Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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ALKOXYLATED, QUATERNIZED
DIAMINE DETERGENT INGREDIENTS
TECHNICAL FIELD
The present invention relates to detergent compositions which comprise
selected
ingredients, including selected quaternized ethoxylated, alkylene diiamine
compounds.
BACKGROUND OF THE INVENTION
The formulation of laundry detergents and other cleaning compositions presents
a
considerable challenge, since modern compositions are required to remove a
variety of
soils and stains from diverse substrates. Thus, laundry detergents, hard
surface cleaners,
shampoos and other personal cleansing compositions, hand dishwashing
detergents and
detergent compositions suitable for use in automatic dishwashers, and the
like, all require
the proper selection and combination of ingredients in order to function
effectively. In
general, such detergent compositions will contain one or more types of
surfactants which
are designed to loosen and remove certain soils and stains. However, while
some
detergent adjuncts and surfactants exhibit optimal performance on certain
types of soils
and stains, they can actually diminish performance on other soils. For
example,
surfactants which remove greasy/oily soils from fabrics can sometimes be sub-
optimal
for removing particulate soils. Moreover, the soils once removed from the
substrate
should be dispersed or suspended in the wash liquor to minimize redeposition
on the
substrate.
Thus, the efficient removal of particulate soils and the suspension of such
soils
can be problematic. Perhaps the most important particulate soils which pose
these
problems are the clay-type soils. Clay soil particles generally comprise
negatively
charged layers of aluminosilicates and positively charged cations (e.g.
calcium) which
are positioned between and hold together the negatively charged layers.
A variety of models can be proposed for compounds which would have clay soil
removal properties. One model requires that the compound have two distinct
characteristics. The first is the ability of the compound to adsorb onto the
negatively
charged layers of the clay particle. The second is the ability of the
compound, once
adsorbed, to push apart (swell) the negatively charged layers so that the clay
particle
loses its cohesive force and can be removed in the wash water.
In addition to clay soil removal, there is a need to keep the removed soil in
suspension during the laundering cycle. Soil which is removed from the fabric
and
suspended in the wash water can redeposit on the surface of the fabric. This
redeposited
soil causes a dulling or "greying" effect which is especially noticeable on
white fabrics.
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To minimise this problem, anti-redeposition agents can be included in the
detergent
composition. For example EP-B-111 965 disclose the use in detergents of
cationic
compounds, which have both clay-soil removal and anti-redeposition properties.
Without being limited by theory, a model proposed for the anti-redeposition
action of the positively charged anti-redeposition compounds is as follows.
Adsorption
of the positively charged molecule on the surface of clay particles in the
wash water
gives the particles the dispersancy properties of the molecule. As more and
more of
these compounds adsorb onto the suspended clay soil particles, the latter
become encased
within a hydrophilic layer. As such, the hydrophilically encased soil is
prevented from
redepositing on fabrics, in particular hydrophobic fabrics such as polyester,
during the
laundering cycle.
A considerable amount of research has been undertaken to find compounds which
will effectively remove soils and prevent their redeposition. Thus, while a
review of the
literature would seem to indicate that a wide selection of surfactants and
other
components is available to the detergent manufacturer, the reality is that
many such
ingredients are specialty chemicals which are not suitable in low unit cost
items such as
home-use laundry detergents. Presumably due to economic considerations, the
fact
remains that most such home-use products such as laundry detergents still
mainly
comprise one or more of the conventional surfactants along with builders and
conventional adjuncts. The need remains to formulate compositions with
additional
adjuncts which function reasonably well with a variety of soils and stains and
a variety of
fabrics.
Accordingly, there is a continuing search for improvements in detergents,
especially laundry and dishwashing detergents and hard surface cleaners.
However, the
challenge to the detergent manufacturer seeking improved performance has been
increased by various factors. For example, some non-biodegradable ingredients
have
fallen into disfavor. Effective phosphate builders have been banned by
legislation in
many countries. Costs associated with certain classes of compounds have
impacted their
use. As a result, the manufacturer is somewhat more limited than the
literature would
suggest in the selection of effective, yet affordable, ingredients. Still, the
consumer has
come to expect high quality and high performance in such compositions even
when
conducting cleaning operations under sub-optimal conditions, e.g., laundering
fabrics in
cool or cold water.
The literature does suggest that various nitrogen-containing compounds would
be
useful in a variety of cleaning compositions. Such materials, typically in the
form of
amino-, amido-, or quaternary ammonium or imidazolinium compounds, are often
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designed for specialty use. For example, various amino and quaternary ammonium
surfactants have been suggested for use in shampoo compositions and are said
to provide
cosmetic benefits to hair. Other nitrogen-containing surfactants are used in
some laundry
detergents to provide a fabric softening and anti-static benefit. For the most
part,
however, the commercial use of such materials is rather limited.
It has now been discovered that certain alkoxylated quaternary diamine (AQD)
compounds can be used in various detergent compositions to boost performance,
especially on particulate soils and for suspension of soils in the wash
liquor.
Importantly, it has further been discovered that low levels of these AQD
compounds
provide superior cleaning performance when used in certain combinations with
otherwise
known or conventional ingredients. Thus, the present invention provides an
improvement in cleaning performance without the need to develop new, expensive
surfactant species.
Moreover, the AQD soil removal/dispersants used in the present manner provide
substantial advantages to the formulator over other dispersants known
heretofore. For
example, the AQD dispersants herein are compatible with the preferred alkyl
sulfate,
alkyl ethoxylated sulfate, and amidopropylamine detersive surfactants.
Moreover, the
AQD dispersants are formulatable over a broad pH range from 5 to 12. The AQD
dispersants are also compatible with various perfume ingredients, unlike other
quats
known in the art.
In addition to the foregoing advantages, the AQD dispersants herein appear to
minimize or eliminate redeposition of fatty acids/oily materials present in an
aqueous
laundry liquor back onto fabrics which have been previously soiled with body
soils.
Accordingly, the AQD dispersants herein have now been found to prevent the
redeposition of polar lipids from an aqueous laundry bath back onto fabrics
from whence
body soils have been removed through the laundering process. Stated otherwise,
in a
laundering liquor, the AQD dispersants herein remove such polar lipids and
keep them
suspended in the aqueous medium, rather than allowing them to redeposit onto
the
cleaned fabrics.
In addition to the foregoing qualities, the AQD dispersants herein are
surprisingly
compatible with the polyanionac materials such as polyacrylates and
acrylate/maleate
copolymers which are used to provide a builder and/or dispersant function with
many
conventional detersive surfactants. Moreover, it has surprisingly been found
that the
combination of the AQD dispersants herein with specific ethoxylated
polyethyleneimines
with a MW of less than about 5,000 provide synergistic cleaning benefits.
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Other advantages for the AQD dispersant herein include their ability to
enhance
enzymatic cleaning and fabric care performance in a laundering liquor. While
not
intending to be limited by theory, it is speculated that enzymes may be
partially
denatured by conventional anionic surfactants. It is further speculated that
the AQD
dispersants herein somehow interact with the anionic surfactants to inhibit
that
degradation. An alternate theory would suggest that, even when enzymes are
used to
degrade soils and stains, the degraded residues must be removed from the
fabric surface.
It may be speculated that the improved suspension of soil performance embodied
in the
AQD dispersants herein simply does a better job in removing these residues
from the
wash liquor and fabric surface.
In addition to the foregoing advantages, the AQD dispersants herein provide
substantial cleaning enhancement with respect to clay soil removal from
fabrics, as
compared with conventional detergent mixtures. Again, while not intending to
be
limited by theory, it may be speculated that conventional cationic surfactants
associate
with the clay in "close-packed" fashion and render the clay more difficult to
remove. In
contrast, the alkoxylated AQD dispersants are believed to provide more open
associations with clays, which are then more readily removed from fabric
surfaces.
Whatever the reason, the compositions herein containing the AQD dispersants
provide
improved performance over conventional dispersants with special regard to clay
soil
removal.
Still further advantages for the AQD dispersants herein have been discovered.
For example, in bleaching compositions which comprise a bleach activator (as
disclosed
herein) it appears that some sort of ion pair or other associative complex is
formed with
the per-acid released from the activator. It may be speculated that this ion
pair is carried
more efficiently into the soil as a new, more hydrophobic agent, thereby
enhancing
bleach performance associated with the use of bleach activators such as
nonanoyloxy
benzene sulfonate {HOBS), tetraacetylethylenediamine (TAED), and peracids.
Quite
low levels of AQD dispersants gives rise to these results.
Moreover, in compositions without bleach, the formulator my choose to use
somewhat higher levels of AQD dispersants to provide enhanced performance
benefits.
These benefits may be associated with the ability of the AQD dispersants
herein to
modify the solution characteristics of conventional anionic surfactants such
as alkyl
sulfates or alkyl ethoxylated sulfates to allow more of the surfactants to be
available to
perform their cleaning function. This is particularly true in situations faced
by the
formulator where the detergent composition is "underbuilt" with respect to
calcium
and/or magnesium water hardness ions
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Mixtures of AQD dispersants can be blended and used to provide a broad
spectrum of cleaning performance over a wide variety of soils and stains and
under a
wide range of usage conditions. Representative, but non-limiting, examples of
such
combinations of AQD dispersants are disclosed in the Examples hereinafter.
Various other advantages of the AQD dispersants over other dispersants known
in the art are described in more detail hereinafter. As will be seen from the
disclosures
herein, the AQD dispersants, used in the manner of the present invention,
successfully
address many of the problems associated with the formulation of modern, high-
performance detergent compositions. In particular, these dispersants allow the
formulation of effective laundry compositions which can be used to remove a
wide
variety of soils and stains under a wide spectrum of usage conditions.
These and other advantages of the present invention will be seen from the
following disclosures.
BACKGROUND ART
US 4,659,802 and US 4,664,848 describe cationic (quaternized) amine
compounds which have clay-soil removal and anti-redeposition properties.
SUMMARY OF THE INVENTION
The present invention relates to cleaning compositions comprising or prepared
by
combining an effective amount of certain alkoxylated (especially ethoxylated)
quaternary
polyamine dispersants and one or more detersive (including fabric care)
adjuncts, as
disclosed hereinafter, The alkoxylated quaternary diamine (AQD) dispersants
used in
the present invention are of the general formula:
A A
Rt-N~ R-N~ Rt 2X~
I
A A
where R is selected from linear or branched C~-C 12 alkylene, C3-C 12
hydroxyalkylene,
C4-C ~ 2 dihydroxyalkyiene, Cg-C 12 dialkylarylene, [(CH2CH20)qCH2CH2]- and -
CH2CH(OH)CH20-(CH2CH20)qCH2CH(OH)CH2]- where q is from about 1 to about
l00. Each R1 is independently selected from C 1-C4 alkyl, C~-C 12 alkylaryl,
or A. A is
of the formula:
(CH-CH2-O)nB
R3
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where R3 is selected from H or C 1-C3 alkyl, n is from about 5 to about 100
and B is
selected from H, C 1-C4 alkyl, acetyl, or benzoyl; X is a water soluble anion
In preferred embodiments, R is selected from C4 to Cg alkylene, Rl is selected
from Cl-C2 alkyl or C2-C3 hydroxyalkyl, and A is:
(CH-CH2-O)nH
R3
where R3 is selected from H or methyl, and n is from about I 0 to about 50.
In another preferred embodiment R is linear or branched C6, R 1 is methyl, R3
is
H, and n is from about 20 to about 50.
AQD's can be synthesized following the methods outline in US. Patent No.
4,664,848, or other ways known to those skilled in the art.
The levels of the AQD dispersants used to prepare finished laundry detergent
compositions can range from about 0.1 % to about 10%, typically from about
0.4% to
about 5%, by weight.
The present invention encompasses the use of the aforesaid AQD dispersants to
enhance the overall cleaning performance of detergent compositions which
contain
otherwise known ingredients. It has now been discovered that the overall
cleaning
performance of such detergent compositions can be improved by the
incorporation of
relatively small quantities of the AQD dispersants. Surprisingly, laundry
cleaning
performance with respect not only to greasy soils, but also body soil, builder
sensitive
soil, bleach sensitive soil, as well as food stains and sock soil is enhanced.
Of course, the
usage levels and mode of use of the AQD dispersants in detergent formulations
of
various types will depend on the desires of the formulator. Representative,
but non-
limiting, examples of such formulations include the following.
Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and a specific surfactants, including alkyl sulfate (AS) and
alkyl
alkoxylated, especially ethoxylated, sulfates (AES). In other preferred
embodiments, the
compositions with AQD dispersants and these surfactants are substantially free
of (i.e.,
have less than 5%, preferably less than 1 %) of linear alkyl benzene sulfonate
(LAS). In
yet other embodiment, in nonaqueous liquid detergent compositions, the AQD is
combined with linear alkyl benzene sulfonate.
Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and selected amine surfactants, such as
amidopropyldimethylamines.
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Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and a polyester or oligoester soil release agent, especially a
non-cotton
soil release polymer or agent.
Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and a polyethoxyated polyethyleneamine polymers or ethoxylated
polyethyleneimine (PEI) polymers with a molecular weight of less than about
5,000,
preferably less than about 2,000, more preferably from about 600 to about
1,000.
Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and an amylase or lipase enzyme, or mixtures thereof.
In yet other embodiments, examples of such formulations include the following:
Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and chelants, especially ethylenediaminedisuccinate {EDDS)
chelant.
Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and a cellulase or protease enzyme, or mixtures thereof.
Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and an alkyl polyglycoside or polyhydroxy fatty acid amide
surfactant.
Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and a non-aqueous liquid carrier matrix.
Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and a detergent granule having a bulk density of 650 g/L, or
greater.
Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and a source of magnesium ions, calcium ions, or mixtures
thereof.
Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and a dye-transfer inhibitor.
Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and a manganese, cobalt or iron bleach catalyst.
Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and a zeolite P or "MAP" builder.
Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and a Mineral Builder.
Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and an oxygen bleach such as percarbonate bleach.
Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and one or more bleach activators.
Detergent compositions which comprise conventional detersive ingredients, an
AQD dispersant and a photobleach.
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The AQD dispersants used in the manner of the present invention also provide
an
improved method for removing and suspending the following soils and stains
from
fabrics: greasy food stain; particulate stain; body soils (including fabric
"dinginess"
caused by small, but noticeable, stain/soil accumulations over time) and other
stains
noted herein. Such stains and soils are removed from fabrics such as cotton,
polyester/cotton blends (P/C) and double-knit polyester (DKPE). The method
comprises
contacting fabrics in need of removal of such soils with an effective amount
of the
compositions herein, in the presence of water, and preferably with agitation.
Various
suitable usage levels and methods are disclosed hereinafter.
With special regard to a fabric laundering context, the AQD compounds herein
have the advantage that they are commercially available and are compatible
with the
various detersive ingredients such as builders, detersive enzymes, and the
like, which are
used in many modern, high quality, fully-formulated laundry detergents.
Moreover, the
AQD compounds exhibit satisfactory stability in the presence of the bleach
ingredients
commonly used in laundry detergent-plus-bleach compositions. Importantly, the
AQD
dispersants herein exhibit superior performance with respect to the removal of
body soils
and everyday soils such as sock soil. In short, the compositions herein
provide improved
performance for cleaning a broad spectrum of soils and stains including body
soils from
collars and cuffs, greasy soils, and enzyme/bleach sensitive stains such as
spinach and
coffee. The compositions herein also provide excellent cleaning on builder
sensitive
stains such as clay, and thus are especially useful in a nil-P context.
Moreover, the AQD dispersants herein provide improved fabric cleaning
performance in the presence of bleach. This improvement in cleaning is seen at
usage
levels as low as 3 parts per million (ppm) of the AQD in the laundry liquor
and is
believed to be associated with increased perhydrolysis.
In addition, the AQD dispersants herein provide improved (even synergistic)
performance with amylase, especially Duramyl~, and lipase, especially Lipolase
Ultra~,
enzymes. This improvement is seen especially in the absence of bleach.
All percentages, ratios and proportions herein are by weight of ingredients
used
to prepare the finished compositions unless otherwise specified. A11 documents
cited
herein are, in relevant part, incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
In one of its several aspects, this invention provides a means for enhancing
the
removal of greasy/oily soils by combining a lipase enzyme with an AQD
dispersant.
Greasy/oily "everyday "soils are a mixture of triglycerides, lipids, complex
polysaccharides, inorganic salts and proteinaceous matter. When soiled
garments are
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stored before washing, some triglycerides are converted by bacterial action to
fatty acids;
lipase enzymes can be used to convert any remaining triglycerides to fatty
acids through-
the-wash. Generally, for formulas relying on hardness control by diffusion
builders (e.g.,
layered silicates) pseudo unbuilt conditions will be present early a the wash
which
features a large intake of cold water. In these first minutes, fatty acids in
the soil interact
with the unbuilt hardness to form insoluble calcium lime-soaps which then
hinder
subsequent soil removal and cause soil residues to remain on the fabric after
the wash.
In unbuilt formulations this greasy/oily stain insolubilization will cause
even more of a
problem. Upon successive wearing/washing, residues build-up, leading to
yellowing and
entrapment of particulate dirt. Eventually, garments become dingy, are
perceived as
unwearable and are often discarded.
It has now been found that detergent compositions containing AQD dispersants
and lipase enzyme deliver superior cleaning and whiteness performance vs.
products
containing either technology alone. Suitable lipase enzymes include those
produced b~
microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC
19.1 S4, 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~luorescens IAM 10S7. This lipase is available
from
Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P
"Amano," hereinafter referred to as "Amano-P". Further suitable lipases are
lipases such
as M 1 LipaseR and LipomaxR (Gist-Brocades). Other suitable commercial lipases
include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromo6acter
viscosum
var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter
viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The
Netherlands, and lipases ex Pseudomonas gladioli. LIPOLASE~ enzyme derived
from
Humicola lanuginosa and commercially available from Novo, see also EP 34l,947,
is a
preferred lipase fox use herein. Lipase and amylase variants stabilized
against peroxidase
enzymes are described in WO 94149S 1 A to Novo. See also WO 9205249 and RD
943 59044.
Highly preferred lipases are the D96L lipolytic enzyme variant of the native
lipase derived from Humicola lanuginosa as described m US Serial No.
08J341,826. (See
also patent application WO 92/0S249 viz. wherein the native lipase ex Humicola
lanuginosa aspartic acid (D) residue at position 96 is changed to Leucine (L).
According
to this nomenclature said substitution of aspartic acid to Leucine in position
96 is shown
as : D96L.) Preferably the Humicola lanuginosa strain DSM 4106 is used.
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In spite of the large number of publications on lipase enzymes, only the
lipase
derived from Humicola lanuginosa and produced in Aspergillus oryzae as host
has so far
found widespread application as additive for fabric washing products. It is
available
from Novo Nordisk under the tradename LipolaseTM, as noted above. In order to
optimize the stain removal performance of Lipolase, Novo Nordisk have made a
number
of variants. As described in WO 92/05249, the D96L variant of the native
Humicola
lanuginosa lipase improves the lard stain removal efficiency by a factor 4.4
over the
wild-type lipase (enzymes compared in an amount ranging from 0.075 to 2.5 mg
protein
per liter). Research Disclosure No. 35944 published on March 10, 1994, by Novo
Nordisk discloses that the lipase variant (D96L) may be added in an amount
corresponding to 0.00l-100- mg (5-500,000 LUlliter) lipase variant per liter
of wash
Liquor.
Lipase enzyme is incorporated into the composition in accordance with the
invention at a level of from 50 LU to 8500 LU per liter wash solution.
Preferably the
variant D96L is present at a level of from l00 LU to 7500 LU per liter of wash
solution.
More preferably at a level of from 150 LU to 5000 LU per liter of wash
solution.
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.
Also suitable are cutinases [EC 3.1.1.S0] 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-A-88/09367
(Genencor).
Amylase - Complete removal of the very hydrophobic "everyday" or "body" soils
is difficult and low levels of residual soils often remain on the fabric after
washing.
These residues build up and act like an amorphous glue between the fibers,
entrapping
particulate dirt and leading to fabric yellowing. It has now further been
discovered that
detergent compositions containing a combination of the water-soluble AQD
dispersants
herein and amylase enzymes delivers superior cleaning and whiteness
performance vs.
compositions containing either technology alone.
Such amylase enzymes include those described in W095/26397 and in co-
pending application by Novo Nordisk PCT/DK96/00056. These enzymes are
incorporated into detergent compositions at a level from 0.00018% to 0.060%
pure
enzyme by weight of the total composition, more preferably from 0.00024% to
0.048%
pure enzyme by weight of total weight composition.
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Specific amylase enzymes for use in the detergent compositions of the present
invention therefore include
(a) a-amylases characterised by having a specific activity at least 25% higher
than the
specific activity of Termamyl~ at a temperature range of 25~C to 55~C and at a
pH value
in the range of 8 to 10, measured by the Phadebas~ a-amylase activity assay.
Such
Phadebas~ a-amylase activity assay is described at pages 9-10, W095/26397.
(b) a-amylases according (a) comprising the amino sequence shown in the SEQ ID
listings in the above cited reference. or an a-amylase being at least 80%
homologous
with the amino acid sequence shown in the SEQ ID listing.
(c) a-amylases according (a) comprising the following amino sequence in the N-
terminal
His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn
Asp.
A polypeptide is considered to be X% homologous to the parent amylase if a
comparison of the respective amino acid sequences, performed via algorithms,
such as
the one described by Lipman and Pearson in Science 227, 1985, p. 1435, reveals
an
identity of X%
(d) a-amylases according (a-c) wherein the a-amylase is obtainable from an
alkalophilic
Bacillus species; and in particular, from any of the strains NCIB 12289, NCIB
12S 12,
NCIB 12513 and DSM 935.
In the context of the present invention, the term "obtainable from" is
intended not only to
indicate an amylase produced by a Bacillus strain byt also an amylase encoded
by a
DNA sequence isolated from such a Bacillus strain and produced in an host
organism
transformed with said DNA sequence.
(e)a-amylase showing positive immunological cross-reactivity with antibodies
raised
against an a-amylase having an amino acid sequence corresponding respectively
to those
a-amylases in (a-d).
(fj Variants of the following parent a-amylases which (i) have one of the
amino acid
sequences shown in corresponding respectively to those a-amylases in (a-e), or
(ii}
displays at least 80% homology with one or more of said amino acid sequences,
and/or
displays immunological cross-reactivity with an antibody raised against an a-
amylase
having one of said amino acid sequences, and/or is encoded by a DNA sequence
wich
hybridizes with the same probe as a DNA sequence encoding an a-amylase having
one
of said amino acid sequence; in which variants
1. at least one amino acid residue of said parent a-amylase has been deleted;
andlor
2.at least one amino acid residue of said parent a-amylase has been replaced
by a
different amino acid residue; and/or
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3. at least one amino acid residue has been inserted relative to said parent a-
amylase;
said variant having an a-amylase activity and exhibiting at least one of the
following
properties relative to said parent a-amylase : increased thermostability,
increased
stability towards oxidation, reduced Ca ion dependency, increased stability
and/or a-
amylolytic activity at neutral to relatively high pH values, increased a-
amylolytic
activity at relatively high temperature and increase or decrease of the
isoelectric point
(pI) so as to better match the pI value for a-amylase variant to the pH of the
medium.
Said variants are described in the patent application PCT/DK96/00056.
Other amylases suitable herein include, for example, a-amylases described in
GB
l,296,839 to Novo; RAPIDASE~, International Bio-Synthetics, Inc. and
TERMAMYL~, Novo. FUNGAMYL~ from Novo is especially useful. Engineering of
enzymes for improved stability, e.g., oxidative stability, is known. See, for
example J.
Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-652i. Certain
preferred
embodiments of the present compositions can make use of amylases having
improved
stability in detergents such as automatic dishwashing types, especially
improved
oxidative stability as measured against a reference-point of TERMAMYL~ in
commercial use in 1993. These preferred amylases herein share the
characteristic of
being "stability-enhanced" amylases, characterized, at a minimum, by a
measurable
improvement in one or more of: oxidative stability, e.g., to hydrogen
peroxide/tetraacetylethylenediamine in buffered solution at pH 9-10; thermal
stability,
e.g., at common wash temperatures such as about 60oC; or alkaline stability,
e.g., at a pH
from about 8 to about 11, measured versus the above-identified reference-point
amylase.
Stability can be measured using any of the art-disclosed technical tests. See,
for example,
references disclosed in WO 9402597. Stability-enhanced amylases can be
obtained from
Novo or from Genencor International. One class of highly preferred amylases
herein
have the commonality of being derived using site-directed mutagenesis from one
or more
of the Bacillus amylases, especially the Bacillus a-amylases, regardless of
whether one,
two or multiple amylase strains are the immediate precursors. Oxidative
stability-
enhanced amylases vs. the above-identified reference amylase are preferred for
use,
especially in bleaching, more preferably oxygen bleaching, as distinct from
chlorine
bleaching, detergent compositions herein. Such preferred amylases include (a)
an
amylase according to the hereinbefore incorporated WO 9402597, Novo, Feb. 3,
1994, as
further illustrated by a mutant in which substitution is made, using alanine
or threonine,
preferably threonine, of the methionine residue located in position 197 of the
B.
licheniformis alpha-amylase, known as TERMAMYL~, or the homologous position
variation of a similar patent amylase, such as B. amyloliquefaciens) B.
subtilis, or B.
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13
stearothermophilus; (b) stability-enhanced amylases as described by Genencor
International in a paper entitled "Oxidatively Resistant alpha-Amylases"
presented at the
207th American Chemical Society National Meeting, March 13-17 1994, by C.
Mitchinson. Therein it was noted that bleaches in automatic dishwashing
detergents
inactivate alpha-amylases but that improved oxidative stability amylases have
been made
by Genencor from B. licheniformis NCIB8061. Methionine (Met) was identified as
the
most likely residue to be modified. Met was substituted, one at a time, in
positions 8, 15,
197, 256, 304, 366 and 438 leading to specific mutants, particularly important
being
M 197L and M 197T with the M 197T variant being the most stable expressed
variant.
Stability was measured in CASCADE~ and SUNLIGHT~; (c) particularly preferred
amylases herein include amylase variants having additional modification in the
immediate parent as described in WO 9510603 A and are available from the
assignee,
Novo, as DURAMYL~. Other particularly preferred oxidative stability enhanced
amylase include those described in WO 94l8314 to Genencor International and WO
9402597 to Novo. Any other oxidative stability-enhanced amylase can be used,
for
example as derived by site-directed mutagenesis from known chimeric, hybrid or
simple
mutant parent forms of available amylases. Other preferred enzyme
modifications are
accessible. See WO 9509909 A to Novo.
Alkyl alkoxylated sulfates and/or alkyl sulfates - The 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 ar hydroxyalkyl group having a C 1 p-C24
alkyl
component, preferably a C 12-C 1 g alkyl or hydroxyalkyi, more preferably C 12-
C 15 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.
Specific examples of substituted ammonium cations include ethanol-, triethanol-
, methyl-
dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as
tetramethyl-ammonium and dimethyl piperidinium cations and those derived from
alkylamines such as ethylarnine, diethylamine, triethylamine, mixtures
thereof, and the
like. Exemplary surfactants are C 12-C 15 alkyl polyethoxylate ( 1.0) sulfate
(C 12-
C 1 SE( 1.0)M), C 12-C 15 ~kYl polyethoxylate {2.25) sulfate (C 12-C 1
SE(2.25)M), C 12-
C 15 alkyl polyethoxylate (3.0) sulfate (C 12-C 1 SE(3.0)M), and C I 2-C 15
alkyl
polyethoxylate (4.0) sulfate (C 12-C 1 SE(4.0)M), wherein M is conveniently
selected from
sodium and potassium.
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14
The alkyl sulfate surfactants hereof are water soluble salts or acids of the
formula
ROS03M wherein R preferably is a Cg-C 1 g hydrocarbyl, preferably an alkyl or
hydroxyalkyl having a C I 0-C 1 g alkyl component, more preferably a C 12-C I
5 alkyl or
hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g.
sodium, potassium,
lithium), or ammonium or substituted ammonium (e.g. methyl-, dimethyl-, and
trimethyl
ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium
and dimethyl piperidinium cations and quaternary ammonium cations derived from
alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures
thereof, and
the like).
Commerical alkyl alkoxylate sulfates comprise a mixture of compounds with
varying degrees of alkoxylation. For example, C 12-1 S Poiyoxyethylene (3)
sulfate from
Shell Chemical Company, Houston, TX, will contain molecules with from zero
ethoxylates to five or more, for an average degree of ethoxylation = 3. The
lower the
average degree of ethoxylation of a given sample, the higher the level of
alkyl sulfate
(EO=0) which may be present in the mixture.
For purposes of this invention, the total amount of alkyl sulfate present in
the
detergent compositions herein include not only the alkyl sulfate added to the
composition
but also any alkyl sulfate which may be present in the alkyl alkoxyate sulfate
surfactant
mixture.
In another embodiment of the invention herein, surprisingly it has been found
that
in liquid detergents, the benefits associated with the AQD dispersant, and its
combination
with ethoxylated polyethyleneimines (PEI), are greatly enhanced when the
surfactant
system of the detergent comprises sodium alkylethoxysulfate (AES) and nil
alkyl sulfate
and alkylbenzenesulfonate. By "nil" is meant less than 5%, preferably less
than 1 %.
In yet another embodiment of the invention herein, surprisingly is has been
found
that in non-aqueous liquid detergents, the benefits associated with the AQD
dispersant
are enhanced when the surfactant system of the detergent comprises linear
alkylbenzenesulfonate.
The amine - Suitable amine surfactants for use herein include amines according
to
the formula:
R3
RZ-X-(CH2)n-N
R4
wherein R1 is a C6-C12 alkyl group; n is from about 2 to about 4, X is a
bridging group
which is selected from NH, CONH, COO, or O or X can be absent; and R3 and R4
are
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IS
individually selected from H, C 1-C4 alkyl, or (CH2-CH2-O(RS)) wherein RS is H
or
methyl.
Preferred amines include the following:
RI-(CH2)2-NH2
RI-O-(CH2)3-NH2
R1-C(O)-NH-{CH2)3-N(CH3)2
CH2-CH (OH) -RS
R1-N
CH2-CH (OH) -R5
wherein R1 is a C6-C12 alkyl group and RS is H or CH3.
In a highly preferred embodiment, the amine is described by the formula:
R 1-C(O)-NH-(CH2)3-N(CH3)2
wherein Rl is Cg-C12 alkyl.
Particularly preferred amines include those selected from the group consisting
of
octyl amine, hexyl amine, decyl amine, dodecyl amine, Cg-C I2
bis(hydroxyethyl)amine,
Cg-C 12 bis(hydroxyisopropyl)amine, and Cg-C 12 amido-propyl dimethyl amine,
and
mixtures.
This invention also provides detergent compositions which deliver effective
cleaning of greasy/oily everyday soils via use of percarbonate bleach with an
AQD
dispersants as disclosed herein. Percarbonate, which delivers peroxide bleach
into the
wash, is a cornerstone technology of modern, ultra-compact granular laundry
detergent
formulas. Peroxide bleach is very hydrophilic and, while it cannot match the
bleaching
effectiveness delivered by peracids (formed for example from peroxide
interaction with
TAED), it is effective at decoloration of pigments (e.g., in particulates or
beverage
stains) and also can help remove the color from the organic residues
associated with
body soils. Unexpectedly, it has now been discovered that compositions
containing
AQD dispersants and percarbonate bleach deliver superior cleaning and
whiteness
performance.
This invention also provides detergent compositions which deliver effective
cleaning of greasy/oily everyday soils by means of hydrophobic bleach
activators used in
combination with a water-soluble. AQD dispersant of the present type. Everyday
soil
cleaning and whiteness benefits for hydrophobic bleach activators and peracids
have
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already been demonstrated. Such materials are, to a limited degree, able to
penetrate
complex/greasy oily soils. It has now been found that detergent and bleach
compositions
containing AQD and hydrophobic bleach activators (including preformed
peracids)
deliver superior cleaning and whiteness performance.
This invention also provides detergent compositions which deliver effective
cleaning of greasy/oily "everyday" soils (and accidental soils), via use of
polyethoxyated-polyamine polymers (PPP) with the AQD dispersants herein. As
noted,
greasy/oily "everyday" soils (e.g., on collars, pillowcases) are a mixture of
triglycerides,
lipids, complex polysaccharides, inorganic salts and proteinaceous matter.
Complete
removal of these very hydrophobic soils is difficult and low levels of
residual stain often
remain on the fabric after washing. To improve performance in this key area,
various
soil dispersant polymers have been developed. Characteristic features of these
materials
include: ( 1 ) a reasonably low molecular weight "hydrophobic" polyamine
backbone
(which is slightly cationic in nature providing an affinity for soils and
fabrics); and (2)
pendant "hydrophilic" polyethoxylate groups which provide steric stabilization
and
greasy soil suspension. During the wash, these polymers work at the stainlwash
liquor
interface.
Surprisingly, it has now been discovered that detergent compositions
containing
the AQD dispersants herein and polyethoxylated-polyamine polymers deliver
superior
cleaning and whiteness performance vs. compositions containing either
technology
alone. Benefits for the mixed system are believed to be the result of: ( 1 )
AQD action on
the stain surface to prevent Iime soap formation and to lift off any calcium
soaps present,
thereby facilitating improved polymer deposition; (2) AQD providing
solubilization deep
into the soil, while the polymer acts as a "grease removal shuttle", stripping
out the
AQD-solubilized stain components and dispersing them into the wash liquor.
The preferred polyethoxylated-polyamines useful herein are generally
polyalkyleneamines (PAA's), polyalkyleneimines (PAI's), preferably
polyethyleneamine
(PEA's), polyethyleneimines (PEI's), or PEA's or PEI's connected by moieties
having
longer R units than the parent PAA's, PAI's, PEA's or PEI's. A common
polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are obtained by
reactions
involving ammonia and ethylene dichloride, followed by fractional
distillation. The
common PEA's obtained are triethylenetetramine (TETA) and
teraethylenepentamine
(TEPA). Above the pentamines, i.e., the hexamines, heptamines, octamines and
possibly
nonamines, the cogenerically derived mixture does not appear to separate by
distillation
and can include other materials such as cyclic amines and particularly
piperazines. There
can also be present cyclic amines with side chains in which nitrogen atoms
appear. See
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17
U.S. Patent 2,792,372, Dickinson, issued May 14, 1957, which describes the
preparation
of PEA's.
Preferred amine polymer backbones comprise R units that are C2 alkylene
(ethylene) units, also known as polyethylenimines (PEI's). Preferred PEI's
have at least
moderate branching, that is the ratio of m to n is less than 4:1, however
PEI's having a
ratio of m to n of about 2:1 are most preferred. Preferred backbones, prior to
modification have the general formula:
H
~2NCH2CH2lri ~CHZCH2~rri ~CH2CH2lri NH2
wherein m and n are the same as defined herein above. Preferred PEI's, prior
to
modification, will have a molecular weight greater than about 200 daltons.
The relative proportions of primary, secondary and tertiary amine units in the
polyamine backbone, especially in the case of PEI's, will vary, depending on
the manner
of preparation. Each hydrogen atom attached to each nitrogen atom of the
polyamine
backbone chain represents a potential site for subsequent substitution,
quaternization or
oxidation.
These polyamines can be prepared, for example, by polymerizing ethyleneimine
in the presence of a catalyst such as carbon dioxide, sodium bisulfate,
sulfuric acid,
hydrogen peroxide, hydrochloric acid, acetic acid, etc.' Specific methods for
preparing
these polyamine backbones are disclosed in U.S. Patent 2,182,306, Ulrich et
al., issued
December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962;
U.S. Patent
2,208,095, Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839,
Crowther,
issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued May 21,
1951; all
herein incorporated by reference.
Examples of modified cotton soil release polymers of the present invention
comprising PEI's, are illustrated in Formulas I - IV:
Formula I depicts a cotton soil release polymer comprising a PEI backbone
wherein a11 substitutable nitrogens are modified by replacement of hydrogen
with a
polyoxyalkyleneoxy unit, -(CH2CH20)7H, having the formula
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I8
[H(OCH,CHzhlzN~ /N[(CH,CH,O)~H]z
~N H(OCHzCHzh.N~N[(CHzCHzOhHjz
(CH'CH20)~H ~ (CHzCH20}~H
[H(OCHzCHZhIzN~ N~ N~ N~ N~ N~N~ N~N~ Nf(~zCHzO)~HIz
(CHZCH20)~H (CHzCHZOhH ~ (CHzCHzOhH
~N~
~ N[(CHzCHzOhtIJz
f~-~(~z~zh)zN ~Nf(CI-IzCHzoh!-11z
Formula I
This is an example of a cotton soil release polymer that is fully modified by
one type of
moiety.
Formula II depicts a cotton soil release polymer comprising a PEI backbone
wherein a11 substitutable primary amine nitrogens are modified by replacement
of
hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH20)~H, the molecule is then
modified by subsequent oxidation of a11 oxidizable primary and secondary
nitrogens to
N-oxides, said cotton soil release agent having the formula
tH(OCHZCHzhlz~ ~K~z~zoh~-Ilz a~ p z0)6H
o~ ~/~Nf(CHz~zOhHlz
H(OC1-IzO z)s '~O ~(~2~20)6H O C(CHzCHzO)~H
O
t N ~ N ~ N CH,CH O
fH(oCHzCHzhlzN~~ ~o~~~~~ 1 ~N~~ ~~ f( . z hi-I1z
b O
O(Cf-IzCHzO)6H ~ O(CHzCHzOI6H
O O .
~N~Nf(CHZCHzOhHlz
[H(~ lz~zl~lzN o~ ~ ~ f(~z~zohHlz
0
Formula II
Formula III depicts a cotton soil release polymer comprising a PEI backbone
wherein all backbone hydrogen atoms are substituted and some backbone amine
units are
quaternized. The substituents are poiyoxyalkyleneoxy units, -(CH2CH20)~H, or
methyl
groups. The modified PEI cotton soil release polymer has the formula
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~3
I
[H(OCHzCHzhlzN N(CHzCH20hH
, _ ~3
'Nj C~ ~3~N~N(CHZCH,OhH
~3 ~ ~3 ~3 CH3
IH(~z~zhlzN~t+~_ N~N~N~N~N~1+~N~N(CH3~Z
I I (
C~ ~3 ~3 ~ C~ CH3
CI +
+C~
fH(~z~zhlzN N~N(~3~
~N(CHs~Z
Formula III
Formula IV depicts a cotton soil release polymer comprising a PEI backbone
wherein the backbone nitrogens are modified by substitution (i.e. by -
{CH2CH20)~H or
methyl), quaternized, oxidized to N-oxides or combinations thereof. The
resulting cotton
soil release polymer has the formula
[H(OCHzCHzhlzN N(CHzCH20hH
_ O CH3
~N~ CI ~a~N~N(CH
i ~ Cl'
O
~3 N~ N(~3h
(~(o~~~ZhhN +~~. N~'~ ~ ~ N~ cr rr~
CH3 O O CH3
CI +, . ....
+ C~_
N(~3h
N(~sh
Formula IV
In the above examples, not all nitrogens of a unit class comprise the same
modification. The present invention allows the formulator to have a portion of
the
secondary amine nitrogens ethoxylated while having other secondary amine
nitrogens
oxidized to N-oxides. This also applies to the primary amine nitrogens, in
that the
formulator may choose to modify all or a portion of the primary amine
nitrogens with
one or more substituents prior to oxidation or quaternization. Any possible
combination
of E groups can be substituted on the primary and secondary amine nitrogens,
except for
the restrictions described herein above.
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The present invention employs an "effective amount" of the AQD dispersant to
improve the performance of cleaning compositions which contain other adjunct
ingredients. By an "effective amount" of the AQD dispersants and adjunct
ingredients
herein is meant an amount which is sufficient to improve, either directionally
or
significantly at the 90% confidence Ievel, the performance of the cleaning
composition
against at least some of the target soils and stains. Thus, in a composition
whose targets
include certain food stains, the formulator will use sufficient AQD to at
least
directionally improve cleaning performance against such stains. Likewise, in a
composition whose targets include clay soil, the formulator will use
sufficient AQD to at
least directionally improve cleaning performance against such soil.
Importantly, in a
fully-formulated laundry detergent the AQD dispersants can be used at levels
which
provide at least a directional improvement in cleaning performance over a wide
variety
of soils and stains, as will be seen from the data presented hereinafter.
As noted, the AQD dispersants are used herein in detergent compositions in
combination with detersive surfactants at levels which are effective for
achieving at least
a directional improvement in cleaning performance. In the context of a fabric
laundry
composition, such "usage levels" can vary depending not only on the type and
severity of
the soils and stains, but also on the wash water temperature, the volume of
wash water
and the type of washing machine.
As can be seen from the foregoing, the amount of AQD dispersant used in a
machine-wash laundering context can vary, depending on the habits and
practices of the
user, the type of washing machine, and the like. In this context, however, one
heretofore
unappreciated advantage of the AQD dispersants is their ability to provide at
least
directional improvements in performance over a spectrum of soils and stains.
V arious other cleaning compositions can also be formulated using an effective
amount of the AQD dispersants in the manner of this invention. Such
compositions
include, but are not limited to, hand dishwashing products (especially liquids
or gels),
hard surface cleaners, shampoos, personal cleansing bars, laundry bars, and
the like.
Since the habits and practices of the users of such compositions show minimal
variation,
it is satisfactory to include from about 0.25% to about 5%, preferably from
about 0.45%
to about 2%, by weight, of the AQD dispersants in such compositions.
Detersive Surfactants - Nonlimiting examples of anionic surfactants useful
herein
typically at levels from about 1 % to about 55%, by weight, primary, branched-
chain and
random C 10-C20 alkyl sulfates ("AS"), the C 10-C 1 g secondary (2,3) alkyl
sulfates of the
formula CH3(CH2)x(CHOS03-M+) CH3 and CH3 (CH2h,(CHOS03-M+) CH2CH3
where x and (y + 1 ) are integers of at least about 7, preferably at least
about 9, and M is a
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water-solubilizing cation, especially sodium, unsaturated sulfates such as
oleyl sulfate,
the C l 0-C 1 g alpha-sulfonated fatty acid esters, the C 10-C 1 g sulfated
alkyl
polyglycosides, the C 10-C 1 g alkyl alkoxy sulfates ("AEXS"; especially EO 1-
7 ethoxy
sulfates), and C l 0-C 1 g alkyl alkoxy carboxylates (especially the EO 1-5
ethoxycarboxylates). The C 12-C 1 g betaines and sul fobetaines ("sultaines"),
C l 0-C 1 g
amine oxides, and the like, can also be included in the overall compositions.
C 10-C20
conventional soaps may also be used. If high sudsing is desired, the branched-
chain
C 10-C 16 soaps may be used. Other conventional useful surfactants are listed
in standard
texts.
Preferably the compositions of the invention are substantial) free of C l l -C
1 g alkyl
benzene sulfonates ("LAS").
Nonionic Surfactants - Nonlimiting examples of nonionic surfactants useful
herein typically at levels from about 1 % to about 55%, by weight include the
alkoxylated
alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's),
alkyl
polyglycosides (APG's), C l0-C 18 glycerol ethers, and the like.
More specifically, the condensation products of primary and secondary
aliphatic
alcohols with from about 1 to about 25 moles of ethylene oxide (AE) are
suitable for use
as the nonionic surfactant in the present invention. The alkyl chain of the
aliphatic
alcohol can either be straight or branched, primary or secondary, and
generally contains
from about 8 to about 22 carbon atoms. Preferred are the condensation products
of
alcohoIs having an alkyl group containing from about 8 to about 20 carbon
atoms, more
preferably from about 10 to about 18 carbon atoms, with from about 1 to about
10 moles,
preferably 2 to 7, most preferably 2 to 5, of ethylene oxide per mole of
alcohol.
Examples of commercially available nonionic surfactants of this type include:
TergitolTM
I S-S-9 (the condensation product of C 11-C 15 linear alcohol with 9 moles
ethylene
oxide) and Tergitol'~M 24-L-6 NMW (the condensation product of C 12-C 14
Pnm~'Y
alcohol with 6 moles ethylene oxide with a narrow molecular weight
distribution), both
marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product
of
C 14-C 15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the
condensation product of C 12-C 13 linear alcohol with 3 moles of ethylene
oxide), Neodol
TM 45-7 (the condensation product of C 14-C 15 linear alcohol with 7 moles of
ethylene
oxide) and NeodolTM 45-5 (the condensation product of C 14-C 15 linear alcohol
with 5
moles of ethylene oxide) marketed by Shell Chemical Company; KyroTM EOB (the
condensation product of C 13-C 15 alcohol with 9 moles ethylene oxide),
marketed by
The Procter & Gamble Company; and Genapol LA 030 or O50 (the condensation
product of C I 2-C 14 alcohol with 3 or 5 moles of ethylene oxide) marketed by
Hoechst.
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The preferred range of HLB in these AE nonionic surfactants is from 8-11 and
most
preferred from 8-10. Condensates with propylene oxide and butylene oxides may
also be
used.
Another class of preferred nonionic surfactants for use herein are the
polyhydroxy fatty acid amide surfactants of the formula.
R2-' ''-N -Z
O R1
wherein R 1 is H, or C 1 _4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or
a mixture
thereof, R2 is C5_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 alkyl or
C15-17 alkyl 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. Typical examples include the C 12-C 1 g and C 12-C 14 N=
methylglucamides. See U.S. 5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty
acid
amides can also be used; see U.S. S,489,393.
Also useful as the nonionic surfactant in the present invention are the
alkylpolysaccharides such as those disclosed in U.S. Patent 4,565,647,
Llenado, issued
January 21, 1986, having a hydrophobic group containing from about 6 to about
30
carbon atoms, preferably from about 10 to about 16 carbon atoms, and a
polysaccharide,
e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10,
preferably
from about 1.3 to about 3, most preferably from about 1.3 to about 2.7
saccharide units.
Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g.,
glucose,
galactose and galactosyl moieties can be substituted for the glucosyl moieties
(optionally
the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus
giving a glucose or
galactose as opposed to a glucoside or gaiactoside). The intersaccharide bonds
can be,
e.g., between the one position of the additional saccharide units and the 2-,
3-, 4-, and/or
6- positions on the preceding saccharide units.
The preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(glYcosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from about
to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3,
preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3
to about 10,
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23
preferably from about 1.3 to about 3, most preferably from about 1.3 to about
2.7. The
glycosyl is preferably derived from glucose. To prepare these compounds, the
alcohol or
alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a
source of
glucose, to form the glucoside (attachment at the 1-position). The additional
glycosyl
units can then be attached between their 1-position and the preceding glycosyl
units 2-,
3-, 4- and/or 6-position, preferably predominately the 2-position.
Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl
phenols are also suitable for use as the nonionic surfactant of the surfactant
systems of
the present invention, with the polyethylene oxide condensates being
preferred. These
compounds include the condensation products of alkyl phenols having an alkyl
group
containing from about 6 to about 14 carbon atoms, preferably from about 8 to
about 14
carbon atoms, in either a straight-chain or branched-chain configuration with
the
alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an
amount
equal to from about 2 to about 25 moles, more preferably from about 3 to about
15
moles, of ethylene oxide per mole of alkyl phenol. Commercially available
nonionic
surfactants of this type include IgepalTM CO-630, marketed by the GAF
Corporation;
and TritonTM X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas
Company. These surfactants are commonly referred to as alkylphenol alkoxylates
(e.g.,
alkyl phenol ethoxylates).
The condensation products of ethylene oxide with a hydrophobic base formed by
the condensation of propylene oxide with propylene glycol are also suitable
for use as
the additional nonionic surfactant in the present invention. The hydrophobic
portion of
these compounds will preferably have a molecular weight of from about 1500 to
about
1800 and will exhibit water insolubility. The addition of polyoxyethylene
moieties to this
hydrophobic portion tends to increase the water solubility of the molecule as
a whole,
and the liquid character of the product is retained up to the point where the
polyoxyethylene content is about 50% of the total weight of the condensation
product,
which corresponds to condensation with up to about 40 moles of ethylene oxide.
Examples of compounds of this type include certain of the commercially-
available
PluronicTM surfactants, marketed by BASF.
Also suitable for use as the nonionic surfactant of the nonionic surfactant
system
of the present invention, are the condensation products of ethylene oxide with
the
product resulting from the reaction of propylene oxide and ethylenediamine.
The
hydrophobic moiety of these products consists of the reaction product of
ethylenediamine and excess propylene oxide, and generally has a molecular
weight of
from about 2500 to about 3000. This hydrophobic moiety is condensed with
ethylene
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24
oxide to the extent that the condensation product contains from about 40% to
about 80%
by weight of polyoxyethylene and has a molecular weight of from about S,000 to
about
11,000. Examples of this type of nonionic surfactant include certain of the
commercially
available TetronicTM compounds, marketed by BASF.
The following illustrates various other adjunct ingredients which may be used
in
the compositions of this invention, but is not intended to be limiting
thereof. While the
combination of the AQD with such adjunct compositional ingredients can be
provided as
finished products in the form of liquids, gels, bars, or the like using
conventional
techniques, the manufacture of the granular laundry detergents herein requires
some
special processing techniques in order to achieve optimal performance.
Accordingly, the
manufacture of laundry granules will be described hereinafter separately in
the Granules
Manufacture section (below), for the convenience of the formulator.
Builders - Detergent builders can optionally but preferably be included in the
compositions herein, for example to assist in controlling mineral, especially
Ca and/or
Mg, hardness in wash water or to assist in the removal of particulate soils
from surfaces.
Builders can operate via a variety of mechanisms including forming soluble or
insoluble
complexes with hardness ions, by ion exchange, and by offering a surface more
favorable to the precipitation of hardness ions than are the surfaces of
articles to be
cleaned. Builder level can vary widely depending upon end use and physical
form of the
composition. Built detergents typically comprise at least about 1 % builder.
Liquid
formulations typically comprise about 5% to about 50%, more typically 5% to
35% of
builder. Granular formulations typically comprise from about 10% to about 80%,
more
typically 15% to 50% builder by weight of the detergent composition. Lower or
higher
levels of builders are not excluded. For example, certain detergent additive
or high-
surfactant formulations can be unbuilt.
Suitable builders herein can be selected from the group consisting of
phosphates
and polyphosphates, especially the sodium salts; silicates including water-
soluble and
hydrous solid types and including those having chain-, layer-, or three-
dimensional-
structure as well as amorphous-solid or non-structured-liquid types;
carbonates,
bicarbonates, sesquicarbonates and carbonate. minerals other than sodium
carbonate or
sesquicarbonate; aluminosilicates; organic mono-, di-, tri-, and
tetracarboxylates
especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium
or
alkanolammonium salt form, as well as oligomeric or water-soluble low
molecular
weight polymer carboxylates including aliphatic and aromatic types; and physic
acid.
These may be complemented by borates, e.g., for pH-buffering purposes, or by
sulfates,
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especially sodium sulfate and any other fillers or carriers which may be
important to the
engineering of stable surfactant and/or builder-containing detergent
compositions.
Builder mixtures, sometimes termed "builder systems" can be used and typically
comprise two or more conventional builders, optionally complemented by
chelants, pH-
buffers or fillers, though these latter materials are generally accounted for
separately
when describing quantities of materials herein. In terms of relative
quantities of
surfactant and builder in the present detergents, preferred builder systems
are typically
formulated at a weight ratio of surfactant to builder of from about 60:1 to
about 1:80.
Certain preferred laundry detergents have said ratio in the range 0.90:1.0 to
4.0:1.0, more
preferably from 0.95:1.0 to 3.0:1Ø
P-containing detergent builders often preferred where permitted by legislation
include, but are not limited to, the alkali metal, ammonium and
alkanolammonium salts
of polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy
polymeric meta-phosphates; and phosphonates.
Suitable silicate builders include alkali metal silicates, particularly those
liquids
and solids having a Si02:Na20 ratio in the range 1.6:1 to 3.2:l, including,
particularly
for automatic dishwashing purposes, solid hydrous 2-ratio silicates marketed
by PQ
Corp. under the tradename BRITESIL~, e.g., BRITESIL H20; and layered
silicates,
e.g., those described in U.S. 4,664,839, May 12, 1987, H. P. Rieck. NaSKS-6,
sometimes abbreviated "SKS-6", is a crystalline layered aluminium-free 8-
Na2Si05
morphology silicate marketed by Hoechst and is preferred especially in
granular laundry
compositions. See preparative methods in German DE-A-3,417,649 and DE-A-
3,742,043. Other layered silicates, such as those having the general formula
NaMSix02x+1 ~YH20 wherein M is sodium or hydrogen, x is a number from 1.9 to
4,
preferably 2, and y is a number from 0 to 20, preferably 0, can also or
alternately be used
herein. Layered silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-
11,
as the a, (3 and y layer-silicate forms. Other silicates may also be useful,
such as
magnesium silicate, which can serve as a crispening agent in granules, as a
stabilising
agent for bleaches, and as a component of suds control systems.
Also suitable for use herein are synthesized crystalline ion exchange
materials or
hydrates thereof having chain structure and a composition represented by the
following
general formula in an anhydride form: xM20ySi02.zM'O wherein M is Na and/or K,
M'
is Ca and/or Mg; y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0 as taught in U.S.
5,427,711,
Sakaguchi et al, June 27, 1995.
Suitable carbonate builders include alkaline earth and alkali metal carbonates
as
disclosed in German Patent Application No. 2,32l,001 published on November 1
S, 1973,
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26
although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and
other
carbonate minerals such as trona or any convenient multiple salts of sodium
carbonate
and calcium carbonate such as those having the composition 2Na2C03.CaC03 when
anhydrous, and even calcium carbonates including calcite, aragonite and
vaterite,
especially forms having high surface areas relative to compact calcite may be
useful, for
example as seeds or for use in synthetic detergent bars.
Aluminosilicate builders are especially useful in granular detergents, but can
also
be incorporated in liquids, pastes or gels. Suitable for the present purposes
are those
having empirical formula: [Mz(A102)z(Si02)v]~xH20 wherein z and v are integers
of at
least 6, the molar ratio of z to v is in the range from i .0 to 0.5, and x is
an integer from
15 to 264. Aluminosilicates can be crystalline or amorphous, naturally-
occurring or
synthetically derived. An aluminosilicate production method is in U.S.
3,985,669,
Krummel, et al, October 12, 1976. Preferred synthetic crystalline
aluminosilicate ion
exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and,
to whatever
extent this differs from Zeolite P, the so-called Zeolite MAP. Natural types,
including
clinoptilolite, may be used. Zeolite A has the formula:
Nal2[(A102)12(Si02)12~'xH20
wherein x is from 20 to 30, especially 27. Dehydrated zeolites (x = 0 - 10)
may also be
used. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in
diameter.
Suitable organic detergent builders include polycarboxylate compounds,
including water-soluble nonsurfactant dicarboxylates and tricarboxylates. More
typically
builder polycarboxylates have a plurality of carboxylate groups, preferably at
least 3
carboxylates. Carboxylate builders can be formulated in acid, partially
neutral, neutral or
overbased form. When in salt form, alkali metals, such as sodium, potassium,
and
lithium, or alkanoiammonium salts are preferred. Polycarboxylate builders
include the
ether polycarboxylates, such as oxydisuccinate, see Berg, U.S. 3,128,287,
April 7, 1964,
and Lamberti et aI, U.S. 3,635,830, January 18, 1972; "TMS/TDS" builders of
U.S.
4,663,071, Bush et al, May 5, 1987; and other ether carboxylates including
cyclic and
alicyclic compounds, such as those described in U.S. Patents 3,923,679;
3,835,l63;
4,158,635; 4,120,874 and 4,102,903.
Other suitable builders are the ether hydroxypolycarboxylates, copolymers of
malefic anhydride with ethylene or vinyl methyl ether; 1, 3, 5-trihydroxy
benzene-2, 4, 6-
trisulphonic acid; carboxymethyloxysuccinic acid; the various alkali metal,
ammonium
and substituted ammonium salts of polyacetic acids such as ethylenediamine
tetraacetic
acid and nitrilotriacetic acid; as well as mellitic acid, succinic acid,
polymaleic acid,
benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble
salts
thereof.
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27
Citrates, e.g., citric acid and soluble salts thereof are important
carboxylate
builders e.g., for heavy duty liquid detergents, due to availability from
renewable
resources and biodegradability. Citrates can also be used in granular
compositions,
especially in combination with zeolite and/or layered silicates.
Oxydisuccinates are also
especially useful in such compositions and combinations.
Where permitted, and especially in the formulation of bars used for hand-
laundering operations, alkali metal phosphates such as sodium
tripolyphosphates, sodium
pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such
as
ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates, e.g., those
of U. S.
3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,13 7 can also be used and
may
have desirable antiscaling properties.
Certain detersive surfactants or their short-chain homologs also have a
builder
action. For unambiguous formula accounting purposes, when they have surfactant
capability, these materials are summed up as detersive surfactants. Preferred
types for
builder functionality are illustrated by: 3,3-dicarboxy-4-oxa-1,6-
hexanedioates and the
related compounds disclosed in U.S. 4,566,984, Bush, January 28, 1986.
Succinic acid
builders include the CS-C20 alkyl and alkenyl succinic acids and salts
thereof. Succinate
builders also include: laurylsuccinate, myristylsuccinate, palmitylsuccinate,
2-
dodecenylsuccinaxe (preferred), 2-pentadecenylsuccinate, and the like. Lauryl-
succinates
are described in European Patent Application 86200690.5/0,200,263, published
November 5, 1986. Fatty acids, e.g., C 12-C 1 g monocarboxylic acids, can also
be
incorporated into the compositions as surfactant/builder materials alone or in
combination with the aforementioned builders, especially citrate and/or the
succinate
builders, to provide additional builder activity. Other suitable
polycarboxylates are
disclosed in U.S. 4,144,226, Crutchfield et al, March t3, I979 and in U.S.
3,308,067,
Diehl, March 7, 1967. See also Diehl, U.S. 3,723,322.
Other types of inorganic builder materials which can be used have the formula
(Mx)i Cay (C03)z wherein x and i are integers from 1 to 15, y is an integer
from 1 to 10,
z is an integer from 2 to 25, Mi are cations, at least one of which is a water-
soluble, and
the equation Ei = 1-15(xi multiplied by the valence of Mi) + 2y = 2z is
satisfied such that
the formula has a neutral or "balanced" charge. These builders are referred to
herein as
"Mineral Builders". Waters of hydration or anions other than carbonate may be
added
provided that the overall charge is balanced or neutral. The charge or valence
effects of
such anions should be added to the right side of the .above equation.
Preferably, there is
present a water-soluble cation selected from the group consisting of hydrogen,
water-
soluble metals, hydrogen, boron, ammonium, silicon, and mixtures thereof, more
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- zs
preferably, sodium, potassium, hydrogen, lithium, ammonium and mixtures
thereof,
sodium and potassium being highly preferred. Nonlimiting examples of
noncarbonate
anions include those selected from the group consisting of chloride, sulfate,
fluoride,
oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and mixtures
thereof.
Preferred builders of this type in their simplest forms are selected from the
group
consisting of Na2Ca(C03)2, K2Ca(C03)2, Na2Ca2(C03)3, NaKCa(C03}2,
NaKCa2(C03)3, K2Ca2(C03)3, and combinations thereof. An especially preferred
material for the builder described herein is Na2Ca(C03)2 in any of its
crystalline
modifications. Suitable builders of the above-defined type are further
illustrated by, and
include, the natural or synthetic forms of any one or combinations of the
following
minerals: Afghanite, Andersonite, AshcroftineY, Beyerite, Borcarite,
Burbankite,
Butschliite, Cancrinite, Carbocernaite, Carletonite, Davyne, DonnayiteY,
Fairchildite,
Fernsurite, Franzinite, Gaudefroyite, Gaylussite, Girvasite, Gregoryite,
Jouravskite,
KamphaugiteY, Kettnerite, Khanneshite, LepersonniteGd, Liottite, MckelveyiteY,
.
Microsommite, Mroseite, Natrofairchildite, Nyerereite, RemonditeCe,
Sacrofanite,
5chrockingerite, Shortite, Surite, Tunisite, Tuscanite, Tyrolite, Vishnevite,
and
Zemkorite. Preferred mineral forms include Nyererite, Fairchildite and
Shortite.
Enzymes - Enzymes can be included in the present detergent compositions for a
variety of purposes, including removal of protein-based, carbohydrate-based,
or
triglyceride-based stains from substrates, for the prevention of refugee dye
transfer in
fabric laundering, and for fabric restoration. Suitable enzymes include
proteases,
amylases, lipases, cellulases, peroxidases, and mixtures thereof of any
suitable origin,
such as vegetable, animal, bacterial, fungal and yeast origin. Preferred
selections are
influenced by factors such as pH-activity and/or stability optima,
thermostability, and
stability to active detergents, builders .and the like. In this respect
bacterial or fungal
enzymes are preferred, such as bacterial amylases and proteases, and fungal
cellulases.
"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain
removing or otherwise beneficial effect in a laundry, hard surface cleaning or
personal
care detergent composition. Preferred detersive enzymes are hydrolases such as
proteases, amylases and lipases. Preferred enzymes for laundry purposes
include, but are
not limited to, proteases, cellulases, lipases and peroxidases. Highly
preferred for
automatic dishwashing are amylases and/or proteases, including both current
commercially available types and improved types which, though more and more
bleach
compatible though successive improvements, have a remaining degree of bleach
deactivation susceptibility.
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Enzymes are normally incorporated into detergent or detergent additive
compositions at levels sufficient to provide a "cleaning-effective amount".
The term
"cleaning effective amount" refers to any amount capable of producing a
cleaning, stain
removal, soil removal, whitening, deodorizing, or freshness improving effect
on
substrates such as fabrics, dishware and the like. In practical terms for
current
commercial preparations, typical amounts are up to about 5 mg by weight, more
typically
0.0I mg to 3 mg, of active enzyme per gram of the detergent composition.
Stated
otherwise, the compositions herein will typically comprise from 0.001% to 5%,
preferably 0.01 %-1 % by weight of a commercial enzyme preparation. Protease
enzymes
are usually present in such commercial preparations at levels sufficient to
provide from
0.005 to 0.1 Anson units (AU) of activity per gram of composition. For certain
detergents, such as in automatic dishwashing, it may be desirable to increase
the active
enzyme content of the commercial preparation in order to minimize the total
amount of
non-catalytically active materials and thereby improve spotting/filming or
other end-
results. Higher active levels may also be desirable in highly concentrated
detergent
formulations.
Suitable examples of proteases are the subtilisins which are obtained from
particular strains of B. subtilis and B. licheniformis. One suitable protease
is obtained
from a strain of Bacillus, having maximum activity throughout the pH range of
8-12,
developed and sold as ESPERASE~ by Novo Industries A/S of Denmark, hereinafter
"Novo". The preparation of this enzyme and analogous enzymes is described in
GB
1,243,784 to Novo. Other suitable proteases include ALCALASE~ and SAVINASE~
from Novo and MAXATASE~ from International Bio-Synthetics, Inc., The
Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9,
1985 and
Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A,
January 9,
l985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in
WO
9318140 A to Novo. Enzymatic detergents comprising protease, one or more other
enzymes, and a reversible protease inhibitor are described in WO 9203529 A to
Novo.
Other preferred proteases include those of WO 95l0591 A to Procter & Gamble .
When
desired, a protease having decreased adsorption and increased hydrolysis is
available as
described in WO 9S07791 to Procter & Gamble. A recombinant trypsin-like
protease for
detergents suitable herein is described in WO 942S583 to Novo.
In more detail, an especially preferred protease, referred to as "Protease D"
is a
carbonyl hydrolase variant having an amino acid sequence not found in nature,
which is
derived from a precursor carbonyl hydrolase by substituting a different amino
acid for a
plurality of amino acid residues at a position in said carbonyl hydrolase
equivalent to
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position +76, preferably also in combination with one or more amino acid
residue
positions equivalent to those selected from the group consisting of +99, +101,
+103,
+104, +i07, +123, +27, +105, +109, +126, +l28, +135, +156, +166, +195, +197,
+204,
+206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the
numbering of Bacillus amyloliquefaciens subtilisin, as described in the patent
applications of A. Baeck, et al, entitled "Protease-Containing Cleaning
Compositions"
having US Serial No. 08/322,676, and C. Ghosh, et al, "Bleaching Compositions
Comprising Protease Enzymes" having US Serial No. 08/322,677, both filed
October 13,
1994.
Celluiases usable herein include both bacterial and fungal types, preferably
having a pH optimum between 5 and 9.5. U.S. 4,435,307, Barbesgoard et al,
March 6,
1984, discloses suitable fungal cellulases from Humicola insolens or Humicola
strain
DSM 1800 or a ceIlulase 212-producing fungus belonging to the genus Aeromonas,
and
cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella
Auricula
Solander. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-
2.095.275
and DE-OS-2.247.832. CAREZYME~ and CELLUZYME~(Novo) are especially
useful. See also WO 9117243 to Novo.
Peroxidase enzymes may be used in combination with oxygen sources, e.g.,
percarbonate, pezborate, hydrogen peroxide, etc., for "solution bleaching" or
prevention
of transfer of dyes or pigments removed from substrates during the wash to
other
substrates present in the wash solution. Known peroxidases include horseradish
peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-
peroxidase.
Peroxidase-containing detergent compositions are disclosed in WO 89099813 A,
October 19, 1989 to Novo and WO 8909813 A to Novo.
A range of enzyme materials and means for their incorporation into synthetic
detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to
Genencor International, WO 8908694 A 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. 4,507,219, 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 stabilised 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,S86, 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 A to Novo.
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31
Enzyme Stabilizin~S,ystem - The enzyme-containing compositions herein may
optionally also comprise from about 0.001 % to about 10%, preferably from
about
0.005% to about 8%, most preferably from about 0.01 % to about 6%, by weight
of an
enzyme stabilizing system. The enzyme stabilizing system can be any
stabilizing system
which is compatible with the detersive enzyme. Such a system may be inherently
provided by other formulation actives, or be added separately, e.g., by the
formulator or
by a manufacturer of detergent-ready enzymes. Such stabilizing systems can,
for
example, comprise calcium ion, boric acid, propylene glycol, short chain
carboxylic
acids) boronic acids, and mixtures thereof, and are designed to address
different
stabilization problems depending on the type and physical form of the
detergent
composition.
One stabilizing approach is the use of water-soluble sources of calcium and/or
magnesium ions in the finished compositions which provide such ions to the
enzymes.
Calcium ions are generally more effective than magnesium ions and are
preferred herein
if only one type of cation is being used. Typical detergent compositions,
especially
liquids, will comprise from about 1 to about 30, preferably from about 2 to
about 20,
more preferably from about 8 to about 12 millimoles of calcium ion per liter
of finished
detergent composition, though variation is possible depending on factors
including the
multiplicity, type and levels of enzymes incorporated. Preferably water-
soluble calcium
or magnesium salts are employed, including for example calcium chloride,
calcium
hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide
and
calcium acetate; more generally, calcium sulfate or magnesium salts
corresponding to the
exemplified calcium salts may be used. Further increased levels of Calcium
andJor
Magnesium may of course be useful, for example for promoting the grease-
cutting action
of certain types of surfactant.
Another stabilizing approach is by use of borate species. See Severson, U.S.
4,537,706. Borate stabilizers, when used, may be at levels of up to 10% or
more of the
composition though more typically, levels of up to about 3% by weight of boric
acid or
other borate compounds such as borax or orthoborate are suitable for liquid
detergent
use. Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-
bromophenylboronic acid or the like can be used in place of boric acid and
reduced
levels of total boron in detergent compositions may be possible though the use
of such
substituted boron derivatives.
Stabilizing systems of certain cleaning compositions, for example automatic
dishwashing compositions, may further comprise from 0 to about 10%, preferably
firom
about 0.01 % to about 6% by weight, of chlorine bleach scavengers, added to
prevent
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32
chlorine bleach species present in many water supplies from attacking and
inactivating
the enzymes; especially under alkaline conditions. While chlorine levels in
water may be
small, typically in the range from about 0.5 ppm to about l.75 ppm, the
available
chlorine in the total volume of water that comes in contact with the enzyme,
for example
during dish- or fabric-washing, can be relatively large; accordingly, enzyme
stability to
chlorine in-use is sometimes problematic. Since perborate or percarbonate,
which have
the ability to react with chlorine bleach, may present in certain of the
instant
compositions in amounts accounted for separately from the stabilizing system,
the use of
additional stabilizers against chlorine, may, most generally, not be
essential, though
improved results may be obtainable from their use. Suitable chlorine scavenger
anions
are widely known and readily available, and, if used, can be salts containing
ammonium
cations with sulfite, bisulfate, thiosulfite, thiosulfate, iodide, etc.
Antioxidants such as
carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic
acid
(EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixtures
thereof can
likewise be used. Likewise, special enzyme inhibition systems can be
incorporated such
that different enzymes have maximum compatibility. Other conventional
scavengers
such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as
sodium
perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate,
as well
as phosphate, condensed phosphate, acetate, benzoate, citrate, formate,
lactate, malate,
tartrate, salicylate, etc., and mixtures thereof can be used if desired. In
general, since the
chlorine scavenger function can be performed by ingredients separately listed
under
better recognized functions, (e.g., hydrogen peroxide sources), there is no
absolute
requirement to add a separate chlorine scavenger unless a compound performing
that
function to the desired extent is absent from an enzyme-containing embodiment
of the
invention; even then, the scavenger is added only for optimum results.
Moreover, the
formulator will exercise a chemist's nonnlal skill in avoiding the use of any
enzyme
scavenger or stabilizer which is majorly incompatible, as formulated, with
other reactive
ingredients. In relation to the use of ammonium salts, such salts can be
simply admixed
with the detergent composition but are prone to adsorb water and/or liberate
ammonia
during storage. Accordingly, such materials, if present, are desirably
protected in a
particle such as that described in US 4,652,392, Baginski et al.
Polymeric Soil Release Asent - Known polymeric soil release agents,
hereinafter
"SRA" or "SRA's", can optionally be employed in the present detergent
compositions. If
utilized, SRA's will generally comprise from 0.0l % to 10.0%, typically from
0. I ~l~ to
5%, preferably from 0.2% to 3.0% by weight, of the composition.
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33
Preferred SRA's typically have hydrophilic segments to hydrophilize the
surface
of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to
deposit
upon hydrophobic fibers and remain adhered thereto through completion of
washing and
rinsing cycles thereby serving as an anchor for the hydrophilic segments. This
can
enable stains occurring subsequent to treatment with SRA to be more easily
cleaned in
later washing procedures.
SRA's can include a variety of charged, e.g., anionic or even cationic (see
U.S.
4,956,447), as well as noncharged monomer units and structures may be linear,
branched
or even star-shaped. They may include capping moieties which are especially
effective
in controlling molecular weight or altering the physical or surface-active
properties.
Structures and charge distributions may be tailored for application to
different fiber or
textile types and for varied detergent or detergent additive products.
Preferred SRA's include oligomeric terephthalate esters, typically prepared by
processes involving at least one transesterification/oligomerization, often
with a metal
catalyst such as a titanium(IV) alkoxide. Such esters may be made using
additional
monomers capable of being incorporated into the ester structure through one,
two, three,
four or more positions, without of course forming a densely crosslinked
overall structure.
Suitable SR.A's include: a sulfonated product of a substantially linear ester
oligomer comprised of an oligomeric ester backbone of terephthaloyl and
oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties
covalently
attached to the backbone, for example as described in U.S. 4,968,45l, November
6, 1990
to J.J. Scheibel and E.P. Gosselink: such ester oligomers can be prepared by
(a)
ethoxylating allyl alcohol, (b) reacting the product of (a) with dimethyl
terephthalate
("DMT") and 1,2-propylene glycol ("PG") in a two-stage transesterification/
oligomerization procedure and (c) reacting the product of (b) with sodium
metabisulfite
in water; the nonionic end-capped 1,2-propylene/polyoxyethylene terephthalate
polyesters of U.S. 4,7l1,730, December 8, 1987 to Gosseiink et al, for example
those
produced by transesterification/oligomerization of poly(ethyleneglycol) methyl
ether,
DMT, PG and poly(ethyleneglycoi) ("PEG"); the partly- and fully- anionic-end-
capped
oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as
oligomers
from ethylene glycol ("EG")) PG, DMT and Na-3,6-dioxa-8-
hydraxyoctanesulfonate; the
nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857,
October 27,
1987 to Gosselink, for example produced from DMT, Me-capped PEG and EG and/or
PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-
sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped
terephthalate esters
of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al, the latter
being
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34
typical of SRA's useful in both laundry and fabric conditioning products, an
example
being an ester composition made from m-sulfobenzoic acid monosodium salt, PG
and
DMT optionally but preferably further comprising added PEG, e.g., PEG 3400.
SRA's also include simple copolymeric blocks of ethylene terephthalate or
propylene terephthalate with polyethylene oxide or polypropylene oxide
terephthalate,
see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July
8, 1975;
cellulosic derivatives such as the hydroxyether cellulosic polymers available
as
METHOCEL from Dow; and the C 1-C4 alkylcelluloses and C4 hydroxyalkyl
celluloses;
see U.S. 4,000,093, December 28, 1976 to Nicol, et al. Suitable SRA's
characterised by
polyvinyl ester) hydrophobe segments include graft copolymers of polyvinyl
ester),
e.g., C 1-C6 vinyl esters, preferably polyvinyl acetate), grafted onto
polyalkylene oxide
backbones. See European Patent Application 0 219 048, published April 22, 1987
by
Kud, et al. Commercially available examples include SOKALAN SRA's such as
SOKALAN HP-22, available from BASF, Germany. Other SRA's are polyesters with
repeat units containing 10-1 S% by weight of ethylene terephthalate together
with 90-
80% by weight of polyoxyethylene terephthalate, derived from a polyoxyethylene
glycol
of average molecular weight 300-S,000. Commercial examples include ZELCON S
126
from Dupont and MILEASE T from ICI.
Another preferred SRA is an oligomer having empirical formula
(CAP)2(EG/PG)5(T)5(SIP)~ which comprises terephthaloyl (T), sulfoisophthaloyl
(SIP),
oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units and which is preferably
terminated with end-caps (CAP), preferably modified isethionates, as in an
oligomer
comprising one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy
and oxy-
1,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 to about
10:1, and two
end-cap units derived from sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said
SRA
preferably further comprises from O.S% to 20%, by weight of the oligomer, of a
crystallinity-reducing stabiliser, for example an anionic surfactant such as
linear sodium
dodecylbenzenesulfonate or a member selected from xylene-, cumene-, and
toluene-
sulfonates or mixtures thereof, these stabilizers or modifiers being
introduced into the
synthesis pot, all as taught in U.S. 5,41 S,807, Gosselink, Pan, Kellett and
Hall, issued
May 16, 1995. Suitable monomers for the above SRA include Na 2-(2-
hydroxyethoxy)-
ethanesulfonate, DMT, Na- dimethyl S-sulfoisophthalate, EG and PG.
Yet another group of preferred SRA's are oligomeric esters comprising: ( 1 ) a
backbone comprising (a) at least one unit selected from the group consisting
of
dihydroxysulfonates, polyhydroxy sulfonates, a unit which is at least
trifunctional
whereby ester linkages are formed resulting in a branched oligomer backbone,
and
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combinations thereof; (b) at least one unit which is a terephthaloyl moiety;
and (c) at
least one unsulfonated unit which is a 1,2-oxyalkyleneoxy moiety; and (2) one
or more
capping units selected from nonionic capping units, anionic capping units such
as
alkoxylated, preferably ethoxylated, isethionates, alkoxylated
propanesulfonates,
alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl
derivatives
and mixtures thereof. Preferred of such esters are those of empirical formula:
{(CAP)x(EG/PG)y'(DEG)y"(PEG)y"'(T)z(SIP)z'(SEG)q(B)m}
wherein CAP, EG/PG, PEG, T and SIP are as defined hereinabove, (DEG)
represents
di(oxyethylene)oxy units; (SEG) represents units derived from the sulfoethyl
ether of
glycerin and related moiety units; (B) represents branching units which are at
least
trifunctional whereby ester linkages are formed resulting in a branched
oligomer
backbone; x is from about 1 to about 12; y' is from about 0.5 to about 25; y"
is from 0 to
about 12; y"' is from 0 to about 10; y'+y"+y"' totals from about 0.5 to about
25; z is from
about 1.5 to about 25; z' is from 0 to about 12; z + z' totals from about 1.5
to about 25; g
is from about 0.05 to about 12; m is from about 0.0I to about 10; and x, y',
y", y"', z, z', q
and m represent the average number of moles of the corresponding units per
mole of said
ester and said ester has a molecular weight ranging from about 500 to about
5,000.
Preferred SEG and CAP monomers for the above esters include Na-2-(2-,3-
dihydroxypropoxy)ethanesulfonate ("SEG"), Na-2-{2-(2-hydroxyethoxy) ethoxy}
ethanesulfonate ("SE3 ") and its homologs and mixtures thereof and the
products of
ethoxylating and sulfonating allyl alcohol. Preferred SRA esters in this class
include the
product of transesterifying and oligomerizing sodium 2-{2-(2-
hydroxyethoxy)ethoxy } ethanesulfonate and/or sodium 2-[2- { 2-(2-
hydroxyethoxy)-
ethoxy}ethoxy]ethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy) ethane
sulfonate, EG, and PG using an appropriate Ti(IV) catalyst and can be
designated as
{CAP)2(T)5(EGIPG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+ -03S[CH2CH20]3.5)-
and B is a unit from glycerin and the mole ratio EG/PG is about 1.7:1 as
measured by
conventional gas chromatography after complete hydrolysis.
Additional classes of SRA's include (I) nonionic terephthalates using
diisocyanate coupling agents to link up polymeric ester structures, see U.S.
4,201,824,
Violland et al. and U.S. 4,240,918 Lagasse et al; (II) SRA's with carboxylate
terminal
groups made by adding trimellitic anhydride to known SRA's to convert terminal
hydroxyl groups to trimellitate esters. With a proper selection of catalyst,
the trimellitic
anhydride forms linkages to the terminals of the polymer through an ester of
the isolated
carboxylic acid of trimellitic anhydride rather than by opening of the
anhydride linkage.
Either nonionic or anionic SRA's may be used as starting materials as long as
they have
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36
hydroxyl terminal groups which may be esterified. See U.S. 4,52S,524 Tung et
al.; (III)
anionic terephthalate-based SRA's of the urethane-linked variety, see U.S.
4,201,824,
Violland et al; (IV) polyvinyl caprolactam) and related co-polymers with
monomers
such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate, including
both
nonionic and cationic polymers, see U.S. 4,579,68l, Ruppert et al.; (V) graft
copolymers,
in addition to the SOKALAN types from BASF made, by grafting acrylic monomers
on
to sulfonated polyesters; these SRA's assertedly have soil release and anti-
redeposition
activity similar to known cellulose ethers: see EP 279, l34 A, 1988, to Rhone-
Poulenc
Chemie; (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate
on to
proteins such as caseins, see EP 457,205 A to BASF ( 1991 ); (VII) polyester-
polyamide
SRA's prepared by condensing adipic acid, caprolactam, and polyethylene
glycol,
especially for treating polyamide fabrics, see Bevan et al, DE 2,335,044 to
Unilever N.
V., 1974. Other useful SRA's are described in U.S. Patents 4,240,918,
4,787,989,
4,525,524 and 4,877,896.
Non-cotton Soil Release Polymers
The non-cotton soil release polymers to be used in the laundry detergent
compositions of the present invention are the following.
Preferred non-cotton soil release went - A. Suitable for use in the laundry
detergent compositions of the present invention are preferred non-cotton soil
release
polymers comprising:
a) a backbone comprising:
i) at least one moiety having the formula:
O O
C-
ii) at least one moiety having the formula:
Rio Rio
-O-R9-(O-R~i O
Rio Rto
wherein R9 is C2-C6 linear alkylene, C3-C6 branched alkylene,
CS-C7 cyclic alkylene, and mixtures thereof; R10
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37
is independently selected from hydrogen or -L-S03-M+; wherein
L is a side chain moiety selected from the group consisting of
alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene,
alkyleneoxyarylene, poly(oxyalkylene), oxyalkyleneoxyarylene,
poly(oxyalkylene)oxyarlyene, alkylenepoly(oxyalkylene),and
mixtures thereof; M is hydrogen or a salt forming cation; i has the
value of 0 or 1;
iii) at least one trifunctional, ester-forming, branching moiety;
iv) at least one 1,2-oxyalkyleneoxy moiety; and
b) one or more capping units comprising:
i) ethoxylated or propoxylated hydroxyethanesulfonate or
ethoxylated or propoxylated hydroxypropanesulfonate units of the
formula (M03S)(CH2)m(R11 O)n-, where M is a salt forming
cation such as sodium or tetralkylammonium, R l l is ethylene or
propylene or a mixture thereof, m is 0 or 1, and n is from 1 to 20;
ii) sulfoaroyl units of the formula -(O)C{C6H4){S03-M+), wherein
M is a salt forming cation;
iii) modified poly(oxyethyiene)oxy monoalkyl ether units of the
formula R120(CH2CH20)k-, wherein R12 contains from 1 to 4
carbon atoms and k is from about 3 to about 100; and
iv) ethoxylated or propoxylated phenolsulfonate end-capping units of
the formula M03S(C6H4)(OR13)n0-, wherein n is from 1 to 20;
M is a salt-forming cation; and R13 is ethylene, propylene and
mixtures thereof.
This type of preferred non-cotton soil release polymer of the present
invention
may be described as having the formula
~(CaP){R4~ ~{A-R 1-A-R2)u(A-R 1-A-R3 )v{A-R 1-A-RS )w
-A-R 1-A-J ({R4)t(Cap)J
wherein A is a carboxy linking moiety having the formula
O
~i
-C-
R1 is arylene, preferably a 1,4-phenylene moiety having the formula
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38
/ \
such that when A units and R 1 units are taken together in the formula A-R 1-A
they form
a terephthalate unit having the formula
O O
-C ~ ~ C
R2 units are ethyleneoxy or 1,2-propyleneoxy. R2 units are combined with
terephthalate moieties to form (A-R1-A-R2) units having the formula
0 0
-c ~ ~ c-o-cHR'cHR~-
wherein R' and R" are either hydrogen or methyl provided that R' and R" are
not both
methyl at the same time.
R3 units are trifunctional, ester-forming, branching moieties having the
formula
O
I
-O-CH2-CH-CH2-O-
Preferably R3 units comprise a glycerol moiety which is placed into the soil
release
polymer backbone to provide a branch point. When R3 units are combined with
terephthalate moieties to form units of the polymer backbone, for example, (A-
R 1-A-
R3)-A-Rl-A units, these units have the formula
O
-C ~ ~ C-O-CH2-CH-CH2-O-C ~ ~ C
0 0 0 0
or the formula
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39
O
CH2
-C ~ ~ C-O-CH2-CH-O-C ~ ~ C
O O O O
wherein one terephthalate residue is taken to be a part of the {A-Rl-A-R3)
unit while the
second terephthalate comprises a part of another backbone unit, such as a (A-R
1-A-R2)
unit, a (A-R 1-A-RS ) unit, a -A-R 1-A-[(R4)t(Cap)] unit or a second (A-R 1-A-
R3 ) unit.
The third functional group, which is the beginning of the branching chain, is
also
typically bonded to a terephthalate residue also a part of a {A-R 1-A-R2)
unit, a (A-R 1-A-
RS) unit, a -A-Rl-A-[(R4)t{Cap)] unit or another (A-R1-A-R3) unit.
An example of a section of a soil release polymer containing a "trifunctional,
ester-forming, branching moiety" R3 unit which comprises a glycerol unit, has
the
formula
-(CH2CH20~-C ~ ~ C-O -
O O
R4 units are R2, R3 or RS units.
RS units are units having the formula
Rto Rio
-O-R~-'(O-R9)i O
R~o Rto
wherein R9 is C2-C6 linear alkylene, C3-C6 branched alkylene, and mixtures
thereof;
preferably R 10 is independently selected from hydrogen or -L-S03-M+; wherein
L is a
side chain moiety selected from the group consisting of alkylene, oxyalkylene,
alkyleneoxyalkylene, arylene, oxyarylene, alkyleneoxyarylene,
poly(oxyalkylene),
oxyalkyleneoxyarylene, poly(oxyalkylene)oxyarlyene,
alkylenepoly(oxyalkylene),and
mixtures thereof; M is hydrogen or a salt forming cation; i has the value of 0
or 1;
Each carbon atom of the R9 units is substituted by R10 units that are
independently selected from hydrogen or -L-S03-M+, provided no more than one -
L-
S03-M+ units is attached to an R9 unit; L is a side chain connecting moiety
selected
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from the group consisting of alkylene, oxyalkylene, alkyleneoxyalkylene,
arylene,
oxyaryiene, alkyleneoxyarylene, poly(oxyalkylene), oxyalkyleneoxyarylene,
poly(oxyalkylene)oxyarlyene, alkylenepoly(oxyalkylene),and mixtures thereof.
M is a cationic moiety selected from the group consisting of lithium, sodium,
potassium, calcium, and magnesium, preferably sodium and potassium.
Preferred RS moieties are essentially R 10 substituted C2-C6 alkylene chains.
The RS units comprise either one C2-C6 alkylene chain substituted by one or
more
independently selected Rl0 moieties (preferred) or two C2-C6 alkylene chains
said
alkylene chains joined by an ether oxygen linkage, each alkylene chain
substituted by
one or more independently selected R 10 moieties, that is RS may comprise two
separate
R9 units, each of which is substituted by one or more independently selected
R10
moieties. Preferably only one carbon atom of each R9 moiety is substituted by
an -L-
S03-M+ unit with the remaining R10 substituents comprising a hydrogen atom.
When
the value of the index i is equal to 1 (two R9 units comprise the RS unit), a
preferred
formula is
Rio R~o Rlo R~o
-O-C C O C ~ -O
R~o Rio Rio Rio
wherein each R9 comprises a C2 alkylene moiety. Preferably one R 1 ~ moiety is
-L-
S03-M~, preferably the C2 carbon is substituted by the -L-S03-M+ moiety, and
the
balance are hydrogen atoms, having therefore a formula:
-CHCH2-O-CH2CH2-
CH2(OCH2CH2~S03-M+
wherein L is a polyethyleneoxymethyl substituent, x is from 0 to about 20.
As used herein, the term "RS moieties consist essentially of units
Rio Rio
-O-'R'~.,(O-R9)i O
R~0 Rlo
having the index i equal to 0 wherein R 10 units are hydrogen and one R 10
units is equal
to -L-S03-M+, wherein L is a side chain connecting moiety selected from the
group
consisting of alkylene, alkenylene, alkoxyalkylene, oxyalkylene, arylene,
alkylarylene,
alkoxyarylene and mixtures thereof', refers to the preferred compounds of the
present
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41
invention wherein the R 10 moieties consist of one -L-S03-M+ moiety and the
rest of the
R10 moieties are hydrogen atoms, for example a
-O-CH2-CH-O-
CH2(OCH2CH2)xSO3- Na+
which is capable of inclusion into the polymeric backbone of the soil release
polymers of
the present invention as an -A-RS-A- backbone segment. The units are easily
incorporated into the oligomer or polymer backbone by using starting materials
having
the general formula
HO-CHz-CH-OH
CH2(OCH2CH2~S03 Na+
wherein x, for the purposes of the L moiety of the present invention, is from
0 to 20.
Other suitable monomers capable of inclusion into the backbone of the type A
preferred non-cotton soil release polymers of the present invention as R5
moieties
includes the alkylene poly(oxyalkylene)oxyarylene containing monomer having
the
general formula
HO-CH2-CH-OH
CH2(OCHZCHZ~O ~!\ S03~Na+
wherein x is 0 to 20. A further example of a preferred monomer resulting in a
preferred
RS unit wherein i is equal to 0, are the sodiosulfopoly(ethyleneoxy)methyl-1,2-
propanediols having the formula
HO-CH2-CH-OH
CH2(OCHZCHZ~SO3 Na+
wherein x is firom 0 to about 20; more preferred are the monomers
OH
i
HO-CH2-CH-CH2-OH o~ HO-CH2-CH-CH2
OCH2CH2S03 Na+ OCH2CH2S03 Na+
The preferred non-cotton soil release agents of the present invention in
addition
to the afore-mentioned R 1, R2, R3, R4, and RS units also comprise one or more
capping
groups, -(Cap). The capping groups are independently selected from ethoxylated
or
propoxylated hydroxyethane and propanesulfonate units of the formula
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42
(M03S)(CH2)m(RI l0)n-, where M is a salt forming canon such as sodium or
tetralkylammonium as described herein above, R11 is ethylene or propylene or a
mixture
thereof, m is 0 or I, and n is from 1 to 20, preferably n is from 1 to about
4; sulfoaroyl
units of the formula -(O)C(C6H4)(S03-M+), wherein M is a salt forming cation
as
described herein above; modified poly(oxyethylene)oxy monoalkyl ether units of
the
formula R 120(CH2CH20)k- wherein R 12 contains from 1 to 4 carbon atoms, R 12
is
preferably methyl, and k is from about 3 to about 100, preferably about 3 to
about 50,
more preferably 3 to about 30; and ethoxylated or propoxylated phenolsulfonate
end-
capping units of the formula M03S(C6H4)(OR13)n0-, wherein n is from to 20; M
is a
salt-forming cation; and R 13 is ethylene, propylene and mixtures thereof.
Most preferred end capping unit is the isethionate-type end capping unit which
is
a hydroxyethane moiety, (M03S)(CH2)m(R11O)n_, preferably R11 is ethyl, m is
equal
to0,andnisfrom2to4.
The value of t is 0 or 1; the value of a is from about 0 to about 60; the
value of v
is from about 0 to about 35; the value of w is from 0 to 35.
Preferred non-cotton soil release polymers of the present invention having the
formula
[(Cap)(R4)t) [(A-R 1-A-R2)u(A-R 1-A-R3)v(A-R 1-A-RS)w
-A-R 1-A-~ ~(R4)t(CaP)l
can be conveniently expressed as the following generic structural formula
0 0 0 0
Na43S(CHzCHzOyz.sCHzCFiz O-C ~ ~ C-OCHzCH O-C ~ ~ C-OCHz fCFi
R a ~ C~'Hz w
OCHzCH2S03Na
CI-Iz
/ ~ O OCHzCH ~O ~ ~ O_p~lz~~pCf.IzCHz~.sS03Na
v v+1
The following structure is an example of the preferred non-cotton soil release
polymers of the present invention.
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43
I \ ~_~:~ ~~ / \
Na03S(CH=CH~O~.sCH~CH,
R ~
1.7-2.1' ~ 2.5
OCH:CH,SO3Na
CH2
O-O /~~ O OCHzCH O-O / \ O_OCHzCH(OCH2~2h~sS~Na
0.15 1.~5
The above-described preferred non-cotton soil release agents are fully
described in
U.S. Patent Application Serial No. 08/545,351 filed November 22, 1995 which is
a
continuation-in-part of U.S. Patent Application Serial No. 08/355,938 filed
December
14, 1994, both of which are incorporated herein by reference. Other non-cotton
soil
release polymers suitable for use in the compositions of the present invention
are further
described herein below.
The preferred non-cotton SRA's can be further described as oligomeric esters
comprising: ( 1 ) a backbone comprising (a) at least one unit selected from
the group
consisting of dihydroxysulfonates, polyhydroxy sulfonates, a unit which is at
least
trifunctional whereby ester linkages are formed resulting in a branched
oligomer
backbone, and combinations thereof; (b) at least one unit which is a
terephthaloyl
moiety; and (c) at least one unsulfonated unit which is a 1,2-oxyalkyleneoxy
moiety; and
(2) one or more capping units selected from nonionic capping units, anionic
capping
units such as alkoxylated, preferably ethoxylated, isethionates, alkoxylated
propanesulfonates, alkoxylated propanedisulfonates, alkoxylated
phenolsulfonates,
sulfoaroyl derivatives and mixtures thereof. Preferred are esters of the
empirical
formula:
{(CAP)x(EG/PG)y'(DEG)y"(PEG)y"'(T)z(SIP)z'(SEG)q(B)m}
wherein CAP, EG/PG, PEG, T and SIP are as defined as terephthaloyl (T),
sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units,
end-caps
(CAP), poly(ethyleneglycol) (PEG), (DEG) represents di(oxyethylene)oxy units,
(SEG)
represents units derived from the sulfoethyl ether of glycerin and related
moiety units,
(B) represents branching units which are at least trifunctional whereby ester
linkages are
formed resulting in a branched oligomer backbone, x is from about 1 to about
12, y' is
from about 0.5 to about 25, y" is from 0 to about 12, y"' is from 0 to about
10, y'+y"+y"'
totals from about 0.5 to about 25, z is from about 1.5 to about 25, z' is from
0 to about
12; z + z' totals from about 1.5 to about 25, q is from about 0.0S to about
12; m is from
about 0.01 to about 10, and x, y', y", y"', z, z', q and m represent the
average number of
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44
moles of the corresponding units per mole of said ester and said ester has a
molecular
weight ranging from about 500 to about 5,000.
Preferred SEG and CAP monomers for the above esters include Na-2-(2-,3-
dihydroxypropoxy)ethanesulfonate ("SEG"), Na-2-{ 2-(2-hydroxyethoxy) ethoxy }
ethanesulfonate ("SE3") and its homologs and mixtures thereof and the products
of
ethoxylating and sulfonating allyl alcohol. Preferred SRA esters in this class
include the
product of transesterifying and oligomerizing sodium 2-{2-(2-hydroxy-
ethoxy)ethoxy}ethanesulfonate and/or sodium 2-[2-{2-(2-hydroxyethoxy)ethoxy}-
ethoxy)ethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy) ethane sulfonate,
EG,
and PG using an appropriate Ti(IV) catalyst and can be designated as
(CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+03S[CH2CH20]3.5)-
and B is a unit from glycerin and the mole ratio EG/PG is about 1.7:1 as
measured by
conventional gas chromatography after complete hydrolysis.
Preferred non-cotton soil release agent - B. A second preferred class of
suitable
SRA's include a sulfonated product of a substantially linear ester oligomer
comprised of
an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units
and allyl-
derived sulfonated terminal moieties covalently attached to the backbone Such
ester
oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the
product of
(a) with dimethyl tere~hthalate ("DMT") and 1,2-propylene glycol ("PG") in a
two-stage
transesterification/oligomerization procedure; and (c) reacting the product of
(b) with
sodium metabisulfite in water.
Suitable for use in the laundry detergent compositions of the present
invention
are preferred non-cotton soil release polymers comprising:
a) one or two terminal units selected from the group consisting of
i) -(CH2)q(CHS03M)CH2S03M,
ii) -(CH2)q(CHS02M)CH2S03M,
iii) -CH2CH2S03M,
iv) and mixtures thereof; wherein q has the value from 1 to about 4,
M is a water soluble cation, preferably sodium;
b) a backbone comprising:
i) arylene units, preferably terephthalate units having the formula:
O O
-C ~ ~ C
ii) ethyleneoxy units having the formula:
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4S
-O(CH~CH20)nCH2CH20-
wherein the value of n is from about 1 to about 20; and
iii) 1,2-propyleneoxy units having the formula:
-O(CH2CH(CH3)O}nCH2CH(CH3)O-
wherein the value of n is from about 1 to about 20, and wherein further the
preferred
backbone of this preferred non-cotton soil release polymer has a backbone
comprising
arylene repeat units which alternate with the ethyleneoxy and 1,2-propyleneoxy
units,
such that the mole ratio of ethyleneoxy to 1,2-propyleneoxy units is from 0:1
to about
0.9:0.1, preferably from about 0:1 to about 0.4:0.6, more preferably the
arylene units
alternate with essentially 1,2-propyleneoxy units.
However, other combinations of the above-identified units may be used to form
non-cotton soil release polymers suitable for use in the compositions of the
present
invention. These combinations are more thoroughly described in U.S. Patent
4,968,451,
Scheibel et al., issued November 6, 1990 and incorporated herein by reference.
Preferred non-cotton soil release agent - C. Suitable for use in the laundry
detergent compositions of the present invention are preferred non-cotton soil
release
polymers having the formula
(CaP) ~(A-R 1-A-R2)u(A-R3-A-R2)v-A-R4-A-) (CaP)
wherein A is a carboxy linking moiety, preferably A is a carboxy linking
moiety having
the formula
O o
ii ii
or -C_-O-
R 1 is an arylene moiety, preferably 1,4-phenylene moiety having the formula
/ \
wherein for R I moieties, the degree of partial substitution with arylene
moieties other
than 1,4-phenylene should be such that the soil release properties of the
compound are
not adversely affected to any great extent. Generally, the partial
substitution which can
be tolerated will depend upon the backbone length of the compound.
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R2 moieties are ethylene moieties or substituted ethylene moieties having C 1-
C4
alkyl or alkoxy substituents. As used herein, the term "the R2 moieties are
essentially
ethylene moieties or substituted ethylene moieties having C 1-C4 alkyl or
alkoxy
substituents" refers to compounds of the present invention where the R2
moieties consist
entirely of ethylene or substituted ethylene moieties or a partially
substituted with other
compatible moieties. Examples of these other moieties include 1,3-propylene,
1,4-
butylene, 1,5-pentylene, or 1,6-hexylene, 1,2-hydroxyalkylenes and
oxyaikylenes.
For the R2 moieties, the degree of partial substitution with these other
moieties
should be such that the soil release properties of the compounds are not
adversely
affected to any great extent. For example, for polyesters made according to
the present
invention with a 75:25 mole ratio of diethylene glycol (-CH2CH20CH2CH2-) to
ethylene glycol (ethylene) have adequate soil release activity.
For the R3 moieties, suitable substituted C2-C 1 g hydrocarbylene moieties can
include substituted C2-C 12 alkylene, alkenylene, arylene, alkarylene and like
moieties,
The substituted alkylene or alkenylene moieties can be linear, branched or
cyclic. AIso,
the R3 can a11 be the same (e.g. a11 substituted arylene) or a mixture (e.g. a
mixture of
substituted arylenes and substituted alkylenes). Preferred R3 moieties are
those which
are substituted 1,3-phenylene, preferably 5-sulfo-1,3-phenylene. R3 moieties
are also -
A-[(R2-A-R4))-Cap wherein R4 is R1, R3, and mixtures thereof.
The preferred (Cap) moieties comprise units having the formula
-[(R.SO~(CHZCH20)n]X
wherein RS is C 1-C4 alkylene, or the moiety -R2-A-R6- wherein R6 is C2-C 12
alkylene,
alkenylene, arylene or alkarylene moiety, X is C 1-C,~ alkyl, preferably
methyl; the
indices m and n are such that the moiety -CH2CH20- comprises at least 50% by
weight
of the moiety
-[(RSO~n(CH2CH20)n]X
provided that when RS is the moiety -R2-A-R6- , m is at least 1; each n is at
least about
10, the indices a and v are such that the sum of a + v is from about 3 to
about 25; the
index w is 0 or at least 1; and when w is at least 1, the indices u, v and w
have the values
such that the sum of a + v + w is from about 3 to about 25.
An example of this type of non-cotton soil release block polyester has the
formula
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o ~ ~ 0 0 0 0 0
X-(OCH,CH,)n-(OC~CO-R2)~ (OC-R3-CO-R2h-OC-R4-CO-(CH,CH~OyX
wherein the R2 moieties are essentially ethylene moieties, 1,2-propylene
moieties, and
mixtures thereof; the R3 moieties are a11 potassium or preferably sodium 5-
sulfo-1,3-
phenylene moieties; the R4 moieties are R1 or R3 moieties, or mixtures
thereof; each X
is ethyl, methyl, preferably methyl; each n is from about 12 to about 43; when
w is 0, a +
v is from about 3 to about 10; when w is at least 1, a + v + w is from about 3
to about 10.
The above non-cotton soil release polymers of the formula
(CaP)[(A-R 1-A-R2)u(A-R3_A-R2)v_A-R4_A_](Cap)
are further described in detail in U.S. Patent 4,702,857, Gosselink, issued
October 27,
1987 and incorporated herein by reference.
In addition to the above-described non-cotton soil release polymers, other
soil
release polymers suitable for use in the liquid laundry detergent compositions
of the
present invention are further described herein below.
Any other anionic non-cotton soil release agent is suitable for use in the
compositions of the present invention alone or in combination except for
carboxy-
methylcellulose (CMC) which cannot be used alone. If the formulator selects
CMC for
use as an anionic soil release agent in the laundry detergent compositions of
the present
invention, carboxymethylcellulose must be present in an amount greater than
0.2% by
weight, of the composition.
Synthesis of an Oli;~omer of Sodium 2-[~2-
Hydroxvethoxv)ethox~lethanesulfonate.
Dimethyl Terephthalate, Sodium 2-(2,3-Dil~droxypropoxylethanesulfonate.
Ethylene
Glycol. and Progvlene Glycol)
To a 250m1, three neck, round bottom flask equipped with a magnetic stirring
bar, modified Claisen head, condenser (set for distillation), thermometer, and
temperature controller (Therm-O-Watch~, I2R) is added sodium 2-[2-(2-
hydroxyethoxy)ethoxy]ethanesulfonate (7.0g, 0.030 mot), dimethyl terephthalate
( 14.4g,
0.074 moI), sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate (6.6g, 0.030 mol),
ethylene glycol (Baker, 14.0g, 0.225 mol), propylene glycol (Fisher, 18.3g,
0.240 mol),
and titanium (IV) propoxide (0.01 g, 0.02% of total reaction weight). This
mixture is
heated to l80~C and maintained at that temperature overnight under argon as
methanol
distills from the reaction vessel. The material is transferred to a 500m1,
single neck,
round bottom flask and heated gradually over about 20 minutes to 240~C in a
Kugelrohr
apparatus (Aldrich) at about 0.1 mm Hg and maintained there for 110 minutes.
The
reaction flask is then allowed to air cool quite rapidly to near room
temperature under
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48
vacuum (~30 min.) The reaction affords 24.4g of the desired oligomer as a
brown glass.
A 13C-NMR(DMSO-d6) shows a resonance for -C(O)OCH2CH20(O)C- at 63.2 ppm
(diester) and a resonance for -C(O)OCH2CH20H at 59.4 ppm (monoester). The
ratio
of the diester peak to monoester peak is measured to be 8. Resonances at 51.5
ppm
and 51.6 ppm representing the sulfoethoxy groups (-CH2S03Na) are also present.
A
1 H-NMR{DMSO-d6) shows a resonance at ~7.9 ppm representing terephthalate
aromatic hydrogens. Analysis by Hydrolysis-GC shows that the mole ratio of
incorporated ethylene glycol to incorporated propylene glycol is 1.6: I . The
solubility is
tested by weighing a small amount of material into a vial, adding enough
distilled water
to make a 35% by weight solution, and agitating the vial vigorously. The
material is
readily soluble under these conditions.
Bleachin~Coimpounds - BleachingAgents and Bleach Activators - The detergent
compositions herein may optionally contain bleaching agents or bleaching
compositions
containing a bleaching agent and one or more bleach activators. When present;
bleaching agents will typically be at levels of from about 1 % to about 30%,
more
typically from about 5% to about 20%, of the detergent composition, especially
for fabric
laundering. if present, the amount of bleach activators will typically be from
about 0.1
to about 60%, more typically from about 0.5% to about 40% of the bleaching
composition comprising the bleaching agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching agents useful for
detergent compositions in textile cleaning, hard surface cleaning, or other
cleaning
purposes that are now known or become known. These include oxygen bleaches as
well
as other bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g.,
mono- or
tetra-hydrate) can be used herein.
Another category of bleaching agent that can be used without restriction
encompasses percarboxylic acid bleaching agents and salts thereof. Suitable
examples of
this class of agents include magnesium monoperoxyphthalate hexahydrate, the
magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric
acid
and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S.
Patent
4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446,
Burns
et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al,
published
February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1,
1983.
Highly preferred bleaching agents also include 6-nonylamino-b-oxoperoxycaproic
acid
as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
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Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching
compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate"
bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium
peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont)
can
also be used.
A preferred percarbonate bleach comprises dry particles having an average
particle size in the range from about 500 micrometers to about l,000
micrometers, not
more than about 10% by weight of said particles being smaller than about 200
micrometers and not more than about 10% by weight of said particles being
larger than
about 1,250 micrometers. Optionally, the percarbonate can be coated with
silicate,
borate or water-soluble surfactants. Percarbonate is available from various
commercial
sources such as FMC, Solvay and Tokai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are
preferably combined with bleach activators, which lead to the in situ
production in
aqueous solution (i.e., during the washing process) of the peroxy acid
corresponding to
the bleach activator. Various nonlimiting examples of activators are disclosed
in U. S.
Patent 4,91 S,854, issued April 10, 1990 to Mao et al, and U.S. Patent
4,412,934. The
nonanoyloxybenzene sulfonate (HOBS) and tetraacetyl ethylene diamine (TAED)
activators are typical, and mixtures thereof can also be used. See also U.S.
4,634,55l for
other typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators are those of the formulae:
R1N(RS)C(O)R2C(O)L or R1C(O)N(RS)R2C(O)L
wherein R 1 is an alkyl group containing from about 6 to about 12 carbon
atoms, R2 is an
alkylene containing from 1 to about 6 carbon atoms, RS is H or alkyl, aryl, or
alkaryl
containing from about 1 to about 10 carbon atoms, and L is any suitable
leaving group.
A leaving group is any group that is displaced from the bleach activator as a
consequence of the nucleophilic attack on the bleach activator by the
perhydrolysis
anion. A preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-
octanamido-caproyl)oxybenzenesulfonate, (6-
nonanamidocaproyI)oxybenzenesulfonate,
(6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described
in U.S.
Patent 4,634,551, incorporated herein by reference.
Another class of bleach activators comprises the benzoxazin-type activators
disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990,
incorporated
herein by reference. A highly preferred activator of the benzoxazin-type is:
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O
II
CEO
o ..~ o
'N
Still another class of preferred bleach activators includes the acyl lactam
activators, especially acyl caprolactams and acyl valerolactams of the
formulae:
O O
II II
O C-C H2-C H2 O C-C H2- ~ H2
II I ~ II I
R6-C-N'C H2-C H2 C H2 R6 C-N.~ C H2-C H2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from I to about
12 carbon atoms. Highly preferred lactam activators include benzoyl
caprolactam,
octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl
caprolactarri,
decanoyl caprolactam, undecenoyl caprolactam, benzoyi valerolactam, octanoyI
valerolactam, decanoyl valeroIactam, undecenoyl valerolactam, nonanoyl
valerolactam,
3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S.
Patent
4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by
reference,
which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed
into sodium
perborate.
Bleaching agents other than oxygen bleaching agents are also known in the art
and can be utilized herein. One type of non-oxygen bleaching agent of
particular interest
includes photoactivated bleaching agents such as the sulfonated zinc and/or
aluminum
phthalocyanines. See U.S. Patent 4,033,718, issued July 5, l977 to Holcombe et
al. If
used, detergent compositions will typically contain from about 0.025% to about
I.25%,
by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of a manganese
compound. Such compounds are well known in the art and include, for example,
the
manganese-based catalysts disclosed in U.S. Pat) 5,246,621, U.S. Pat.
5,244,594; U.S.
Pat. 5,194,416; U. S. Pat. 5,114,606; and European Pat. App. Pub. Nos. S49,271
A 1,
549,272A I , 544,440A2, and 544,490A 1; Preferred examples of these catalysts
include
MnIV2(u-O)3(I,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, ~II12(u_O)I(u_
OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)2, MnIV4(u-O)6(1,4,7-
triazacyclononane)4(C104)4, ~ MnIIIMnIV4(u-O)1(u-OAc)2-(1,4,7-trimethyl-1,4,7-
triazacyclononane)2(C104)3, MnIV( I ,4,7-trimethyl- l,4,7-triazacyclononane)-
(OCH3)3(PF6), and mixtures thereof Other metal-based bleach catalysts include
those
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disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of manganese
with
various complex ligands to enhance bleaching is also reported in the following
United
States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117;
5,274,147;
5,153.161; and 5,227,084.
As a practical matter, and not by way of limitation, the compositions and
processes herein can be adjusted to provide on the order of at least one part
per ten
million of the active bleach catalyst species in the aqueous washing liquor,
and will
preferably provide from about 0.1 ppm to about 700 ppm, more preferably from
about 1
ppm to about 500 ppm, of the catalyst species in the laundry liquor.
Cobalt bleach catalysts useful herein are known, and are described, for
example,
in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inor~.
Bioinor~.
Mech., ( 1983), 2, pages 1-94. The most preferred cobalt catalyst useful
herein are cobalt
pentaamine acetate salts having the formula [Co{NH3)50Ac) Ty, wherein "OAc"
represents an acetate moiety and "Ty" is an anion, and especially cobalt
pentaamine
acetate chloride, (Co(NH3)50Ac]C12; as well as [Co(NH3)50Ac](OAc)2;
(Co(NH3)SOAc](PF6)2; (Co(NH3)SOAc](S04); (Co(NH3)50Ac](BF4)2; and
[Co(NH3)50Ac](N03)2 {herein "PAC").
These cobalt catalysts are readily prepared by known procedures, such as
taught
for example in the Tobe article and the references cited therein, in U.S.
Patent 4,810,410,
to Diakun et al, issued March 7,1989, J. Chem. Ed. ( 1989), 66 ( I 2), 1043-
45; The
Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-
Hall;
l970), pp. 461-3; Inorg. Chem., 18, 1497-l502 (1979); Inorg-Chem., 21, 288l-
2885
( 1982); Inor;~. Chem., 18, 2023-2025 ( 1979); Inorg. Synthesis, 173-176 (
1960); and
Journal of Physical Chemistry, 56, 22-25 (1952).
As a practical matter, and not. by way of limitation, the automatic
dishwashing
compositions and cleaning processes herein can be adjusted to provide on the
order of at
least one part per hundred million of the active bleach catalyst species in
the aqueous
washing medium, and will preferably provide from about 0.0l ppm to about 25
ppm,
more preferably from about 0.05 ppm to about 10 ppm, and most preferably from
about
0.1 ppm to about 5 ppm, of the bleach catalyst species in the wash liquor. In
order to
obtain such levels in the wash liquor of an automatic dishwashing process,
typical
automatic dishwashing compositions herein will comprise from about 0.0005% to
about
0.2%, more preferably from about 0.004% to about 0.08%, of bleach catalyst,
especially
manganese or cobalt catalysts, by weight of the cleaning compositions.
Clay Soil Removal/Anti-redeposition Aeents - The compositions of the present
invention can also optionally contain water-soluble ethoxylated amines having
clay soil
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removal and antiredeposition properties. Granular detergent compositions which
contain
these compounds typically contain from about 0.01 % to about 10.0% by weight
of the
water-soluble ethoxylates amines; liquid detergent compositions typically
contain about
0.01 % to about 5%.
The most preferred soil release and anti-redeposition agent is ethoxylated
tetraethylenepentamine. Exemplary ethoxylated amines are further described in
U.S.
Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred
clay soil
removal-antiredeposition agents are the cationic compounds disclosed in
European
Patent Application 111,96S, Oh and Gosselink, published June 27, 1984. Other
clay soil
removal/antiredeposition agents which can be used include the ethoxylated
amine
polymers disclosed in European Patent Application 111,984, Gosselink,
published June
27, 1984; the zwitterionic polymers disclosed in European Patent Application
112,592,
Gosselink, published July 4, 1984; and the amine oxides disclosed in U. S.
Patent
4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or
anti
redeposition agents known in the art can also be utilized in the compositions
herein. See
U.S. Patent 4,891,160, VanderMeer, issued January 2, 1990 and WO 95/32272,
published November 30, 1995. Another type of preferred antiredeposition agent
includes
the carboxy methyl cellulose (CMC) materials. These materials are well known
in the
art.
Polymeric Dispersin~gents - Polymeric dispersing agents can advantageously
be utilized at levels from about 0.1 % to about 7%, by weight, in the
compositions herein,
especially in the presence of zeolite and/or layered silicate builders.
Suitable polymeric
dispersing agents include polymeric polycarboxylates and polyethylene glycols,
although
others known in the art can also be used. It is believed, though it is not
intended to be
limited by theory, that polymeric dispersing agents enhance overall detergent
builder
performance, when used in combination with other builders (including lower
molecular
weight polycarboxylates) by crystal growth inhibition, particulate soil
release
peptization, and anti-redeposition.
Polymeric polycarboxylate materials can be prepared by polymerizing or
copolymerizing suitable unsaturated monomers, preferably in their acid form.
Unsaturated monomeric acids that can be polymerized to form suitable polymeric
polycarboxylates include acrylic acid, malefic acid (or malefic anhydride),
fumaric acid,
itaconic acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic acid.
The presence in the polymeric polycarboxylates herein or monomeric segments,
containing no carboxylate radicals such as vinylmethyl ether, styrene,
ethylene, etc. is
suitable provided that such segments do not constitute more than about 40% by
weight.
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Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid.
Such acrylic acid-based polymers which are useful herein are the water-soluble
salts of
polymerized acrylic acid. The average molecular weight of such polymers in the
acid
form preferably ranges from about 2,000 to 10,000, more preferably from about
4,000 to
7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of
such acrylic
acid polymers can include, for example, the alkali metal, ammonium and
substituted
ammonium salts. Soluble polymers of this type are known materials. Use of
polyacrylates of this type in detergent compositions has been disclosed, for
example, in
Diehl, U.S. Patent 3,308,067, issued march 7, l967.
Acrylic/maleic-based copolymers may also be used as a preferred component of
the dispersing/anti-redeposition agent. Such materials include the water-
soluble salts of
copolymers of acrylic acid and malefic acid. The average molecular weight of
such
copolymers in the acid form preferably ranges from about 2,000 to 100,000,
more
preferably from about 5,000 to 75,000, most preferably from about 7,000 to
65,000. The
ratio of acrylate to maleate segments in such copolymers will generally range
from about
30:l to about 1:1, more preferably from about l0:1 to 2:I. Water-soluble salts
of such
acrylic acidfmaleic acid copolymers can include, for example, the alkali
metal,
ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers
of
this type are known materials which are described in European Patent
Application No.
66915, published December 15, 1982, as well as in EP 193,360, published
September 3,
1986, which also describes such polymers comprising hydroxypropylacrylate.
Still other
useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers.
Such
materials are also disclosed in EP 193,360, including, for example, the
45/45/10
terpolymer of acrylic/maleic/vinyl alcohol.
Another polymeric material which can be included is polyethylene glycol (PEG).
PEG can exhibit dispersing agent performance as well as act as a clay soil
removal-
antiredeposition agent. Typical molecular weight ranges for these purposes
range from
about 500 to about 100,000, preferably from about 1,000 to about 50,000, more
preferably from about 1,500 to about 10,000.
Polyaspartate and polyglutamate dispersing agents may also be used, especially
in conjunction with zeolite builders. Dispersing agents such as polyaspartate
preferably
have a molecular weight (avg.) of about 10,000.
Brightener - Any optical brighteners or other brightening or whitening agents
known in the art can be incorporated at levels typically from about 0.01 % to
about 1.2%,
by weight, into the detergent compositions herein. Commercial optical
brighteners
which may be useful in the present invention can be classified into subgroups,
which
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include, but are not necessarily limited to, derivatives of stilbene,
pyrazoline, coumarin,
carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and
6-
membered-ring heterocycles, and other miscellaneous agents. Examples of such
brighteners are disclosed in "The Production and Application of Fluorescent
Brightening
Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
Specific examples of optical brighteners which are useful in the present
compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on
December 13, 1988. These brighteners include the PHORWHITE series of
brighteners
from Verona. Other brighteners disclosed in this reference include: Tinopal
UNPA,
Tinopal CBS and Tinopal SBM; available from Ciba-Geigy; Artic White CC and
Artic
White CWD, the 2-(4-styryl-phenyl)-2H-naptho[1,2-d]triazoles; 4,4'-bis-(1,2,3-
triazol-2-
yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins. Specif c
examples of
these brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-
bis(benzimidazol-2-
yl)ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-
styryl-
naptho[1,2-d]oxazole; and 2-(stilben-4-yl)-2H-naphtho[1,2-d]triazole. See also
U.S.
Patent 3,646,015, issued February 29, 1972 to Hamilton.
Dve Transfer Inhibiting A ents - The compositions of the present invention
may also include one or more materials effective for inhibiting the transfer
of dyes from
one fabric to another during the cleaning process. Generally, such dye
transfer inhibiting
agents include polyvinyl pyrrolidone polymers, polyarnine N-oxide polymers,
copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese
phthalocyanine,
peroxidases, and mixtures thereof. .If used, these agents typically comprise
from about
0.01 % to about 10% by weight of the composition, preferably from about 0.01 %
to about
5%, and more preferably from about 0.05% to about 2%.
More specifically, the polyami~ne N-oxide polymers preferred for use herein
contain units having the following structural formula: R-Ax-P; wherein P is a
polymerizable unit to which an N-O group can be attached or the N-O group can
form
part of the polymerizable unit or the N-O group can be attached to both units;
A is one of
the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or l; and R
is aliphatic,
ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any
combination
thereof to which the nitrogen of the N-O group can be attached or the N-O
group is part
of these groups. Preferred polyamine N-oxides are those wherein R is a
heterocyclic
group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and
derivatives
thereof.
The N-O group can be represented by the following general structures:
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O O
(Rt hc- i 'yR2)y~ =N yR~ )x
(R3)z
wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups
or
combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group
can be
attached or form part of any of the aforementioned groups. The amine oxide
unit of the
polyamine N-oxides has a pKa <10, preferably pKa <7, more preferred pKa <6.
Any polymer backbone can be used as long as the amine oxide polymer formed is
water-soluble and has dye transfer inhibiting properties. Examples of suitable
polymeric
backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide,
polyimides,
polyacrylates and mixtures thereof. These polymers include random or block
copolymers
where one monomer type is an amine N-oxide and the other monomer type is an N-
oxide.
The amine N-oxide polymers typically have a ratio of amine to the amine N-
oxide of
10:1 to 1:1,000,000. However, the number of amine oxide groups present in the
polyamine oxide polymer can be varied by appropriate copolymerization or by an
appropriate degree of N-oxidation. The polyamine oxides can be obtained in
almost any
degree of polymerization. Typically, the average molecular weight is within
the range of
500 to l,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to
100,000.
This preferred class of materials can be referred to as "PVNO".
The most preferred polyamine N-oxide useful in the detergent compositions
herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight
of about
50,000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as
a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI
has an
average molecular weight range from S,000 to 1,000,000, more preferably from
5,000 to
200,000, and most preferably from 10,000 to 20,000. {The average molecular
weight
range is determined by light scattering as described in Barth, et al.,
Chemical Analysis,
Vol 1l3. "Modern Methods of Polymer Characterization", the disclosures of
which are
incorporated herein by reference.) The PVPVI copolymers typically have a molar
ratio
of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably
from 0.8:1
to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either
linear or
branched.
The present invention compositions also may employ a polyvinylpyrrolidone
("PVP") having an average molecular weight of from about 5,000 to about
400,000,
preferably from about 5,000 to about 200,000, and more preferably from about
5,000 to
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56
about 50,000. PVP's are known to persons skilled in the detergent field; see,
for
example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference.
Compositions containing PVP can also contain polyethylene glycol ("PEG")
having an
average molecular weight from about 500 to about 100,000, preferably from
about 1,000
to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered
in wash
solutions is from about 2:1 to about 50:1, and more preferably from about 3:1
to about
10:1.
The detergent compositions herein may also optionally contain from about
0.005% to 5% by weight of certain types of hydrophilic optical brighteners
which also
provide a dye transfer inhibition action. If used, the compositions herein
will preferably
comprise from about 0.01% to 1% by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having the structural formula:
Ri Rz
N H H N
N O>--N O C=C O N-'O N
~N H I-I N
R2 503M S~3M R~
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2
is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino,
chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, Rl is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
canon such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-
triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This
particular
brightener species is commercially marketed under the tradename Tinopal-LJNPA-
GX by
Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical
brightener useful in the detergent compositions herein.
When in the above formula, R 1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-
anilino-6-(N-
2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic
acid di-
sodium salt. This particular brightener species is commercially marketed under
the
tradename Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation
such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-
2-
yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener
species is
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57
commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy
Corporation.
The specific optical brightener species selected for use in the present
invention
provide especially effective dye transfer inhibition performance benefits when
used in
combination with the selected polymeric dye transfer inhibiting agents
hereinbefore
described. The combination of such selected polymeric materials (e.g., PVNO
and/or
PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal
SBM-
GX andJor Tinopal AMS-GX) provides significantly better dye transfer
inhibition in
aqueous wash solutions than does either of these two detergent composition
components
when used alone. Without being bound by theory, it is believed that such
brighteners
work this way because they have high affinity for fabrics in the wash solution
and
therefore deposit relatively quick on these fabrics. The extent to which
brighteners
deposit on fabrics in the wash solution can be defined by a parameter called
the
"exhaustion coefficient". The exhaustion coefficient is in general as the
ratio of a) the
brightener material deposited on fabric to b) the initial brightener
concentration in the
wash liquor. Brighteners with relatively high exhaustion coefficients are the
most
suitable for inhibiting dye transfer in the context of the present invention.
Of course, it will be appreciated that other, conventional optical brightener
types
of compounds can optionally be used in the present compositions to provide
conventional
fabric "brightness" benefits, rather than a true dye transfer inhibiting
effect. Such usage
is conventional and well-known to detergent formulations.
Chelatinn Agents - The detergent compositions herein may also optionally
contain one or more iron andlor manganese chelating agents. Such chelating
agents can
be selected from the group consisting of amino carboxylates, amino
phosphonates,
polyfunctionally-substituted aromatic chelating agents and mixtures therein,
all as
hereinafter defined. Without intending to be bound by theory, it is believed
that the
benefit of these materials is due in part to their exceptional ability to
remove iron and
manganese ions from washing solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,
nitrilotri-
acetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates,
diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal,
ammonium, and
substituted ammonium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as chelating agents in the
compositions of the invention when at lease low levels of total phosphorus are
permitted
in detergent compositions, and include ethylenediaminetetrakis
(methylenephosphonates)
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S8
as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or
alkenyl
groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful in the
compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor
et al.
Preferred compounds of this type in acid form are dihydroxydisulfobenzenes
such as 1,2-
dihydroxy-3,S-disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate
("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233,
November
3, 1987, to Hartman and Perkins.
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,
the chelating agents will comprise from about 0.1 % to about 3.0% by weight of
such
compositions.
Suds Suppressors - Compounds for reducing or suppressing the formation of suds
can be incorporated into the compositions of the present invention. Suds
suppression can
be of particular importance in the so-called "high concentration cleaning
process" as
described in U.S. 4,489,455 and 4,489,574 and in front-loading European-style
washing
machines.
A wide variety of materials may be used as suds suppressors, and suds
suppressors are well known to those skilled in the art. See, for example, Kirk
Othmer
Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447
(John
Wiley & Sons, Inc., 1979). One category of suds suppressor of particular
interest
encompasses monocarboxylic fatty acid and soluble salts therein. See U.S.
Patent
2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic
fatty
acids and salts thereof used as suds suppressor typically have hydrocarbyl
chains of 10 to
about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts
include the
alkali metal salts such as sodium, potassium, and lithium salts, and ammonium
and
alkanolammonium salts.
The detergent compositions herein may also contain non-surfactant suds
suppressors. These include, for example: high molecular weight hydrocarbons
such as
paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid
esters of monovalent
alcohols, aliphatic C 1 g-C40 ketones (e.g., stearone), etc. Other suds
inhibitors include
N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to
tetra-
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alkyldiamine chlortriazines formed as products of cyanotic chloride with two
or three
moles of a primary or secondary amine containing 1 to 24 carbon atoms,
propylene
oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester
and
monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate
esters. The
hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
The liquid
hydrocarbons will be liquid at room temperature and atmospheric pressure, and
will have
a pour point in the range of about -40~C and about 50~C, and a minimum boiling
point
not less than about 110~C (atmospheric pressure). It is also known to utilize
waxy
hydrocarbons, preferably having a melting point below about 100~C. The
hydrocarbons
constitute a preferred category of suds suppressor for detergent compositions.
Hydrocarbon suds suppressors are described, for example, in U.S. Patent
4,265,779,
issued May 5, 1981 to Gandolfo et al. The hydrocarbons, thus, include
aliphatic,
alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons
having from
about 12 to about 70 carbon atoms. The term "paraffin," as used in this suds
suppressor
discussion, is intended to include mixtures of true paraffins and cyclic
hydrocarbons.
Another preferred category of non-surfactant suds suppressors comprises
silicone
suds suppressors. This category includes the use of polyorganosiloxane oils,
such as
polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or
resins, and
combinations of polyorganosiloxane with silica particles wherein the
polyorganosiloxane
is chemisorbed or fused onto the silica. Silicone suds suppressors are well
known in the
art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5,
1981 to
Gandolfo et al and European Patent Application No. 89307851.9, published
February 7,
l990, by Starch, M. S. .
Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which
relates to compositions and processes for defoaming aqueous solutions by
incorporating
therein small amounts of polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described, for instance, in
German
Patent Application DOS 2,124,526. Silicone defoamers and suds controlling
agents in
granular detergent compositions are disclosed in U.S. Patent 3,933,672,
Bartolotta et al,
and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein is a suds
suppressing
amount of a suds controlling agent consisting essentially of
(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to
about
1,500 cs. at 25~C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane
resin composed of (CH3)3Si01~2 units of Si02 units in a ratio of from
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(CH3)3 Si01/2 units and to Si02 units of from about 0.6:l to about 1.2:1;
and
(iii) from about 1 to about 20 parts per l00 parts by weight of (i) of a solid
silica
gel.
In the preferred silicone suds suppressor used herein, the solvent for a
continuous
phase is made up of certain polyethylene glycols or polyethylene-polypropylene
glycol
copolymers or mixtures thereof (preferred), or polypropylene glycol. The
primary
silicone suds suppressor is branched/crosslinked and preferably not linear.
To illustrate this point further, typical liquid laundry detergent
compositions with
controlled suds will optionally comprise firom about 0.001 to about 1,
preferably from
about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight
% of said
silicone uds suppressor, which comprises ( 1 ) a nonaqueous emulsion of a
primary
antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous
siloxane or
a silicone resin-producing silicone compound, (c) a finely divided filler
material, and (d~
a catalyst to promote the reaction of mixture components (a), (b) and (c), to
form
silanolates; (2) at least one nonionic silicone surfactant; and (3)
polyethylene glycol or a
copolymer of polyethylene-polypropylene glycol having a solubility in water at
room
temperature of more than about 2 weight %; and without polypropylene glycol.
Similar
amounts can be , used in granular compositions, gels, etc. See also U.S.
Patents
4,978,471, Starch, issued December 18, 1990, and 4,983,3l6, Starch, issued
January 8,
1991, 5,288,43I, Huber et al., issued February 22, 1994, and U.S. Patents
4,639,489 and
4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35.
The silicone suds suppressor herein preferably comprises polyethylene glycol
and
a copolymer of polyethylene glycol/polypropylene glycol, alt having an average
molecular weight of less than about 1,000, preferably between about 100 and
800. The
polyethylene glycol and polyethylene/polypropylene copolymers herein have a
solubility
in water at room temperature of more than about 2 weight %, preferably more
than about
5 weight %.
The preferred solvent herein is polyethylene glycol having an average
molecular
weight of less than about 1,000, more preferably between about 100 and 800,
most
preferably between 200 and 400, and a copolymer of polyethylene
glycoUpolypropylene
glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of between
about 1:1
and 1:10, most preferably between 1:3 and 1:6, of polyethylene
glycol:copolymer of
polyethylene-polypropylene glycol.
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The preferred silicone suds suppressors used herein do not contain
polypropylene
glycol, particularly of 4,000 molecular weight. They also preferably do not
contain
block copolymers of ethylene oxide and propylene oxide, like PLURONIC L 101.
Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-
alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the
silicones
disclosed in U.S. 4,798,679, 4,075,l I8 and EP 150,872. The secondary alcohols
include
the C6-C I 6 alkyl alcohols having a C 1-C I 6 chain. A preferred alcohol is 2-
butyl
octanol, which is available from Condea under the trademark ISOFOL I2.
Mixtures of
secondary alcohols are available under the trademark ISALCHEM 123 from
Enichern.
Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a
weight
ratio of 1:5 to 5:1.
For any detergent compositions to be used in automatic laundry washing
machines, suds should not form to the extent that they overflow the washing
machine.
Suds suppressors, when utilized, are preferably present in a "suds suppressing
amount.
By "suds suppressing amount" is meant that the formulator of the composition
can select
an amount of this suds controlling agent that will sufficiently control the
suds to result in
a low-sudsing laundry detergent for use in automatic laundry washing machines.
The compositions herein will generally comprise from 0% to about 10% of suds
suppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and
salts
therein, will be present typically in amounts up to about 5%, by weight, of
the detergent
composition. Preferably, from about 0.5% to about 3% of fatty monocarboxylate
suds
suppressor is utilized. Silicone suds suppressors are typically utilized in
amounts up to
about 2.0%, by weight, of the detergent composition, although higher amounts
may be
used. This upper limit is practical in nature, due primarily to concern with
keeping costs
minimized and effectiveness of lower amounts for effectively controlling
sudsing.
Preferably from about 0.0l % to about 1 % of silicone suds suppressor is used,
more
preferably from about 0.25% to about 0.5%. As used herein, these weight
percentage
values include any silica that may be utilized in combination with
polyorganosiloxane, as
well as any adjunct materials that may be utilized. Monostearyl phosphate suds
suppressors are generally utilized in amounts ranging from about 0.1 % to
about 2%, by
weight, of the composition. Hydrocarbon suds suppressors are typically
utilized in
amounts ranging from about 0.0l % to about 5.0%, although higher levels can be
used.
The alcohol suds suppressors are typically used at 0.2%-3% by weight of the
finished
compositions.
Alkoxylated Polycarboxylates - Alkoxylated polycarboxylates such as those
prepared from polyacrylates are useful herein to provide additional grease
removal
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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.
Fabric Softeners - Various through-the-wash fabric softeners, especially the
impalpable smectite clays of U.S. Patent 4,062,64?, Storm and Nirschl, issued
December
I3, 1977, as well as other softener clays known in the art, can optionally be
used
typically at levels of from about 0.5% to about 10% by weight in the present
compositions to provide fabric softener benefits concurrently with fabric
cleaning. Clay
softeners can be used in combination with amine and cationic softeners as
disclosed, for
example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent
4,291,071,
Hams et al, issued September 22, I981.
Perfumes - Perfumes and perfumery ingredients useful in the present
compositions and processes comprise a wide variety of natural and synthetic
chemical
ingredients, including, but not limited to, aldehydes, ketones, esters, and
the like. Also
included are various natural extracts and essences which can comprise complex
mixtures
of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk,
patchouli,
balsamic essence, sandalwood oil, pine oil, cedar, and the like. Finished
perfumes can
comprise extremely complex mixtures of such ingredients. Finished perfumes
typically
comprise from about 0.0l % to about 2%, by weight, of the detergent
compositions
herein, and individual perfumery ingredients can comprise from about 0.0001 %
to about
90% of a finished perfume composition.
Non-limiting examples of perfume ingredients useful herein include: 7-acetyl-
1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene; ionone methyl;
ionone
gamma methyl; methyl cedrylone; methyl dihydrojasmonate; methyl 1,6,l0-
trimethyl-
2,5,9-cyclododecatrien-1-yl ketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;
4-acetyl-6-
tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-butanone; benzophenone;
methyl
beta-naphthyl ketone; 6-acetyl-1,1,2,3,3,S-hexamethyl indane; 5-acetyl-3-
isopropyl-
1,1,2,6-tetramethyl indane; 1-dodecanal, 4-(4-hydroxy-4-methylpentyl)-3-
cyclohexene-
1-carboxaldehyde; 7-hydroxy-3,7-dimethyl ocatanal; 10-undecen-1-al; iso-
hexenyl
cyclohexyl carboxaldehyde; formyl tricyclodecane; condensation products of
hydroxycitronellal and methyl anthranilate, condensation products of
hydroxycitronellal
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and indol, condensation products of phenyl acetaldehyde and indol; 2-methyl-3-
(para-
tert-butylphenyl)-propionaldehyde; ethyl vanillin; heliotropin; hexyl cinnamic
aldehyde;
amyl cinnamic aldehyde; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;
coumarin; decalactone gamma; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic
acid
lactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzo-
pyrane; beta-naphthol methyl ether; ambroxane; dodecahydro-3a,6,6,9a-
tetramethyl-
naphtho[2,1 b]furan; cedrol, 5-(2,2,3-trimethylcyclopent-3-enyl)-3-
methylpentan-2-ol; 2-
ethyi-4-(2,2,3-trimethyl-3-cyclopenten-1-yi)-2-buten-1-ol; caryophyllene
alcohol;
tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl salicylate; cedryl
acetate; and
para-(tert-butyl) cyclohexyl acetate.
Particularly preferred perfume materials are those that provide the largest
odor
improvements in finished product compositions containing cellulases. These
perfumes
include but are not limited to: hexyl cinnamic aldehyde; 2-methyl-3-(para-tert-
butylphenyl)-propionaldehyde; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-
tetramethyt
naphthalene; benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; para-
tert-butyl
cyclohexyl acetate; methyl dihydro jasmonate; beta-napthol methyl ether;
methyl beta-
naphthyl ketone; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;
1,3,4,6,7,8-
hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyrane; dodecahydro-
3a,6,6,9a-tetramethylnaphtho[2,1b]furan; anisaldehyde; coumarin; cedrol;
vanillin;
cyclopentadecanolide; tricyclodecenyl acetate; and tricyclodecenyl propionate.
Other perfume materials include essential oils, resinoids, and resins from a
variety of sources including, but not limited to: Peru balsam, Olibanum
resinoid, styrax,
labdanum resin, nutmeg, cassia oil, benzoin resin, coriander and lavandin.
Still other
perfume chemicals include phenyl ethyl alcohol, terpineol, linalool, linalyl
acetate,
geraniol, nerol, 2-(1,1-dimethylethyl)-cyclohexanol acetate, benzyl acetate,
and eugenol.
Carriers such as diethylphthalate can be used in the finished perfume
compositions.
Other Ingredients - A wide variety of other ingredients useful in detergent
compositions can be included in the compositions herein, including other
active
ingredients, carriers, hydrotropes, processing aids, dyes or pigments,
solvents for liquid
formulations, solid fillers for bar compositions, etc. If high sudsing is
desired, suds
boosters such as the C 1 p-C 16 alkanolamides can be incorporated into the
compositions,
typically at 1 %-10% levels. The C 10-C 14 monoethanol and diethanol amides
illustrate a
typical class of such suds boosters. Use of such suds boosters with high
sudsing adjunct
surfactants such as the amine oxides, betaines and sultaines noted above is
also
advantageous. If desired, water-soluble magnesium and/or calcium salts such as
MgCl2,
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64
MgS04, CaCl2, CaS04 and the like, can be added at levels of, typically, 0.1%-
2%, to
provide additional suds and to enhance grease removal performance.
V arious detersive ingredients employed in the present compositions optionally
can be further stabilized by absorbing said ingredients onto a porous
hydrophobic
substrate, then coating said substrate with a hydrophobic coating. Preferably,
the
detersive ingredient is admixed with a surfactant before being absorbed into
the porous
substrate. In use, the detersive ingredient is released from the substrate
into the aqueous
washing liquor, where it performs its intended detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica
(trademark
SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution
containing
3%-5% of C I 3_ 15 e~oxylated alcohol (EO 7) nonionic surfactant. Typically,
the
enzyme/surfactant solution is 2.5 X the weight of silica. The resulting powder
is
dispersed with stirring in silicone oil (various silicone oil viscosities in
the range of 500-
12,500 can be used). The resulting silicone oil dispersion is emulsified or
otherwise
added to the final detergent matrix. By this means, ingredients such as the
aforementioned enzymes, bleaches, bleach activators, bleach catalysts,
photoactivators,
dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be
"protected" for
use in detergents, including liquid laundry detergent compositions.
Liquid detergent compositions can contain water and other solvents as
carriers.
Low molecular weight primary or secondary alcohols exemplified by methanol,
ethanol,
propanol, and isopropanol are suitable. Monohydric alcohols are preferred for
solubilizing surfactant, but polyols such as those containing from 2 to about
6 carbon
atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene
glycol,
glycerine, and 1,2-propanediol) can also be used. The compositions may contain
from
S% to 90%, typically 10% to 50% of such carriers.
The detergent compositions herein will preferably be formulated such that,
during
use in aqueous cleaning operations, the wash water will have a pH of between
about 6. S
and about 11, preferably between about 7.5 and 10.5. Liquid dishwashing
product
formulations preferably have a pH between about 6.8 and about 9Ø Laundry
products
are typically at pH 9-I I. Techniques for controlling pH at recommended usage
levels
include the use of buffers, alkalis, acids, etc., and are well known to those
skilled in the
art.
Granules Manufacture
Adding the alkoxylated cationics of this invention into a crutcher mix,
followed
by conventional spray drying, helps remove any residual, potentially
malodorous, short-
chain amine contaminants. In the event the formulator wishes to prepare an
admixable
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particle containing the alkoxylated cationics for use in, for example, a high
density
granular detergent, it is preferred that the particle composition not be
highly alkaline.
Processes for preparing high density (above 540 g/1) granules are described in
U.S.
Patent 5,366,652. Such particles may be formulated to have an effective pH in-
use of 9,
or below, to avoid the odor of impurity amines. This can be achieved by adding
a small
amount of acidity source such as boric acid, citric acid, or the like, or an
appropriate pH
buffer, to the particle. In an alternate mode, the prospective problems
associated with
amine malodors can be masked by use of perfume ingredients, as disclosed
herein.
Liquid Deterrgents
The manufacture of heavy duty liquid detergent compositions, especially those
designed for fabric laundering, which comprise a non-aqueous carrier medium
can be
prepared according to the disclosures of U.S. Patents 4,753,S70; 4,767,558;
4,772,413;
4,889,652; 4,892,673; GB-A-2,158,838; GB-A-2,195,125; GB-A-2,195,649; U.S.
4,988,462; U.S. 5,266,233; EP-A-225,654 (6/I6/87); EP-A-S10,762 (10/28I92); EP-
A-
540,089 (5/5/93); EP-A-540,090 (5l5/93); U.S. 4,6l5,820; EP-A-565,017
(10/l3/93);
EP-A-030,096 (6/10/81 ), incorporated herein by reference. Such compositions
can
contain various particulate detersive ingredients (e.g., bleaching agents, as
disclosed
hereinabove) stably suspended therein. Such non-aqueous compositions thus
comprise a
LIQUID PHAS$ and, optionally but preferably, a SOLID PHASE, all as described
in
more detail hereinafter and in the cited references. The AQD dispersants are
incorporated in the compositions at the levels and in the manner described
hereinabove
for the manufacture of other laundry detergent compositions.
The compositions of this invention can be used to form aqueous washing
solutions for use in the laundering and bleaching of fabrics. Generally, an
effective
amount of such compositions is added to water, preferably in a conventional
fabric
laundering automatic washing machine, to form such aqueous
laundering/bleaching
solutions. The aqueous washing/bleaching solution so formed is then contacted,
preferably under agitation, with the fabrics to be laundered and bleached
therewith.
An effective amount of the liquid detergent compositions herein added to water
to
form aqueous laundering/bleaching solutions can comprise amounts sufficient to
form
from about 500 to 7,000 ppm of composition in aqueous solution. More
preferably, from
about 800 to 3,000 ppm of the detergent compositions herein will be provided
in aqueous
washing/bleaching solution.
The following examples are illustrative of the present invention, but are not
meant to limit or otherwise define its scope. A11 parts, percentages and
ratios used herein
are expressed as percent weight unless otherwise specified.
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66
In the following Examples a11 levels are quoted as % by weight of the
composition.
EXAMPLE I
The following liquid detergent compositions are made
Ingredient Example Example Example
a b c
Wt % Wt % Wt%
C12-l5alkyl polyethoxylate (1.8)21.4 20.2 --
sulfate
C12-l5alkyl polyethoxylate (2.5)- - 19.0
sulfate
Ethanol 3.7 3.6 3.4
Monoethano lamine 1 (0 1.0 1.0
C 10 amidopropyldimethyl amine 0.5 0.5 --
Propandiol 6.8 6.4 6.2
C12-l3Alky1 polyethoxylate (9) 0.7 0.6 2.0
C12-14 alkyl glucose amide 2.7 2.5 3.5
C12-14 fatty acid 2.0 2.0 2.0
Sodium toluene sulfonate 2.3 2.5 2.5
Citric acid 3.5 3.0 3.0
Borax 2.5 2.5 2.5
Sodium hydroxide (to pH 8.0) 2.5 2.5 3.0
Lipolase (100KLU/g) 0.1 0.08 0.04
Amylase {300KNU/g) 0.2 0.2 0.1
Carezyme (SOOOcevu/g) 0.05 0.5 0.3
Protease (32glL) 0.9 0.8 1.0
Soil Release Polymer* 0.2 0.5 0.3
AQD** 1.0 2.0 1.2
Polyethyleneimine, MW 600 ethoxylated1.0 -- --
(20 moles EO/nitrogen)
Water, perfiune, enzymes, suds to 100% to 100% to 100%
suppressor,
brightener &
other optional ingredients
* Oligomer of Sodium 2-[2-(2-Hydroxyethoxy)ethoxy]ethanesulfonate, Dimethyl
Terephthalate, Sodium 2-(2,3-Dihydroxypropoxy)ethanesulfonate, Ethylene
Glycol,
and Propylene Glycol) or mixtures of those per U.S. Patent 5,415,807
** 24-ethoxylated quaternized hexamethylenediamine
EXAMPLE II
The following liquid detergent compositions are made
Insredient Example Example Example
a b c
Wt % Wt % Wt%
C12-l5alkyl polyethoxylate 12.5 21.9 20.0
(3) sulfate
C12-15 alkyl sulfate 7.7 -- --
Ethanol 5.5 5.5 5.5
Monoethanolamine to pH to pH to pH 7.8
7.8 7.8
C10 amidopropyldimethylamine 1.2 1.2 1.5
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67
Propandiol 8.4 8.5 8.5
C 12-l3Alkyl polyethoxylate 2.5 2.8 2.7
(6.5)
C12-14 alkyl glucose amide 3.8 4.2 4.1
C 12-16 fatty acid 4.5 4.5 4.5
Sodium xylene sulfonate 1.9 1.9 1.9
Citric acid 3.0 3.0 3.0
Sodium hydroxide 0.7 0.4 0.9
Protease enzyme (32g/L) 1.5 1.5 1.5
Amylase (300 KNU/g) 0.1 0.4 0.14
Carezyme (S000 cevu/g) 0.8 0.1 0.5
Lipolase Ultra ( 100 KLUIg) 0.1 0.2 0.15
AQD* 3.0 3.0 2.0
Polyethyleneimine, MW 1200 -- -- 1.00
ethoxylated
(7 moles EO/nitrogen)
Soil Release Polymer** 0.3 0.3 0.3
Water, perfume, enzymes, fluorscentto I00% to 100% to l00%
brightener, stabilizers, suds
suppressor &
other optional ingredients
* 24-ethoxylated quaternized hexamethylenediamine
** Oligomer of Sodium 2-[2-(2-Hydroxyethoxy)ethoxy]ethanesulfonate, Dimethyl
Terephthalate, Sodium 2-(2,3-Dihydroxypropoxy)ethanesulfonate, Ethylene
Glycol,
and Propylene Glycol)
EXAMPLE III
The following liqtfid detergent compositions are made
-In reg_ diem Example
a
Wt
C 12-15alkyl polyethoxylate (3) 4.0
sulfate
C 12-15 alkyl sulfate, branched 14.0
Ethanol 2.2
Monoethanolamine 4.5
C8-10 amidopropyldimethylamine 1.3
Propandiol 9.0
C13-lSAlkyl polyethoxylate (4.0) 4.5
C 12-14 alkyl glucose amide 4.0
C12-16 fatty acid 7.5
Rapeseed fatty acid 3.2
Citric acid 1.0
Sodium hydroxide 2.4
Protease enzyme (34 g/1) 0.6
Duramyl 0.1
Termamyl (300KNU/g) 0.1
Carezyme (5000 Cevu/g) 0.03
Lipolase Ultra (100KLU/g) 0.1
Endolase (3000 cevu/g) 0.2
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AQD* 1.3
PEI 600-E20** 1.3
Soil Release Polymer* * * 0.2
Water, perfume, enzymes, fluorscent to 100%
brightener,
stabilizers, suds suppressor & other
optional
ingredients
* * 24-ethoxylated quaternized hexamethylenediamine
* * Ethoxylated polyethyleneimine E20 having an average M W of approximately
600
* * * Oligomer of Sodium 2-[2-(2-Hydroxyethoxy)ethoxy]ethanesulfonate,
Dimethyl
Terephthalate, Sodium 2-(2,3-Dihydroxypropoxy)ethanesulfonate, Ethylene
Glycol,
and Propylene Glycol)
