
especially
Pseudomonas species.
Antimicrobial preservatives useful in the present invention include biocidal
compounds, i.e., substances that kill microorganisms, or biostatic compounds,
i.e.,
substances that inhibit and/or regulate the growth of microorganisms.
(1) Oreanic Sulfur Compounds
Preferred water-soluble preservatives for use in the present invention are
organic
sulfur compounds. Some non-limiting examples of organic sulfur compounds
suitable for
use in the present invention are:
(a) 3-Isothiazolone Compounds - A preferred preservative is an antimicrobial,
organic preservative containing 3-isothiazolone groups having the formula:
RI O
I N
~Y
wherein Y is an unsubstituted alkyl, alkenyl, or alkynyl group of from about 1
to about 18
carbon atoms, an unsubstituted or substituted cycloalkyl group having from
about a 3 to
about a 6 carbon ring and up to 12 carbon atoms, an unsubstituted or
substituted aralkyl
group of up to about 10 carbon atoms, or an unsubstituted or substituted aryl
group of up
to about 10 carbon atoms; R1 is hydrogen, halogen, or a (C 1-C4) alkyl group;
and R2 is
hydrogen, halogen, or a (C1-C4) alkyl group.
Preferably, when Y is methyl or ethyl, R1 and R2 should not both be hydrogen.
Salts of these compounds formed by reacting the compound with acids such as
hydrochloric, nitric, sulfuric, etc. are also suitable.
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This class of compounds is disclosed in U.S. Pat. No. 4,265,899, Lewis et al.,
issued May 5, 1981, and incorporated herein by reference. Examples of said
compounds
are: S-chloro-2-methyl-4-isothiazolin-3-one; 2-n-butyl-3-isothiazolone; 2-
benzyl-3-
isothiazolone; 2-phenyl-3-isothiazolone, 2-methyl-4,5-dichloroisothiazolone; ;
5-chloro-
2-methyl-3-isothiazolone; 2-methyl-4-isothiazolin-3-one; and mixtures thereof.
A
preferred preservative is a water-soluble mixture of S-chloro-2-methyl-4-
isothiazolin-3-
one and 2-methyl-4-isothiazolin-3-one, more preferably a mixture of about 77%
5-chloro-
2-methyl-4-isothiazolin-3-one and about 23% 2-methyl-4-isothiazolin-3-one, a
broad
spectrum preservative available as a 1.5% aqueous solution under the trade
name
Kathon~ CG by Rohm and Haas Company.
When Kathon~ is used as the preservative in the present invention it is
present at
a level of from about 0.0001 % to about 0.01 %, preferably from about 0.0002%
to about
0.005%, more preferably from about 0.0003% to about 0.003%, most preferably
from
about 0.0004% to about 0.002%, by weight of the composition.
Other isothiazolins include 1,2-benzisothiazolin-3-one, available under the
trade
name Proxel~ products; and 2-methyl-4,5-trimethylene-4-isothiazolin-3-one,
available
under the trade name Promexal~. Both Proxel and Promexal are available from
Zeneca.
They have stability over a wide pH range (i.e., 4-12). Neither contain active
halogen and
are not formaldehyde releasing preservatives. Both Proxel and Promexal are
effective
against typical Gram negative and positive bacteria, fungi and yeasts when
used at a level
from about 0.001% to about 0.5%, preferably from about 0.005% to about 0.05%,
and
most preferably from about 0.01 % to about 0.02% by weight of the usage
composition.
(b) Sodium Pyrithione - Another preferred organic sulfur preservative is
sodium pyrithione, with water solubility of about 50%. When sodium pyrithione
is used
as the preservative in the present invention it is typically present at a
level of from about
0.0001% to about 0.01%, preferably from about 0.0002% to about 0.005%, more
preferably from about 0.0003% to about 0.003%, by weight of the usage
composition.
Mixtures of the preferred organic sulfur compounds can also be used as the
preservative in the present invention.
(2) HaloQenated Compounds
Preferred preservatives for use in the present invention are halogenated
compounds. Some non-limiting examples of halogenated compounds suitable for
use in
the present invention are:
(a) 5-bromo-5-nitro-1,3-dioxane, available under the trade name Bronidox L~
from Henkel. Bronidox L~ has a solubility of about 0.46% in water. When
Branidox is
used as the preservative in the present invention it is typically present at a
level of from
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WO 99/55817 PCTNS98/08629
about 0.0005% to about 0.02%, preferably from about 0.001 % to about 0.01 %,
by weight
of the usage composition;
(b) 2-bromo-2-nitropropane-1,3-diol, available under the trade name Bronopol~
from Inolex can be used as the preservative in the present invention. Bronopol
has a
solubility of about 25% in water. When Bronopol is used as the preservative in
the
present invention it is typically present at a level of from about 0.002% to
about 0.1 %,
preferably from about 0.005% to about 0.05%, by weight of the usage
composition;
(c) 1,1'-hexamethylene bis(5-{p-chlorophenyl)biguanide), commonly known as
chlorhexidine, and its salts, e.g., with acetic and gluconic acids can be used
as a
preservative in the present invention. The digluconate salt is highly water-
soluble, about
70% in water, and the diacetate salt has a solubility of about 1.8% in water.
When
chlorohexidine is used as the preservative in the present invention it is
typically present at
a level of from about 0.0001 % to about 0.04%, preferably from about 0.0005%
to about
0.01 %, by weight of the usage composition.
(d) 1,1,1-Trichloro-2-methylpropan-2-ol, commonly known as chlorobutanol,
with water solubility of about 0.8%; a typical effective level of
chlorobutanol is from
about 0.1% to about 0.5%, by weight of the usage composition;
(e) 4,4'- (Trimethylenedioxy)bis-(3-bromobenzamidine) diisethionate, or
dibromopropamidine, with water solubility of about 50%; when
dibromopropamidine is
used as the preservative in the present invention it is typically present at a
level of from
about 0.0001% to about 0.05%, preferably from about 0.0005% to about 0.01% by
weight
of the usage composition.
Mixtures of the preferred halogenated compounds can also be used as the
preservative in the present invention.
(3) Cyclic Organic Nitrosen Compounds
Preferred water-soluble preservatives for use in the present invention are
cyclic
organic nitrogen compounds. Some non-limiting examples of cyclic organic
nitrogen
compounds suitable for use in the present invention are:
(a) Imidazolidinedione Compounds - Preferred preservatives for use in the
present
invention are imidazolidione compounds. Some non-limiting examples of
imidazolidinedione compounds suitable for use in the present invention are:
1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione, commonly
known as dimethyloldimethylhydantoin, or DMDM hydantoin, available as, e.g.,
Glydant
~ from Lonza. DMDM hydantoin has a water solubility of more than 50% in water,
and
is mainly effective on bacteria. When DMDM hydantoin is used, it is preferable
that it be
used in combination with a broad spectrum preservative such as Kathon CG~, or
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formaldehyde. A preferred mixture is about a 95:5 DMDM hydantoin to 3-butyl-2-
iodopropynylcarbamate mixture, available under the trade name Glydant Plus~
from
Lonza. When Glydant Plus~ is used as the preservative in the present
invention, it is
typically present at a level of from about 0.005% to about 0.2% by weight of
the usage
composition;
N-[ 1,3-bis(hydroxymethyl)2, 5-dioxo-4-imidazolidinyl)-N,N'-
bis(hydroxymethyl) urea, commonly known as diazolidinyl urea, available under
the trade
name Germall II~ from Sutton Laboratories, Inc. (Sutton) can be used as the
preservative
in the present invention. When Germall II~ is used as the preservative in the
present
invention, it is typically present at a level of from about 0.01 % to about
0.1 % by weight
of the usage composition;
N,N"-methylenebis {N'-[ 1-(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl]urea} ,
commonly known as imidazolidinyl urea, available, e.g., under the trade name
Abiol~
from 3V-Sigma, Unicide U-13~ from Induchem, Germall 115 from (Sutton) can be
used as the preservative in the present invention. When imidazolidinyl urea is
used as the
preservative, it is typically present at a level of from about 0.05% to about
0.2%, by
weight of the usage composition.
Mixtures of the preferred imidazolidinedione compounds can also be used as the
preservative in the present invention.
(b) Polymethoxy Bicyclic Oxazolidine - Another preferred water-soluble
cyclic organic nitrogen preservative is polymethoxy bicyclic oxazolidine,
having the
general formula:
CH2(OCH2~H
O~N ~O
where n has a value of from about 0 to about 5, and is available under the
trade name
Nuosept~ C from Hills America. When Nuosept~ C is used as the preservative, it
is
typically present at a level of from about 0.005% to about 0.1 %, by weight of
the usage
composition.
Mixtures of the preferred cyclic organic nitrogen compounds can also be used
as
the preservative in the present invention.
(4) Low Molecular Weight Aldehydes
(a) Formaldehyde - A preferred preservative for use in the present invention
is
formaldehyde. Formaldehyde is a broad spectrum preservative which is normally
available as formalin which is a 37% aqueous solution of formaldehyde. When
formaldehyde is used as the preservative in the present invention, typical
levels are from
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32
about 0.003% to about 0.2%, preferably from about 0.008% to about 0.1%. more
preferably from about 0.01 % to about 0.05%, by weight of the usage
composition.
(b) Glutaraldehyde - A preferred preservative for use in the present invention
is
glutaraldehyde. Glutaraldehyde is a water-soluble, broad spectrum preservative
commonly available as a 25% or a 50% solution in water. When glutaraldehyde is
used
as the preservative in the present invention it is typically present at a
level of from about
0.005% to about 0.1%, preferably from about 0.01% to about 0.05%, by weight of
the
usage composition.
(5) Ouaternarv Compounds
Preferred preservatives for use in the present invention are cationic and/or
quaternary compounds. Such compounds include polyaminopropyl biguanide, also
known as polyhexamethylene biguanide having the general formula:
HCl~NH2-(CH2)3-[-(CH2)3-NH-C(=NH)-NH-C(=NH~HCl)-NH-(CH2)3-Jx-(CH2)3-
NH-C(=NH)-NH~CN
Polyaminopropyl biguanide is a water-soluble, broad spectrum preservative
which
is available as a 20% aqueous solution available under the trade name Cosmocil
CQ~
from ICI Americas, Inc., or under the trade name Mikrokill~ from Brooks, Inc.
1-(3-Chlorallyl) -3,5,7-triaza-1-azoniaadamantane chloride, available, e.g.,
under
the trade name Dowicil 200 from Dow Chemical, is an effective quaternary
ammonium
preservative; it is freely soluble in water; however, it has the tendency to
discolor
(yellow), therefore it is not highly preferred.
Mixtures of the preferred quaternary ammonium compounds can also be used as
the preservative in the present invention.
When quaternary ammonium compounds are used as the preservative in the
present invention, they are typically present at a level of from about 0.005%
to about
0.2%, preferably from about 0.01 % to about 0.1 %, by weight of the usage
composition.
(6). Dehvdroacetic Acid
A preferred preservative for use in the present invention is dehydroacetic
acid.
Dehydroacetic acid is a broad spectrum preservative preferably in the form of
a sodium or
a potassium salt so that it is water-soluble. This preservative acts more as a
biostatic
preservative than a biocidal preservative. When dehydroacetic acid is used as
the
preservative it is typically used at a level of from about 0.005% to about
0.2%, preferably
from about 0.008% to about 0.1 %, more preferably from about 0.01 % to about
0.05%, by
weight of the usage composition.
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33
(?) Phenvl and Phenolic Compounds
Some non-limiting examples of phenyl and phenolic compounds suitable for use
in the present invention are:
4,4'-diamidino-a,w-diphenoxypropane diisethionate, commonly known as
propamidine isethionate, with water solubility of about 1 b%; and 4,4'-
diamidino-a,w-
diphenoxyhexane diisethionate, commonly known as hexamidine isethionate.
Typical
effective level of these salts is about 0.0002% to about 0.05% by weight of
the usage
composition.
Other examples are benzyl alcohol, with a water solubility of about 4%; 2-
phenylethanol, with a water solubility of about 2%; and 2-phenoxyethanol, with
a water
solubility of about 2.67%; typical effective level of these phenyl and phenoxy
alcohol is
from about 0.1 % to about 0.5%, by weight of the usage composition.
(8) Mixtures thereof
It is preferred that no, or essentially no, volatile low molecular weight
monohydric
alcohols such as ethanol and/or isopropanol are intentionally added to the
composition of
the present invention since these volatile organic compounds will contribute
both to
flammability problems and environmental pollution problems. If small amounts
of low
molecular weight monohydric alcohols are present in the composition of the
present
invention due to the addition of these alcohols to such things as perfumes and
as
stabilizers for some preservatives, it is preferable that the level of
monohydric alcohol be
less than about 5%, preferably less than about 3%, more preferably less than
about 1%.
(9) Mixtures thereof
The preservatives of the present invention can be used in mixtures in order to
control a broad range of microorganisms.
Bacteriostatic effects can sometimes be obtained for aqueous compositions by
adjusting the composition pH to an acid pH, e.g., less than about pH 4,
preferably less
than about pH 3, or a basic pH, e.g., greater than about 10, preferably
greater than about
11.
( 10) Preferred preservatives
Preferably the preservatives used in the compositions of the present invention
are
selected from the group consisting of isothiazolones; Bronopol; hydantoins;
oxazolidines; glutaraldehyde; isethionates; quats (benzalkoniums); and
mixtures thereof.
Other Deter~~nt Components
The laundry detergent and/or fabric care compositions of the invention may
also
contain additional detergent and/or fabric care components. The precise nature
of these
additional components, and levels of incorporation thereof will depend on the
physical
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34
form of the composition, and the nature of the cleaning operation for which it
is to be
used.
Examples of other components used in detergent compositions include, but are
not
limited to, soil-suspending agents, soil-release agents, optical brighteners,
abrasives,
bactericides, tarnish inhibitors, coloring agents, and/or encapsulated or non-
encapsulated
perfumes, examples of which are disclosed in U.S. Patent Nos. 5,707,950,
5,576,282 and
5,728,671.
It is well known in the art that free chlorine in tap water rapidly
deactivates the
enzymes comprised in detergent compositions. Therefore, using chlorine
scavenger such
as perborate, ammonium sulfate, sodium sulphite or polyethyleneimine at a
level above
0.1 % by weight of total composition, in the formulas will provide improved
through the
wash stability of the detergent enzymes. Compositions comprising chlorine
scavenger are
described in the European patent application 92870018.6 filed January 31,
1992.
Alkoxylated polycarboxylates such as those prepared from polyacrylates are
useful
herein to provide additional grease removal performance. Such materials are
described in
WO 91 /08281 and PCT 90/01815 at p. 4 et seq., incorporated herein by
reference.
Chemically, these materials comprise polyacrylates having one ethoxy side-
chain per
every 7-8 acrylate units. The side-chains are of the formula -
(CH2CH20)m(CH2)nCH3
wherein m is 2-3 and n is 6-12. The side-chains are ester-linked to the
polyacrylate
"backbone" to provide a "comb" polymer type structure. The molecular weight
can vary,
but is typically in the range of about 2000 to about 50,000. Such alkoxylated
polycarboxylates can comprise from about 0.05% to about 10%, by weight, of the
compositions herein.
Detergent Composition Form
The laundry detergent and/or fabric care compositions according to the
invention
can be liquid, paste, gels, bars, tablets, spray, foam, powder or granular
forms. Granular
compositions can also be in "compact" form, the liquid compositions can also
be in a
"concentrated" form.
The compositions of the invention may for example, be formulated as hand and
machine laundry detergent compositions including laundry additive compositions
and
compositions suitable for use in the soaking and/or pre-treatment of stained
fabrics, rinse
added fabric softener compositions. Pre-or post treatment of fabric include
gel, spray and
liquid fabric care compositions. A rinse cycle with or without the presence of
softening
agents is also contemplated.
When formulated as compositions suitable for use in a laundry machine washing
method, the compositions of the invention preferably contain both a surfactant
and a
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builder compound and additionally one or more detergent components preferably
selected
from organic polymeric compounds, bleaching agents, additional enzymes, suds
suppressors, dispersants, lime-soap dispersants, soil suspension and anti-
redeposition
agents and corrosion inhibitors. Laundry compositions can also contain
softening agents,
as additional detergent components.
The compositions of the invention can also be used as detergent additive
products.
Such additive products are intended to supplement or boost the performance of
conventional detergent compositions.
If needed the density of the laundry detergent compositions herein ranges from
400 to 1200 g/litre, preferably 600 to 950 g/litre of composition measured at
20°C.
The "compact" form of the 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 S% 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 sulphates and chlorides.
A preferred filler salt is sodium sulphate.
Liquid detergent compositions according to the present invention can also be
in a
"concentrated form", in such case, the liquid detergent 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 detergent is preferably
less
than 40%, more preferably less than 30%, most preferably less than 20% by
weight of the
detergent composition.
The compositions of the present invention can be incorporated into a spray
dispenser that can create an article of manufacture that can facilitate the
cleaning and/or
fabric care of fabric. Compositions containing from 1 ppm to 50 ppm of pure
transferase
enzyme by weight of total composition and 0.01 % to 20% of its corresponding
substrate
by weight of total composition, are preferably sprayed onto the fabrics and
therefore
typically packaged in a spray dispenser.
The spray dispenser can be any of the manually activated means for producing a
spray of liquid droplets as is known in the art, e.g. trigger-type, pump-type,
non-aerosol
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36
self pressurized, and aerosol-type spray means. It is preferred that at least
about 70%,
more preferably, at least about 80%, most preferably at least about 90% of the
droplets
have a particle size of smaller than about 200 microns.
The spray dispenser can be an aerosol dispenser. Said aerosol dispenser
comprises
a container which can be constructed of any of the conventional materials
employed in
fabricating aerosol containers. The dispenser must be capable of withstanding
internal
pressure in the range of from about 20 to about 110 p.s.i.g., more preferably
from about
20 to about 70 p.s.i.g. The one important requirement concerning the dispenser
is that it
be provided with a valve member which will permit the wrinkle reducing
composition
contained in the dispenser to be dispensed in the form of a spray of very
fine, or finely
divided, particles or droplets. The aerosol dispenser utilizes a pressurized
sealed
container from which the wrinkle reducing composition is dispensed through a
special
actuator/valve assembly under pressure. The aerosol dispenser is pressurized
by
incorporating therein a gaseous component generally known as a propellant.
Common
aerosol propellants, e.g., gaseous hydrocarbons such as isobutane, and mixed
halogenated
hydrocarbons, are not preferred. Halogenated hydrocarbon propellants such as
chlorofluoro hydrocarbons have been alleged to contribute to environmental
problems.
Preferred propellants are compressed air, nitrogen, inert gases, carbon
dioxide, etc. A
more complete description of commercially available aerosol spray dispensers
appears in
U.S. Pat. Nos.: 3,436,772, Stebbins, issued Apr.B, 1969; and 3,600,325,
Kaufman et al.,
issued Aug. 17, 1971; both of said references are incorporated herein by
reference.
Preferably the spray dispenser can be a self pressurized non-aerosol container
having a convoluted liner and an elastomeric sleeve. Said self pressurized
dispenser
comprises a liner/sleeve assembly containing a thin, flexible radially
expandable
convoluted plastic liner of from about 0.010 to about 0.020 inch thick, inside
an
essentially cylindrical elastomeric sleeve. The liner/sleeve is capable of
holding a
substantial quantity of odor-absorbing fluid product and of causing said
product to be
dispensed. A more complete description of self pressurized spray dispensers
can be
found in U.S. Pat. Nos.: 5,111,971, Winer, issued May 12, 1992; and 5,232,126,
Winer,
issued Aug. 3, 1993; both of said references are herein incorporated by
reference.
Another type of aerosol spray dispenser is one wherein a barrier separates the
wrinkle
reducing composition from the propellant (preferably compressed air or
nitrogen), as is
disclosed in U.S. Pat. No. 4,260,110, issued Apr. 7, 1981, incorporated herein
by
reference. Such a dispenser is available from EP Spray Systems, East Hanover,
N.J.
More preferably, the spray dispenser is a non-aerosol, manually activated,
pump-
spray dispenser. Said pump-spray dispenser comprises a container and a pump
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37
mechanism which securely screws or snaps onto the container. The container
comprises a
vessel for containing the wrinkle reducing composition to be dispensed.
The pump mechanism comprises a pump chamber of substantially fixed, volume,
having an opening at the inner end thereof. Within the pump chamber is located
a pump
stem having a piston on the end thereof disposed for reciprocal motion in the
pump
chamber. The pump stem has a passageway there through with a dispensing outlet
at the
outer end of the passageway and an axial inlet port located inwardly thereof.
The container and the pump mechanism can be constructed of any conventional
material employed in fabricating pump-spray dispensers, including, but not
limited to:
polyethylene; polypropylene; polyethlyleneterephthalate; blends of
polyethylene, vinyl
acetate, and rubber elastomer. Other materials can include stainless steel. A
more
complete disclosure of commercially available dispensing devices appears in:
U.S. Pat.
Nos.: 4,895,279, Schultz, issued Jan. 23, 1990; 4,735,347, Schultz et al.,
issued Apr. S,
1988; and 4,274,560, Carter, issued Jun. 23, 19$1; all of said references are
herein
incorporated by reference.
Most preferably, the spray dispenser is a manually activated trigger-spray
dispenser. Said trigger-spray dispenser comprises a container and a trigger
both of which
can be constructed of any of the conventional material employed in fabricating
trigger-
spray dispensers, including, but not limited to : polyethylene, polypropylene,
polyacetal,
polycarbonate, polyethylene-terephthalate , polyvinyl chloride, polystyrene,
blends of
polyethylene, vinyl acetate, and rubber elastomer. Other materials can include
stainless
steel and glass. The trigger-spray dispenser does not incorporate a propellant
gas. The
trigger-spray dispenser herein is typically one which acts upon a discrete
amount of the
wrinkle reducing composition itself, typically by means of a piston or a
collapsing
bellows that displaces the composition through a nozzle to create a spray of
thin liquid.
Said trigger-spray dispenser typically comprises a pump chamber having either
a piston or
bellows which is movable through a limited stroke response to the trigger for
varying the
volume of said pump chamber. This pump chamber or bellows chamber collects and
holds the product for dispensing. The trigger spray dispenser typically has an
outlet
check valve for blocking communication and flow of fluid through the nozzle
and is
responsive to the pressure inside the chamber. For the piston type trigger
sprayers, as the
trigger is compressed, it acts on the fluid in the chamber and the spring,
increasing the
pressure on the fluid. For the bellows spray dispenser, as the bellows is
compressed, the
pressure increases on the fluid. The increase in fluid pressure in either
trigger-spray
dispenser acts to open the top outlet check valve. The top valve allows the
product to be
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38
forced through the swirl chamber and out the nozzle to form a discharge
pattern. An
adjustable nozzle cap can be used to vary the pattern of the fluid dispensed.
For the piston spray dispenser, as the trigger is released, the spring acts on
the
piston to return to its original position. For the bellows spray dispenser,
the bellows acts
as the spring to return to its original position. This action causes a vacuum
in the
chamber. The responding fluid acts to close the outlet valve while opening the
inlet valve
drawing product up the chamber from the reservoir.
A more complete disclosure of commercially available dispensing devices
appears
in U.S. Pat. Nos.: 4,082,223, Nozawa, issued Apr. 4, 1978; 4,161,288,
McKinney, issued
Jul. 7, 1985; 4,434,917, Saito et al., issued Mar. 6, 1984; and 4,819,835,
Tasaki, issued
Apr. 11, 1989; 5,303,867, Peterson, issued Apr. 19, 1994; all of said
references are
incorporated herein by reference.
A broad array of trigger sprayers or finger pump sprayers are suitable for use
with
the compositions of this invention. These are readily available from suppliers
such as
Calmar, Inc., City of Industry, California; CSI (Continental Sprayers, Inc.),
St. Peters,
Missouri; Berry Plastics Corp., EvansviIle, Indiana - a distributor of Guala ~
sprayers; or
Seaquest Dispensing, Cary, Ill.
The preferred trigger sprayers are the blue inserted Guala ~ sprayer,
available
from Berry Plastics Corp., the Calmar TS800-lA~ sprayers, available from
Calmar Inc.,
or the CSI T7500~ available from Continental Sprayers Inc., because of the
fine uniform
spray characteristics, spray volume and pattern size. Any suitable bottle or
container can
be used with the trigger sprayer, the preferred bottle is a 17 fl-oz. bottle
(about 500 ml) of
good ergonomics similar in shape to the Cinch~ bottle. It can be made of any
materials
such as high density polyethylene, polypropylene, polyvinyl chloride,
polystyrene,
polyethylene terephthalate, glass or any other material that forms bottles.
Preferably, it is
made of high density polyethylene or polyethylene terephthalate.
For smaller four fl-oz size (about 118 ml), a finger pump can be used with
canister
or cylindrical bottle. The preferred pump for this application is the
cylindrical Euromist
II~ from Seaquest Dispensing.
Methods of Washing andJor Fabric Care
The compositions of the invention may be used in essentially any washing,
cleaning and/or fabric care methods, including soaking methods, spray-on
treatment
methods, pre-treatment methods, methods with rinsing steps for which a
separate rinse aid
composition may be added, post-treatment methods and drying methods wherein
the
composition may be added during the drying cycle, especially when an automatic
dryer is
used.
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39
In another aspect of the invention, there is also provided a method for
providing ,
refurbishing or restoring tensile strength, anti-wrinkle, anti-bobbling and
anti-shrinkage
properties to fabrics, as well as providing static control, fabric softness,
colour appearance
and fabric anti-wear properties and cleaning benefits on treated fabrics upon
domestic
treatment which comprises the step of contacting the fabric with a composition
comprising a transferase enzyme. The contacting step may occur in an aqueous
medium
such as in a rinse cycle, soaking, pre- or post-treatment processes or in an
non-aqueous
medium such as occurs during a tumble-drying process in the presence or
absence of the
corresponding natural substrate. The substrate of the transferase enzyme can
be the fabric
itself, stains and/or soils, added in any treatment including pre- or post-
treatment from the
textile industry and/or from any washing and/or fabric care process, and/or
added together
with the transferase-containing composition.
The process of the invention is conveniently carried out in the course of the
cleaning process. The method of cleaning is preferably carried out at
S°C to 95°C,
especially between 10°C and 60°C. The pH of the treatment
solution is preferably from 7
to 12.
The following examples are meant to exemplify compositions of the present
invention, but are not necessarily meant to limit or otherwise define the
scope of the
invention.
In the detergent compositions, the enzymes levels are expressed by pure enzyme
by weight of the total composition and unless otherwise specified,~the
detergent
ingredients are expressed by weight of the total compositions. T,lie
abbreviated component
identifications therein have the following meanings:
LAS . Sodium linear C 12 alkyl benzene sulphonate
TAS . Sodium tallow alkyl sulphate
CXYAS . Sodium C 1 X - C 1 y alkyl sulfate
25EY . A C12_C15 predominantly linear primary alcohol condensed
with an average of Y moles of ethylene oxide
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CXYEZ : A C I X - C I y predominantly linear primary alcohol condensed
with an average of Z moles of ethylene oxide
XYEZS ~ C 1 X - C 1 Y sodium alkyl sulfate condensed with an average of
Z moles of ethylene oxide per mole
QAS . R2.N+(CH3 ~(C2H4pH) with R2 = C I 2-C 14
Soap . Sodium linear alkyl carboxylate derived from a 80/20 mixture
of tallow and coconut oils.
Nonionic ~ C 13-C I S mixed ethoxylated/propoxylated fatty alcohol with
an average degree of ethoxylation of 3.8 and an average degree
of propoxylation of 4.5 sold under the tradename Plurafac
LF404 by BASF Gmbh.
CFAA ~ C 12-C 14 ~'1 N-methyl glucamide
TFAA ~ C 16-C 18 ~kYl N-methyl glucamide.
TPKFA . C 12-C 14 topped whole cut fatty acids.
DEQA . Di-(tallow-oxy-ethyl) dimethyl ammonium
chloride.
DEQA ( 1 ) . Di-(oleyloxyethyl) dimethyl ammonium methylsulfate.
DEQA (2) . Di-(soft-tallowyloxyethyl) hydroxyethyl
methyl ammonium
methylsulfate.
DTDMAMS . Ditallow dimethyl ammonium methylsulfate.
Glycoperse S-20 . Polyethoxylated sorbitan monostearate available form Lonza.
Clay . Calcium bentonite clay, Bentonite L, available from Southern
Clay Products.
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SDASA . 1:2 ratio of stearyIdimethyl amineariple-pressed stearic acid.
Neodol 45-13 . C14-C15 linear primary alcohol ethoxylate, sold by Shell
Chemical CO.
Silicate : Amorphous Sodium Silicate (Si02:Na20 ratio = 2.0)
NaSKS-6 . Crystalline layered silicate of formula S-Na2Si205,
Carbonate . Anhydrous sodium carbonate with a particle size between 200
ltm and 900pm.
Bicarbonate . Anhydrous sodium bicarbonate with a particle size between
400 p,m and 1200p,m.
STPP . Anhydrous sodium tripolyphosphate
~~1A . Copolymer of 1:4 maleic/acrylic acid, average molecular
weight about 70,000-80,000
Zeolite A . Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si02)12~ 27H20 having a primary particle size in
the range from 0.1 to 10 micrometers
Citrate . Tri-sodium citrate dihydrate of activity 86,4% with a particle
size distribution between 425 ~m and 850 pm.
Citric : Anhydrous citric acid
PB 1 : Anhydrous sodium perborate monohydrate bleach, empirical
formula NaB02.H202
PB4 : Anhydrous sodium perborate tetrahydrate
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Percarbonate . Anhydrous sodium percarbonate bleach of empirical formula
2Na2C03.3H202
TAED . Tetraacetyl ethylene diamine.
NOBS . Nonanoyloxybenzene sulfonate in the form of the sodium salt.
Photoactivated Bleach . Sulfonated zinc phtalocyanine encapsulated in dextrin
soluble
polymer.
Transferase . Transferase EC 2.4.1.24 sold by Genencor under the tradename
Transglucosidase L-S00 and Transferase EC 2.3.2.13 available
from Novo Nordisk under the name transglutaminase.
Substrate : Maltose, e.g. Maltose M5885 sold by Sigma and/or Starch,
e.g. YES2760 sold by Sigma or an amino acid, di/tri/poly
peptide and/or protein.
Protease . Proteolytic enzyme sold under the tradename Savinase,
Alcalase, Durazym by Novo Nordisk A/S, Maxacal, Maxapem
sold by Gist-Brocades and proteases described in patents
W091/06637 and/or W095/10591 and/or EP 251 446.
Amylase . Amylolytic enzyme sold under the tradename Purafact Ox
AmR described in WO 94/18314, W096/05295 sold by
Genencor; Termamyl~, Fungamyl~ and Duramyl~, all
available from Novo Nordisk A/S and those described in
W095/26397.
Lipase . Lipolytic enzyme sold under the tradename Lipolase, Lipolase
Ultra by Novo Nordisk A/S or Lipomax by Gist-Brocades.
Cellulase . Cellulytic enzyme sold under the tradename Carezyme,
Celluzyme and/or Endolase by Novo Nordisk AIS:
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CMC . Sodium carboxymethyl cellulose.
HEDP . 1,1-hydroxyethane diphosphonic acid.
DETPMP , Diethylene triamine penta (methylene phosphoric acid),
marketed by Monsanto under the Trade name bequest 2060.
PVNO : Poly(4-vinylpyridine)-N-Oxide.
PVPVI . Poly (4-vinylpyridine)-N-oxide/copolymer of vinyl-imidazole
and vinyl-pyrrolidone.
Brightener 1 . Disodium 4,4'-bis(2-sulphostyryl)biphenyl.
Brightener 2 . Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)
stilbene-2:2'-disulfonate.
Silicone antifoam : Polydimethylsiloxane foam controller with siloxane-
oxyalkylene copolymer as dispersing agent with a ratio of said
foam controller to said dispersing agent of 10:1 to 100:1.
Granular Suds . 12% Silicone/silica, 18% stearyl alcoho1,70% starch in
Suppressor granular form
SRP 1 . Sulfobenzoyl or sodium isethionate end capped esters with
oxyethylene oxy and terephtaloyl backbone.
SRP 2 : Diethoxylated poly (1,2 propylene terephtalate) short block
polymer.
Sulphate : Anhydrous sodium sulphate.
HMWPEO : High molecular weight polyethylene oxide
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Encapsulated perfume . Insoluble fragrance delivery technology utilising
zeolite 13x,
particles perfume and a dextrose/glycerin agglomerating binder.
Example 1
The following laundry detergent compositions were prepared in accordance with
the
invention:
I II III IV V VI
LAS 8.0 8.0 8.0 8.0 8.0 8.0
C25E3 3.4 3.4 3.4 3.4 3.4 3.4
QAS - 0.8 0.8 - 0.8 0.8
Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1
Carbonate 13.0 13.0 13.0 27.0 27.0 27.0
Silicate 1.4 1.4 1.4 3.0 3.0 3.0
Sulfate 26.1 26.1 26.1 26.1 16.1 16.1
PB4 9.0 9.0 9.0 9.0 9.0 9.0
TAED 1.5 1.5 1.5 1.5 1.5 1.5
DETPMP 0.25 0.25 0.25 0.25 0.25 0.25
HEDP 0.3 0.3 0.3 0.3 0.3 0.3
Transferase 1.0 0.1 0.05 0.02 0.1 0.5
Substrate 0.1 - 5.0 - 10.0 15.0
Protease 0.00260.0026 0.0026 0.0026 0.0026 0.0026
~Yl~ ~ - 0.0009 0.0009 0.0009 0.0009 0.0009
AA 0.3 0.3 0.3 0.3 0.3 0.3
CMC 0.2 0.2 0.2 0.2 0.2 0.2
I II III IV V VI
Photoactivated bleach15 15 15 15 15 15
(ppm)
Brightener 1 0.09 0.09 0.09 0.09 0.09 0.09
Perfume 0.3 0.3 0.3 0.3 0.3 0.3
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Silicone antifoam 0.5 0.5 0.5 0.5 0.5 0.5
Misc/minors to 100%
Density in g/litre 850 850 850 850 850 850
Example 2
The following granular laundry detergent compositions of bulk density 750
g/litre were
prepared in accord with the invention:
I II III IV V
LAS 5.25 5.25 5.6 4.8 4.8
TAS 1.25 1.25 1.9 1.6 1.6
C45AS - - 2.2 3.9 3.9
C25AE3S - - 0.8 1.2 1.2
C45E7 3.25 3.25 - 5.0 5.0
C25E3 - - 5.5 - _
QAS 0.8 0.8 2.0 2.0 2.0
STPP 19.7 19.7 - - -
Zeolite A - - 19.5 19.5 19.5
NaSKS-6/citric acid - - 10.6 10.6 10.6
(79:21 )
Carbonate 6.1 6.1 21.4 21.4 21.4
Bicarbonate - - 2.0 2.0 2.0
Silicate 6.8 6.8 - _ _
Sodium sulfate 39.8 39.8 - 4.3 4.3
PB4 5.0 5.0 12.7 - -
TAED 0.5 0.5 3.1 - -
DETPMP 0.25 0.25 0.2 0.2 0.2
HEDP - - 0.3 0.3 0.3
Transferase 0.02 1.5 0.1 0.5 0.0008
Substrate - 0.1 5.0 10.0 12.0
Protease 0.0026 0.0026 0.0085 0.045 0.045
I II III IV V
Lipase 0.003 0.003 0.003 0.003 0.003
Cellulase 0.0006 0.0006 0.0006 0.0006 0.0006
~Yl~e 0.0009 0.0009 0.0009 0.0009 0.0009
0.8 0.8 1.6 1.6 1.6
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CMC 0.2 0.2 0.4 0.4 0.4
Photoactivated bleach15 ppm 15 ppm 27 ppm 27 ppm 27
(ppm) ppm
Brightener 1 0.08 0.08 0.19 0.19 0.19
Brightener 2 - - 0.04 0.04 0.04
Encapsulated perfume0.3 0.3 0:3 0.3 0.3
particles
Silicone antifoam 0.5 0.5 2.4 2.4 2.4
Minors/misc to 100%
Example 3
The following detergent formulations, according to the present invention were
prepared,
where I is a phosphorus-containing detergent composition, II is a zeolite-
containing
detergent composition and III is a compact detergent composition:
I II III IV V
Blown Powder
STPP 24.0 24.0 - 24.0 24.0
Zeolite A - - 24.0 - _
C45AS 9.0 9.0 6.0 13.0 13.0
2.0 2.0 4.0 2.0 2.0
LAS 6.0 6.0 8.0 11.0 11.0
TAS 2.0 2.0 - - _
Silicate 7.0 7.0 3.0 3.0 3.0
CMC I.0 1.0 1.0 0.5 0.5
Brightener 2 0.2 0.2 0.2 0.2 0.2
Soap 1.0 1.0 1.0 1.0 1.0
DETPMP 0.4 0.4 0.4 0.2 0.2
Spray On
C45E7 2.5 2.5 2.5 2.0 2.0
C25E3 2.5 2.5 2.5 2.0 2.0
Silicone antifoam0.3 0.3 0.3 0.3 0.3
Perfume 0.3 0.3 0.3 0.3 0.3
Dry additives
I II III IV V
Carbonate 6.0 6.0 13.0 15.0 15.0
PB4 18.0 18.0 18.0 10.0 10.0
PB1 4.0 4.0 4.0 0 0
TAED 3.0 3.0 3.0 1.0 1.0
Photoactivated 0.02 0.02 0.02 0.02 0.02
bleach
Transferase 0.005 1.0 0.1 0.2 0.0004
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Substrate - 0.1 10.0 10.0 S.0
Protease 0.01 0.01 0.01 0.01 0
01
Lipase 0.009 0.009 0.009 0.009 .
0.009
~Yl~e 0.002 0.002 0.003 0.001 0.001
Dry mixed sodium 3.0 3.0 3.0 5.0 S.0
sulfate
Balance (Moisture 100.0 100.0 100.0 100.0 100.0
&
Miscellaneous)
Density (g/litre) 630 630 670 670 670
Example 4
The following nil bleach-containing detergent formulations of particular use
in the
washing of colored clothing, according to the present invention were prepared:
I II III IV
Blown Powder
Zeolite A 15.0 15.0 15.0 -
Sodium sulfate 0.0 0.0 5.0 -
LAS 3.0 3.0 3.0 -
DETPMP 0.4 0.4 0.5 -
CMC 0.4 0.4 0.4
MA/AA 4.0 4.0 4.0 -
Agglomerates
C45AS - - - 11.0
LAS 6.0 6.0 5.0 -
TAS 3.0 3.0 2.0 -
Silicate 4.0 4.0 4.0 -
Zeolite A 10.0 10.0 15.0 13.0
CMC - - - 0.5
MA/AA - - - 2.0
Carbonate 9.0 9.0 7.0 7.0
Spray On
Perfume 0.3 0.3 0.3 0.5
C45E7 4.0 4.0 4.0 4.0
I II III IV
C25E3 2.0 2.0 2.0 2.0
Dry additives
- - - 3.0
NaSKS-6 - - - 12.0
Citrate 10.0 10.0 - g.p
Bicarbonate 7.0 7.0 3.0 5.0
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Carbonate 8.0 8.0 5.0 7.0
PVPVI/PVNO 0.5 0.5 0.5 0.5
Transferase 0.025 0.8 0.5 0.01
Substrate - 0.1 10.0 5.0
Protease 0.026 0.026 0.016 0.047
Lipase 0.009 0.009 0.009 0.009
Amylase 0.005 0.005 0.005 0.005
Cellulase 0.006 0.006 0.006 0.006
Silicone antifoam 5.0 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 0.0 9.0 0.0
Balance (Moisture 100.0 100.0 100.0 100.0
and
Miscellaneous)
Density (g/litre) 700 700 700 700
Example 5
The following
detergent
formulations,
according
to the present
invention
were prepared:
I II III IV V
LAS 20.0 20.0 14.0 24.0 22.0
QAS 0.7 0.7 1.0 - 0.7
TFAA - - 1.0 - _
C25E5/C45E7 - - 2.0 - 0.5
C45E3S - - 2.5 - -
STPP 30.0 30.0 18.0 30.0 22.0
Silicate 9.0 9.0 S.0 10.0 8.0
Carbonate 13.0 13.0 7.5 - 5.0
Bicarbonate - _ 7.5 _ -
DETPMP 0.7 0.7 1.0 - -
SRP 1 0.3 0.3 0.2 - 0.1
I II III IV V
MA/AA 2.0 2.0 1.5 2.0 1.0
CMC 0.8 0.8 0.4 0.4 0.2
Transferase 0.001 1.0 0.01 0.5 0.01
Substrate 0.1 - S.0 20.0 -
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Protease 0.008 0.008 0.01 0.026 0.026
Amylase 0.007 0.007 0.004 - 0.002
Lipase 0.004 0.004 0.002 0.004 0.002
Cellulase 0.0015 0.0015 0.0005 - _
Photoactivated70ppm 70ppm 45ppm - lOppm
bleach (ppm)
Brightener 0.2 0.2 0.2 0.08 0.2
1
PB1 6.0 6.0 2.0 - _
NOBS 2.0 2.0 1.0 - _
Balance (Moisture100 100 100 100 100
and Miscellaneous)
Example 6
The following detergent formulations, according to the present invention were
prepared:
I II III IV
Blown Powder
Zeolite A 30.0 22.0 6.0 6.7
Na SkS-6 - - - 3.3
Polycarboxylate _ _ - 7.1
Sodium sulfate 19.0 5.0 7.0 -
M~~ 3.0 3.0 6.0 -
LAS 14.0 12.0 22.0 21.5
C45AS 8.0 7.0 7.0 5.5
Cationic _ _
- 1.0
Silicate - 1.0 5.0 I1.4
I II III IV
Soap - - 2.0 -
Brightener 1 0.2 0.2 0.2 -
Carbonate 8.0 16.0 20.0 10.0
DETPMP - 0.4 0.4 -
Spray On
C45E7 1.0 1.0 1.0 3.2
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Dry additives
PVPVI/PVNO 0.5 0.5 0.5 -
Transferase 1.0 0.01 0.5 0.1
Substrate 0.1 - 10.0 10.0
Protease 0.052 0.01 0.01 0.01
Lipase 0.009 0.009 0.009 0.009
Amylase 0.001 0.001 0.001 0.001
Cellulase 0.0002 0.0002 0.0002 0.0002
NOBS - 6.1 4.5 3.2
PB 1 1.0 5.0 6.0 3.9
Sodium sulfate - 6.0 - to balance
Balance (Moisture 100 100 100
and
Miscellaneous)
Example 7
The following high and bleach-containing
density detergent
formulations,
according
to
the present invention
were prepared:
I II III IV
Blown Powder
Zeolite A 15.0 15.0 1 S.0 15.0
Sodium sulfate 0.0 0.0 5.0 0.0
LAS 3.0 3.0 3.0 3.0
QAS - - 1.5 1.5
I II III IV
DETPMP 0.4 0.4 0.4 0.4
CMC 0.4 0.4 0.4 0.4
MA/AA 4.0 4.0 2.0 2.0
Agglomerates
LAS 5.0 S.0 5.0 5.0
TAS 2.0 2.0 2.0 1.0
Silicate 3.0 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0 8.0
Carbonate 8.0 8.0 8.0 4.0
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Spray On
Perfume 0.3 0.3 0.3 0
3
C4SE7 2.0 2.0 2.0 .
2
0
C2SE3 2.0 2.0 _ .
_
Dry additives
Citrate S.0 S.0 - I2
0
Bicarbonate _ - 3.0 .
_
Carbonate 8.0 8.0 1 S.0 10
0
TAED 6.0 6.0 2.0 .
S.0
PB1 14.0 14.0 7.0 10.0
Polyethylene oxide -
of MW
- - 0.2
5,000,000
Bentonite clay - -
- 10.0
Transferase 0.001 1.0 0.01 O.S
Substrate - - S.0 10.0
Protease 0.01 0.01 0.01 0.01
Lipase 0.009 0.009 0.009 0.009
Amylase O.OOS O.OOS O.OOS O.OOS
Cellulase 0.002 0.002 0.002 0.002
Silicone antifoam S.0 S.0 S.0 S.0
Dry additives
Sodium sulfate 0.0 0.0 3.0 0.0
Balance {Moisture 100.0 100.0 100.0 100.0
and
Miscellaneous)
Density (g/litre) 8S0 8S0 8S0 8S0
Example 8
The following high density detergent formulations, according to the present
invention
were prepared:
I I II II
Agglomerate
C4SAS 11.0 11.0 14.0 14.0
Zeolite A 1 S.0 1 S.0 6.0 6.0
Carbonate 4.0 4.0 8.0 8.0
4.0 4.0 2.0 2.0
CMC O.S O.S O.S O.S
DETPMP 0.4 0.4 0.4 0.4
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Spray On
C25E5 5.0 5.0 5.0 5.0
Perfume 0.5 0.5 0.5 0.5
Dry Adds
HEDP 0.5 0.5 0.3 0.3
SKS 6 13.0 13.0 10.0 10.0
Citrate 3.0 3.0 1.0 1.0
TAED 5.0 5.0 7.0 7.0
Percarbonate 20.0 20.0 20.0 20.0
SRP 1 0.3 0.3 0.3 0.3
Transferase 0.025 0.5 0.1 0.01
Substrate 0.01 - 12.0 5.0
Protease 0.014 0.014 0.014 0.014
Lipase 0.009 0.009 0.009 0.009
Cellulase 0.001 0.001 0.001 0.001
Amylase 0.005 0.005 0.005 0.005
Silicone antifoam 5.0 5.0 5.0 5.0
Brightener 1 0.2 0.2 0.2 0.2
Brightener 2 0.2 0.2 - _
Balance (Moisture 100 100 100 100
and
Miscellaneous)
Density (g/litre) 850 850 850 850
Example 9
The following granular the presentvention
detergent formulations, in were
according to
prepared:
I II III IV V
LAS 21.0 25.0 18.0 18.0 -
Coco C12-14 AS - - - - 21.9
AE3S - - 1.5 1.5 2.3
Decyl dimethyl hydroxyethyl - 0.4 0.7 0.7 0.8
NH4+Cl
Nonionic 1.2 - 0.9 0.5 -
Coco C12-14 Fatty - - - - 1.0
Alcohol
STPP 44.0 25.0 22.5 22.5 22.5
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Zeolite A 7.0 10.0 - _ g,0
M~~' - - 0.9 0.9 -
SRP 1 0.3 0.15 0.2 0.1 0.2
CMC 0.3 2.0 0.75 0.4 1.0
Carbonate 17.5 29.3 5.0 I3.0 15.0
Silicate 2.0 - 7.6 7.9 -
Transferase 0.001 0.5 0.01 0.5 0.05
Substrate - 0.05 5.0 10.0 -
Protease 0.007 0.007 0.007 0.007 0.007
Amylase - 0.004 0.004 0.004 0.004
Lipase 0.003 0.003 0.003 - _
Cellulase - 0.001 0.001 0.001 0.001
NOBS - - - 1.2 1.0
PB I - - - 2.4 I .2
Diethylene triamine - - - 0.7 1.0
penta acetic
acid
Diethylene triamine - - 0.6 -
penta
methyl phosphonic acid
Mg Sulfate _ _
0.8 _
Photoactivated bleach 45 50 ppm 15 ppm 45 ppm 42
ppm ppm
Brightener 1 0.05 - 0.04 0.04 0.04
Brightener 2 0.1 0.3 0.05 0.13 0.13
Water and Minors up to
100%
Example 10
The following liquid detergent formulations, according to the present
invention were
prepared:
I II III IV V VI VII VIII
LAS 10.0 13.0 9.0 - 25.0 - -
C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 I5.0
I II III IV V VI VII VIII
C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0
C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0
TFAA - - - 4.5 - 6.0 8.0 8.0
QAS - - - - 3.0 1.0 - -
TPKFA 2.0 - 13.0 2.0 - 15.0 7.0 7.0
Rapeseed - - - 5.0 - - 4.0 4.0
fatty
acids
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Citric 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1
0
Dodecenyl/ 12.0 10.0 - - 15.0 - _ .
_
tetradecenyl
succinic acid
Oleic acid 4.0 2.0 1.0 - 1.0 - - _
Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0
1,2 Propanediol4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.-
Mono Ethanol - - - 5.0 - - 9.0 9.0
Amine
Tri Ethanol - - g _ _ - _ -
Amine
NaOH (pH) 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2
Ethoxylated 0.5 - 0.5 0.2 - - 0.4 0.3
tetraethylene
pentamine
DETPMP 1.0 i .0 0.5 1.0 2.0 1.2 1.0 -
SRP2 0.3 - 0.3 0.1 - - 0.2 0.1
PVNO _ _ _ _ _ _ _ 0.10
Transferase .001 0.01 1.0 0.05 0.5 0.01 0.01 0.01
Substrate 0.1 - 0.01 - 10.0 5.0 - S.0
Protease .005 .005 .004 .003 0.08 .005 .003 .006
Lipase - .002 - .0002 - - .003 .003
Amylase .002 .002 .005 .004 .002 .008 .005 .005
Cellulase - - - .0001 - - .0004 .0004
Boric acid 0.1 0.2 - 2.0 1.0 1.5 2.5 2.5
Na formate - - 1.0 - - _ _ -
Ca chloride - 0.015 - 0.01 - - _ _
Bentonite clay - - - - 4.0 4.0 -
Suspending clay- - - - 0.6 0.3 - -
SD3
Balance Moisture100 100 100 100 100 100 100 100
and Miscellaneous
Example 11
Granular fabric softening the
detergent compositions through wash"
which provide
"
capability were
prepared in
accord with
the present
invention
I II III IV
45AS - - 10.0 10.0
LAS 7.6 7.6 -
68AS 1.3 1.3 - -
45E7 4.0 4.0 -
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25E3 - - S.0 5.0
Coco-alkyl-dimethyl hydroxy-1.4 1.4 1.0 1.0
ethyl ammonium chloride
Citrate 5.0 5.0 3.0 3.0
Na-SKS-6 - - 11.0 11.0
Zeolite A 15.0 15.0 15.0 15.0
M~~ 4.0 4.0 4.0 4.0
DETPMP 0.4 0.4 0.4 0.4
PB 1 15.0 15.0 - _
Percarbonate - - 15.0 15.0
TAED 5.0 5.0 5.0 5.0
Smectite clay 10.0 10.0 5.0 5.0
HMWPEO - - 0.1 0.1
Transferase 0.001 0.01 0.8 0.0005
Substrate - 5.0 - S.0
Protease 0.02 0.02 0.01 0.01
Lipase 0.02 0.02 0.01 0.01
Amylase 0.03 0.03 0.005 0.005
Cellulase 0.001 0.001 -
Silicate 3.0 3.0 5.0 5.0
Carbonate 10.0 10.0 10.0 10.0
Granular suds suppressor1.0 1.0 4.0 4.0
CMC 0.2 0.2 0.1 0.1
Water/minors Up to
100%
Example 12
The following pre- or post treatment compositions were prepared in accord with
the
present invention
I II III IV
DEQA (2) - - 20.0 20.0
Transferase 0.8 0.05 0.05 0.15
Substrate - 10.0 10.0 5.0
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Cellulase - - 0.001 0.001
HCL - - 0.03 0.03
Antifoam agent - - 0.01 0.01
Blue dye 25ppm 25ppm 25ppm 25ppm
CaCl2 - - 0.20 0.20
Preservatives 0.05 0.05 0.05 0.05
Perfume 0.90 0.90 0.90 0.90
Water / minors Up to 100%
Example 13
The following fabric softener composition was prepared in accord with the
present
invention
I II III IV
DEQA 2.6 2.6 19.0 19.0
Stearic acid of 0.3 0.3 - _
IV=0
Hydrochloride 0.02 0.02 0.02 0.02
acid
Transferase 0.001 0.5 0.01 0.1
Substrate - 0.1 5.0 5.0
Perfume 1.0 1.0 1.0 1.0
Silicone antifoam0.01 0.01 0.01 0.01
Electrolyte - - 1000ppm 1000ppm
Dye lOppm lOppm 25ppm 25ppm
Preservative 0.05 0.05 0.05 0.05
Water and minors 100% 100% 100% 100%
Example 14
Dryer activated
color care compositions
and dryer added
fabric conditioner
compositions
were prepared
in accord with
the present invention
I II III IV V VI
DEQA ( 1 ) 39 - - 39.2 - -
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DEQA (2) - 50 - - 51.8 -
DTDMAMS - - 26 - - -
SDASA 54 27 42 54.4 40.2 70.0
Transferase 0.1 1.0 0.01 0.15 0.1 0.5
Substrate 0.1 0.1 - - 10.0 10.0
Neodo145-13 - - - - - 13.0
Ethanol - - - - - 1.0
Glycoperse S-20 - 15 - - 15.4 -
Glycerol monostearate- - 26 - - _
Perfume 2 2 1 1.6 1.5 0.75
Clay 3 3 3 - - -
Example 1 S
Spray-on compositions
were prepared
in accord with
the present invention
I II III IV
Substrate 10.0 10.0 1.0 0.1
Transferase 0.001 0.001 0.01 0.1
Polymer (e.g. - - 0.1 -
Starch)
AcOH 0.032 0.032 0.032 0.032
NaOAc 0.031 0.031 0.031 0.031
Antifoam agent 0.01 0.01 0.01 0.01
Perfume 0.01 0.01 0.01 0.01
Water/Minors Up to 100%
Examgle 16
Syndet bar fabric detergent compositions were prepared in accord with the
present
invention
I II III IV
C26 AS 20.00 20.00 20.00 20.00
CFAA 5.0 5.0 5.0 5.0
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LAS (CI 1-13) 10.0 10.0 10.0 10.0
Sodium carbonate 25.0 25.0 25.0 25.0
Sodium pyrophosphate ?.0 7.0 7.0 7.0
STPP 7.0 7.0 7.0 7.0
Zeolite A S.0 S.0 5.0 5.0
CMC 0.2 0.2 0.2 0.2
Polyacrylate (MW 1400)0.2 0.2 0.2 0.2
Coconut monethanolamide5.0 5.0 5.0 5.0
Transferase 0.001 0.05 0.5 0.01
Substrate 0.1 5.0 8.0 5.0
Amylase 0.01 0.02 0.01 0.01
Protease 0.3 - 0.5 0.05
Brightener, perfume 0.2 0.2 0.2 0.2
CaS04 1.0 1.0 1.0 1.0
MgS04 1.0 1.0 1.0 1.0
Water 4.0 4.0 4.0 4.0
Filler* : balance to
100%
*Can be selected from convenient materials such as CaC03, talc, clay
(KaoIinite,
Smectite), silicates, and the like.
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.
