Note: Descriptions are shown in the official language in which they were submitted.
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ALKOXYLATED, QUATERNIZED
POLYAMINE DETERGENT INGREDIENTS
TECHNICAL FIELD
The present invention relates to detergent compositions which comprise
selected ingredients, including selected quaternized alkoxylated polyamine
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
their
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
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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. 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 compound
which will effectively remove soils an dprevent 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, tf~e 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.
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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 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 palyamine
(AQP) 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
AQP
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 AQP soil removal/dispersants used in the present manner
provide substantial advantages to the formulator over other dispersants known
heretofore. For example, the AQP dispersants herein are compatible with the
preferred alkyl sulfate, alkyl ethoxylated sulfate, and amidopropylamine
detersive
surfactants. Moreover, the AQP dispersants are formulatable over a broad pH
range
from S to 12. The AQP dispersants are also compatible with various perfume
ingredients, unlike other quats known in the art.
In addition to the foregoing advantages, the AQP 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 AQP 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 AQP 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 AQP dispersants herein are
surprisingly compatible with the polyanionic 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
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4
been found that the combination of the AQP dispersants herein with specific
ethoxylated polyethyleneimines with a MW of less than about 5,000 provide
synergistic cleaning benefits.
Other advantages for the AQP 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 AQP 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 AQP 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 AQP 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 AQP 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 AQP
dispersants provide improved performance over conventional dispersants with
special regard to clay soil removal.
Still further advantages for the AQP dispersants herein have been discovered.
For example, in bleaching compositions (or wherein the bleach is added
separately
to the wash liquor) 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), tetraacetylethylediamine (TAED), or peracids. Quite
low levels of AQP dispersants gives rise to these results.
Moreover, in compositions without bleach, the formulator my choose to use
somewhat higher levels of AQP dispersants to provide enhanced performance
benefits. These benefits may be associated with the ability of the AQP
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
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S
available to perform their cleaning function. This is particularly true in
situations
faced by the formulator where the detergent composition is "underbuiit" with
respect
to calcium and/or magnesium water hardness ions
Mixtures of AQP 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 AQP dispersants are disclosed in the Examples hereinafter.
Various other advantages of the AQP dispersants over other dispersants
known in the art are described in more detail hereinafter. As will be seen
from the
disclosures herein, the AQP dispersants, used in the manner of the present
invention,
successfully address many of the problems associated with the formulation of
modem, 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
polyamine (AQP) dispersants used in the present invention are of the general
formula:
A A A
R~-N~ R N~ R N~ R~ (m + 2 X~
I I I )
A R~ m A
where R is selected from linear or branched C2-C12 alkylene, C3-C12
hydroxyalkylene, C4-C 12 dihydroxyalkylene, Cg-C 12 dialkylarylene,
((CH2CH20)qCH2CH2]- and -CH2CH(OH)CH20-
(CH2CH20)qCH2CH(OH)CH2]- where q is from about I to about 100. If present,
Each R 1 is independently selected from C 1-C4 alkyl, C ~-C 12 alkylaryl, or
A. R 1
may be absent on some nitrogens; however, at least three nitrogens must be
quaternized.
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A is of the formula:
(CH-CH2-O)nB
R3
where R3 is selected from H or C1-C3 alkyl, n is from about 5 to about 100 and
B is
selected from H, C 1-C4 alkyl, acetyl, or benzoyl; m is from about 1 to about
4, and
X is a water soluble anion
In preferred embodiments, R is selected from C4 to Cg alkylene, R1 is
selected from C 1-C2 alkyl or C2-C3 hydroxyalkyl, and A is:
(CH-CH2-O)nH
R3
where R3 is selected from H or methyl, and n is from about 10 to about 50; and
m is
1.
In another preferred embodiment R is linear or branched C6, R 1 is methyl,
R3 is H, and n is from about 20 to about 50, and m is 1..
The levels of the AQP 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 AQP 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 AQP 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 AQP
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 AQP dispersant and a specific surfactants, including alkyl sulfate (AS) and
alkyl
alkoxylated, especially ethoxylated, sulfates (AES). In other preferred
embodiments, the compositions with AQP 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 AQP is combined with linear alkyl benzene sulfonate.
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Detergent compositions which comprise conventional detersive ingredients,
an AQP dispersant and selected amine surfactants, such as
amidopropyldimethylamines.
Detergent compositions which comprise conventional detersive ingredients,
an AQP 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 AQP 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 I,000.
Detergent compositions which comprise conventional detersive ingredients,
an AQP 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 AQP dispersant and chelants, especially ethylenediaminedisuccinate (EDDS)
chelant.
Detergent compositions which comprise conventional detersive ingredients,
an AQP dispersant and a cellulase or protease enzyme, or mixtures thereof.
Detergent compositions which comprise conventional detersive ingredients,
an AQP dispersant and an alkyl polyglycoside or polyhydroxy fatty acid amide
surfactant.
Detergent compositions which comprise conventional detersive ingredients,
an AQP dispersant and a non-aqueous liquid Garner matrix.
Detergent compositions which comprise conventional detersive ingredients,
an AQP dispersant and a detergent granule having a bulk density of 650 g/L, or
greater.
Detergent compositions which comprise conventional detersive ingredients,
an AQP dispersant and a source of magnesium ions, calcium ions, or mixtures
thereof.
Detergent compositions which comprise conventional detersive ingredients,
an AQP dispersant and a dye-transfer inhibitor.
Detergent compositions which comprise conventional detersive ingredients,
an AQP dispersant and a manganese, cobalt or iron bleach catalyst.
Detergent compositions which comprise conventional detersive ingredients,
an AQP dispersant and a zeolite P or "MAP" builder.
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Detergent compositions which comprise conventional detersive ingredients,
an AQP dispersant and a Mineral Builder.
Detergent compositions which comprise conventional detersive ingredients,
an AQP dispersant and an oxygen bleach such as percarbonate bleach.
Detergent compositions which comprise conventional detersive ingredients,
an AQP dispersant and one or more bleach activators.
Detergent compositions which comprise conventional detersive ingredients,
an AQP dispersant and a photobleach.
The AQP 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 AQP 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 modem, high quality, fully-formulated laundry
detergents. Moreover, the AQP compounds exhibit satisfactory stability in the
presence of the bleach ingredients commonly used in laundry detergent-plus-
bleach
compositions. Importantly, the AQP 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 AQP 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 AQP in the laundry
liquor and
is believed to be associated with increased perhydrolysis.
In addition, the AQP 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.
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9
A11' 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 AQP
dispersant. Greasy/oily "everyday "soils are a mixture of triglycerides,
lipids,
complex polysaccharides, inorganic salts and proteinaceous matter. When soiled
garments are 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 AQP
dispersants and lipase enzyme deliver superior cleaning and whiteness
performance
vs. products containing either technology alone. Suitable lipase enzymes
include
those produced by microorganisms of the Pseudomonas group, such as Pseudomonas
stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable
lipases
include those which show a positive immunological crass-reaction with the
antibody
of the lipase, produced by the microorganism Pseudomonas fluorescens 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. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo
Jozo Co., Tagata, Japan; Chramobacter 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 341,947, is a preferred lipase
for use
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herein. Lipase and amylase variants stabilized against peroxidase enzymes are
described in WO 9414951 A to Novo. See also WO 9205249 and RD 94359044.
Highly preferred lipases are the D96L lipolytic enzyme variant of the native
lipase derived from Humicola lanuginosa as described in US Serial No.
08I341,826.
(See also patent application WO 92/05249 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.
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 LU/liter) lipase
variant per liter of wash liquor.
Lipase enzyme is incorporated into the composition in accordance with the
invention at a level of from SO LU to 8S00 LU per liter wash solution.
Preferably the
variant D96L is present at a level of from 100 LU to 7500 LU per liter of wash
solution. More preferably at a level of from 1 SO LU to 5000 LU per liter of
wash
solution.
The lipases and/or cutinases are normally incorporated in the detergent
composition at levels from 0.000l % to 2% of active enzyme by weight of the
detergent composition.
Also suitable are cutinases [EC 3.1.1.50) which can be considered as a
special kind of lipase, namely lipases which do not require interfacial
activation.
Addition of cutinases to detergent compositions have been described in e.g. WO-
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
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been discovered that detergent compositions containing a combination of the
water-
soluble AQP 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 0.000l8% 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.
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
l2289,
NCIB 12512, 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).
(f) 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)
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12
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-
amyiase having one of said amino acid sequences, and/or is encoded by a DNA
sequence wick 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;
and/or
2.at least one amino acid residue of said parent a-amylase has been replaced
by a
different amino acid residue; and/or
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 1,296,839 to Novo; RAPIDASE~, International Bio-Synthetics, lnc. 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-
6521.
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
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13
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 TEP;MAMYL~, or the homologous
position variation of a similar parent amylase, such as B. amyloliquefaciens>
B.
subtilis, or B. 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, l97, 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 9418314 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.
Alkvl 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 1 p-C24 alkyl or hydroxyalkyl group having a C
10-
C24 alkyl component, preferably a C 12-C 1 g alkyl or hydroxyalkyl, 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-
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14
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 ethylamine, diethyIamine,
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 I 2-C 15 alkyl
polyethoxylate
(2.25) sulfate (C 12-C I SE(2.25)M), C 12-C 15 alkyl polyethoxylate (3.0)
sulfate (C 12-
C I $E(3.0)M), and C 12-C 15 alkyl polyethoxylate (4.0) sulfate (C I 2-C 1
SE(4.0)M),
wherein M is conveniently selected from sodium and potassium.
The alkyl sulfate surfactants hereof are water soluble salts or acids of the
formula ROS03M wherein R preferably is a Cg-Clg hydrocarbyl, preferably an
alkyl or hydroxyalkyl having a C 1 p-C 1 g alkyl component, more preferably a
C 12-
C 15 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-I 5 Polyoxyethylene (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 AQP 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
AQP
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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
R1-X-(CH2)n-N
R4
wherein R 1 is a C6-C ~ 2 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 Rq are individually selected from H, CI-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
Rl -C(O)-NH-(CH2)3-N(CH3)2
CH2-CH (OH) -R5
R1-N
CH2-CH (OH) -R5
wherein RI is a C6-C12 alkyl group and RS is H or CHI.
In a highly preferred embodiment, the amine is described by the formula:
R1-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 12
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
AQP
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
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16
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 AQP 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 AQP dispersant of the present type.
Everyday soil cleaning and whiteness benefits for hydrophobic bleach
activators and
peracids have 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 AQP 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 AQP 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 stain/wash liquor interface.
Surprisingly, it has now. been discovered that detergent compositions
containing the AQP 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 ) AQP action on the stain surface to prevent lime soap formation and
to lift off
any calcium soaps present, thereby facilitating improved polymer deposition;
(2)
AQP providing solubilization deep into the soil, while the polymer acts as a
"grease
removal shuttle", stripping out the AQP-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
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17
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 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
~2NCH2CH2~ri ~CH2CH2~tri ~CH2CH2~ri 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 poiyamine 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:
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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, -(CH2CH~0)~H, having the formula
[H(OCHzCFfzhIzN\ ~N[(C~-~zCHzO)~H)z
I'N r~(O~z~zh.N~N[(CIIzCHzOhHIz
(CHzCHzOhH ~ (CHzCFIzOy~H
~~(~z~zhIzN~N~N~N~N~N~N~N~IV~N[(~z~zOhHlz
(~z~zOhH (Cf IzCHzOy,H ~ (CHzC7izOy~H
~N~
N~ N[(CHz~zOhHlz
~H(~z~zhlzN
~Nf(~z~zOh~-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 all substitutable primary amine nitrogens are modified by replacement
of
hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH~0)~H, the molecule is then
modified by subsequent oxidation of all oxidizable primary and secondary
nitrogens
to N-oxides,.said cotton soil release agent having the formula
O(CHzCHzO)6H
[I-~(~~zhlzN NI(cHz~zOhHlz
N O~ ~~N[(~z~zOhHlz
H(OCHO Hz)b "O O(CEizCHzO)6H O O(CHzCHzO)~H
O
t N ~ N
NI(CI-lz~z0)zHJz
IH(OCI-IzCHz},lzN ~ N a N~
O
O(~z~z016H O(CFizCHzO~H
N O
[H(OCHzCHzhlzN~ ~~N[(CFIzCHzO),Hlz
Formula II
Formula III depicts a cotton soil release polymer comprising a PEI backbone
wherein a11 backbone hydrogen atoms are substituted and some backbone amine
units are quaternized. The substituents are polyoxyalkyleneoxy units, -
(CH2CH20)~H, or methyl groups. The modified PEI cotton soil release polymer
has the formula
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19
CH3
[H(OCH,CHz}~)zN N(CHzCH,OhH
~N~ C~ ~3~N~N(CH,CH,Oy~H
~1 ~ ~3 ~3 CH3
IH(~z~zh)zN~N~_ N~N~N~N~N~N~_ N~N(~~h
CI ~3 (_'H3 ~ CI CH3
Cl
Formula III
CI
N(CHs~
N(CH3}z
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
cH,
lH(~z~zhlzN N(CHzCHZOhH
_ 0 ~3
~NJ C~ ~3~N~N(CH,CHZOhH
Cl'
O
CH3 ~ ~3. ~3
IH(OCHzCHzhlzN~ +~~N~ i ~TI~N~N~1+~N~'~N(~s~Z
C~' ~3 O ~ ~ CI C1-13
C~ +..
+ C1'
N(~s3~
Formula IV
In the above examples, not a11 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.
The present invention employs an "effective amount" of the AQP dispersant
to improve the performance of cleaning compositions which contain other
adjunct
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ingredients. By an "effective amount" of the AQP dispersants and adjunct
ingredients herein is meant an amount which is sufficient to improve, either
directionally or significantly at the 90% confidence level, 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 AQP to at least directionally improve cleaning performance against
such
stains. Likewise, in a composition whose targets include clay soil, the
formulator
will use sufficient AQP to at least directionally improve cleaning performance
against such soil. Importantly, in a fully-formulated laundry detergent the
AQP
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 AQP 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 AQP 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 AQP dispersants is their ability to
provide
at least directional improvements in performance over a spectrum of soils and
stains.
Various other cleaning compositions can also be formulated using an
effective amount of the AQP 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 AQP dispersants in
such
compositions.
Detersive Surfactants - Nonlimiting examples of anionic surfactants useful
herein typically at levels from about I% to about 55%, by weight, primary,
branched-chain and random C l 0-C20 alkyl sulfates ("AS"), the C 1 p-C 1 g
secondary
(2,3) alkyl sulfates of the formula CH3(CH2)x(CHOS03 M+) CH3 and CH3
(CH2)y(CHOS03-M+) CH2CH3 where x and (y + 1 ) are integers of at least about
7,
preferably at least about 9, and M is a water-solubilizing cation, especially
sodium,
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21
unsaturated sulfates such as oleyl sulfate, the C 10-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 10-C 1 g alkyl alkoxy
carboxylates (especially the EO 1-5 ethoxycarboxylates). The C 12-C 1 g
betaines and
sulfabetaines ("sultaines"), C 10-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 1 p-C 16 soaps may be used. Other
conventional useful surfactants are listed in standard texts.
Preferably the compositions of the invention are substantiall free of C 11-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 10-C 1 g 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 alcohols 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 15-S-9 (the condensation product
of C 11-
C 15 linear alcohol with 9 moles ethylene oxide) and TergitoITM 24-L-6 NMW
(the
condensation product of C 12-C 14 primary alcohol with 6 moles ethylene oxide
with
a narrow molecular weight distribution), both marketed by Union Carbide
Corporation; NeodolTM 45-9 (the condensation product of C 14-C 15 linear
alcohol
with 9 moles of ethylene oxide), NeodolT'" 23-3 (the condensation product of C
12-
C 13 linear alcohol with 3 moles of ethylene oxide), NeodolTM 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 12-C 14 alcohol with 3 or 5 moles of ethylene oxide)
marketed by Hoechst. The preferred range of HLB in these AE nonionic
surfactants
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22
is from 8-11 and most preferred from 8-10. Condensates with propylene oxide
and
butyiene 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- i ~N ~Z~
O R'
wherein R 1 is H, or C 1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a
mixture thereof, R2 is CS_31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl
having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected
to the
chain, or an alkoxylated derivative thereof. Preferably, R 1 is methyl, R2 is
a straight
CI1-15 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 I 2-
C 18
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. 5,489,393.
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, l 986, 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 gaIactosyl moieties can be
substituted for
the glucosyl moieties (optionally the hydrophobic group is attached at the 2-,
3-, 4-,
etc. positions thus giving a glucose or galactose as opposed to a glucoside or
galactoside). The intersaccharide bonds can be, e.g., between the one position
of the
additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the
preceding
saccharide units.
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 10 to about 18, preferably from about 12 to about 14,
carbon
atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x
is from
about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably
from
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23
about I.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-
63Q,
marketed by the GAF Corporation; and TritonTM X-45, X-I 14, 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~l0 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 oxide to the extent that the condensation product contains from about
40%
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24
to about 80% by weight of polyoxyethylene and has a molecular weight of from
about 5,000 to about 11,000. Examples of this type of nonionic surfactant
include
certain of the commercially available 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 AQP 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
a 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 phytic acid. These may be complemented by borates, e.g., for pH-
buffering purposes, or by sulfates, especially sodium sulfate and any other
fillers or
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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 l.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
-Na2Si0$ 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-S, NaSKS-7 and NaSKS-11, as the a, (3 and y layer-silicate forms. Other
silicates may also be useful, such as magnesium silicate, whfch 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: xM20~ySiO2.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 0.00S to
1.0 as
taught in U.S. 5,427,711, Sakaguchi et al, June 27, 199S.
Suitable carbonate builders include alkaline earth and alkali metal carbonates
as disclosed in German Patent Application No. 2,321,001 published on November
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26
1 S, 1973, 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 1.0 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, l976. 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~'~20 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 alkanolammonium 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 al, 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; 3,835,163; 4,1 S8,635; 4,120,874 and 4, l02,903.
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, carboxy-
methyloxysuccinic 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
3,422,137 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-dodecenylsuccinate (preferred), 2-
pentadecenylsuccinate, and the like. Lauryl-succinates are described in
European
Patent Application 86200690.5l0,200,263, published November 5, l986. 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 13, 1979 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 firom 1 to 1 S, 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,
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WO 98I15608 PCT/US97/17308
28
silicon, arid mixtures thereof, more 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,
Cancrznite,
Carbocernaite, Carletonite, Davyne, DonnayiteY, Fairchildite, Ferrisurite,
Franzinite, Gaudefroyite, Gaylussite, Girvasite, Gregoryite, Jouravskite,
KamphaugiteY, Kettnerite, Khanneshite, LepersonniteGd, Liottite, MckelveyiteY,
Microsommite, Mroseite, Natrofairchildite, Nyerereite, RemonditeCe,
Sacrofanite,
Schrockingerite, 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 0.01 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, 198S. 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 9510591 A to Procter & Gamble . When
desired, a protease having decreased adsorption and increased hydrolysis is
available
as described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like
protease for detergents suitable herein is described in WO 9425583 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
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hydrolase equivalent to 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, +107, +123, +27, +105, +l09, +126, +128,
+ 13 5, + 15 6, + 166, + 195, + 19 7, +204, +206, +2 I 0, +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.
Cellulases 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 cellulase 212-producing fungus belonging to the genus
Aeromonas, and cellulase extracted from the hepatopancreas of a marine
mollusk,
Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-
2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. 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, perborate, 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. 4,1 O 1,457,
Place et al,
July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, l985. 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, 198l.
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 200,586, October 29, 1986, Venegas. Enzyme
stabilisation
systems are also described, for example, in U.S. 3,519,S70. A useful Bacillus,
sp.
AC 13 giving proteases, xylanases and cellulases, is described in WO 9401532 A
to
Novo.
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Enzyme Stabilizin~S_ystem - The enzyme-containing compositions herein
may optionally also comprise from about 0.00l % 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 andlor
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,S37,706. 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
from about 0.01 % to about 6% by weight, of chlorine bleach scavengers, added
to
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32
prevent 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
1.75 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,
fonmate, lactate, riialate, 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 normal 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 Agent - 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 0.01 % to 10.0%,
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33
typically from 0.1% to S%, preferably from 0.2% to 3.0% by weight, of the
composition.
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.
4,968,451,
November 6, I990 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. 4,711,730, December
8,
1987 to Gosselink et al, for example those produced by
transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT,
PG
and poly(ethyleneglycol) ("PEG"); the partly- and fully- anionic-end-capped
oligomeric esters of U.S. 4,721,580, 3anuary 26, 1988 to Gosselink, such as
oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-
hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric
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34
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 typical of
SRA's
useful in both laundry and fabric conditioning products, an example being an
ester
composition made from m-suIfobenzoic 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. 3,9S9,230 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 SR.A's such as SOKALAN HP-22, available
from BASF, Germany. Other SRA's are polyesters with repeat units containing 10-
15% by weight of ethylene terephthalate together with 90-80% by weight of
polyoxyethylene terephthalate, derived from a polyoxyethylene glycol of
average
molecular weight 300-5,000. Commercial examples include ZELCON 5126 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 0.5% 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. 5,415,807,
Gosselink,
Pan, Kellett and Hall, issued May 16, 1995. Suitable monomers for the above
SRA
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include Na 2-(2-hydroxyethoxy)-ethanesulfonate, DMT, Na- dimethyl 5-
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
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; q is from about 0.05 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
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(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 EGIPG is
about 1.7:1 as measured by conventional gas chromatography after complete
hydrolysis.
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Additional classes of SRA's include (I) nonionic terephthalates using
diisocyanate coupling agents to link up polymeric ester structures, see U.S.
4,20I,824, Violland et aI. 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 trimeIlitic 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 hydroxyl terminal groups which may be
esterified. See U.S. 4,525,S24 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. 4,579,681, 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 279,134 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
2,33S,044 to Unilever N. V., 1974. Other useful SRA's are described in U.S.
Patents
4,240,918, 4,787,989, 4,525,S24 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 a; end t-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 ~ ~ C
ii) at least one moiety having the formula:
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37
Rio Rio
I I
-O-R9-(O-R'~i O
Rio R~o
wherein R9 is C2-C6 linear alkylene, C3-C6 branched
alkylene, CS-C7 cyclic alkylene, and mixtures thereof; R10
is independently selected from hydrogen or -L-503-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(R1 lO)n_, where M is a salt
forming cation such as sodium or tetralkylammonium, R11 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(oxyethylene)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
firom 1 to 20; M is a salt-forming cation; and R 13 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-l ~(R4)t(CaP)~
wherein A is a carboxy linking moiety having the formula
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38
O
ii
-C-
R 1 is arylene, preferably a 1,4-phenylene moiety having the formula
/ \
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
O O
-C f ~ 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-CHz-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
O O O O
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)J 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-Rl-A-
R2) unit,
a (A-R 1-A-RS ) unit, a -A-R 1-A-[(R4)t(Cap)] unit or another (A-R 1-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
.O-(CH(CH3~H20r-
-(CH2CH20y~-C ~ ~ C-O ~~O-C ~ ~ C-O~.O-C / ~ C-
O O O O p~0
R4 units are R2, R3 or RS units.
RS units are units having the formula
. Rlo Rio
i i
-'O-R~'-'(O-R9)i O_
Rio Rio
wherein R9 is C2-C6 linear alkylene, C3-C6 branched alkylene, and mixtures
thereof; preferably R10 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
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L-S03-M+ units is attached to an R9 unit; L is a side chain connecting moiety
selected from the group consisting of alkylene, oxyalkyIene,
alkyleneoxyalkylene,
arylene, oxyarylene, 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 R10 substituted C2-C6 alkylene chains.
The RS units comprise either one C2-C6 alkylene chain substituted by one or
more
independently selected R 10 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 R 10 moieties. Preferably only one carbon atom of each R9 moiety is
substituted by an -L-S03-M+ unit with the remaining R 10 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 Rto Rio Rio
-O-C C O C --C -O
Rio Rio Rio Rto
wherein each R9 comprises a C2 alkylene moiety. Preferably one R 10 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)xS03-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 R10
I
-O-R9-_'(O-R9)i O
Rio Rio
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,
aryIene,
alkylarylene, alkoxyarylene and mixtures thereof', refers to the preferred
compounds
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41
of the present 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-CHI-CH-O-
CH2(OCH2CH2)xS03 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-CH2-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 RS
moieties
includes the alkylene poly(oxyalkylene)oxyarylene containing monomer having
the
general formula
HO-CH,-CH-OH
' I
CHZ(OCHZCH2~0 / \ 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(OCH2CH2~SOg Na+
wherein x is from 0 to about 20; more preferred are the monomers
OH
I
HO-CH2-CH-CHZ-OH or HO-CH2-CH-CH2
OCHZCHZS03 Na+ OCH2CH2S03 Na+
The preferred non-cotton soil release agents of the present invention in
addition to the afore-mentioned Rl, 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 (M03S)(CH2)m(R11 p)n-, where M is a salt forming cation such as sodium
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42
or tetralkylammonium as described herein above, RI I 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 R120(CH2CH20)k- wherein R12 contains from I to 4 carbon
atoms, R12 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 R13 is ethylene, propylene
and
mixtures thereof.
Most preferred end capping unit is the isethionate-type end capping unit
which is a hydroxyethane moiety, (M03 S)(CH2)m(R I I O)n-, preferably R I I is
ethyl, m is equal to 0, and n is from 2 to 4.
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
f(CaP)(R4)tJ UA-R I -A-R2)u(A-R I -A-R3)v(A-R I -A-RS)w
-A-R I -A-~ ~(R4~(CaP)~
can be conveniently expressed as the following generic structural formula
o- 0 0 0
Na03S(CHZCHZO~.sCHZCHz O-C / ~ C-OCHzCH O-C / ~ C-OCHZCH
R I
u~ ~ w
OCHZCH~S03Na
O_~2~~~z~2h~sS~Na
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
0 0 0 0
NaQ~S(CH:CN_Oy~.SCH=CH~ O-C ~ ~ C-OCH,CH O-C ~ ~ C-OCH_,CH
R
i.7-2.2- ~ - 2.5
OCI-IZCH~S03Na
O-C ~ ~ C-OCtI2CH 0~-O ~ ~ C-OCH=CH(OCH,CHz}~.SS03Na
0.15 I.IS
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(EG1PG)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 moles of the corresponding units per
mole
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44
of said ester and said ester has a molecular weight ranging from about 500 to
about
s,ooo.
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[CH2-
CH20]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 terephthalate ("DMT") and I,2-
propylene glycol ("PG") in a two-stage transesterification/oligomerization
procedure; and (c) reacting the product of (b) witt>'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 I 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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-O(CH2CH20)nCH2CH20-
wherein the value of n is from about I to about 20; and
iii) 1,2-propyleneoxy units having the formula:
-O(CH2CH(CH3)O~CH2CH(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-R1-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
0 0
ii ii
-~C- or -C-O-
R 1 is an arylene moiety, preferably 1,4-phenylene moiety having the formula
/ \
wherein for R1 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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46
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 oxyalkylenes.
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 (-CH2CH_
20CH2CH2-) 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. Also, the R3 can all be the same (e.g. all 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
-[(R50}m(CH2CH20}n)X
wherein RS is C1-C4 aIkylene, or the moiety -R2-A-R6- wherein R6 is C2-C12
alkylene, alkenylene, arylene or alkarylene moiety, X is C 1-C4 alkyl,
preferably
methyl; the indices m and n are such that the moiety -CH2CH20- comprises at
least
50% by weight of the moiety
-[(R50~(CH2CH20)~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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47
o ~ ~ 0 0 0 0 0
X-(OCHaCH~)n-(OC~CO-R2)~ (OC-R3-CO-R2)~-OC-R4-CO-(CH,CH,O~-X
wherein the R2 moieties are essentially ethylene moieties, 1,2-propylene
moieties,
and mixtures thereof; the R3 moieties are all potassium or preferably sodium 5-
sulfo-1,3-phenyiene 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)E(A-R 1-A-R2)u(A-R3 _A_R2)v_p_R4_A_~(Cap)
are further described in detail in U.S. Patent 4,702,85?, 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 Oligomer of Sodium 2-(2-(2
Hvdroxvethoxy)ethoxy]ethanesulfonate, Dimethyl Terephthalate, Sodium 2-(2,3
Dihvdroxvpropoxy)ethanesulfonate) Ethylene Glycol, and Propylene 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 mol), dimethyl terephthalate
(14.4g, 0.074 mol), 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 180~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
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48
near room temperature under 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 1.6:1. 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.
Bleaching Compounds - Bleachin~AQents and Bleach Activators - The
detergent compositions herein may optionally contain bleaching agents or
bleaching
compositions containing a bleaching agent and one or more bleach activators.
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-6-oxoperoxycaproic acid as described in U.S. Patent
4,634,551, issued January 6, 1987 to Burns et al.
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49
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 4,915,854, 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,S51 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 alkyiene 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-nonanamidocaproyl)oxybenzenesul-
fonate, (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
I I
CEO
C
''
N
Still another class of preferred bleach activators includes the acyl lactam
activators, especially acyl caprolactams and acyl valerolactams of the
formulae:
O O
Il II
O C-C H2-C H2\ O C-C H2- ~ H2
R6-C-NBC H2-C H2 C H2 R6-C-NBC HZ-C H2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from 1 to
about 12 carbon atoms. Highly preferred lactam activators include benzoyl
caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam,
nonanoyl
caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl
valerolactam,
octanoyl valerolactam, decanoyl valerolactam, 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, l985, 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 4,033,7l8, issued July 5, 1977 to
Holcombe et al. If used, detergent compositions will typically contain from
about
0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc
phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of a
manganese compound. Such compounds are well known in the art and include, for
example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,62I, U.S.
Pat.
5,244,S94; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App.
Pub.
Nos. 549,271 A 1, 549,272A 1, 544,440A2, and 544,490A 1; Preferred examples of
these catalysts include MnIV2(u-O)3(1,4,7-trimethyl-l,4,7-triazacyclononane)2-
(PF6)2~ ~III2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(CI04)2,
~IV4(u-O)6(1,4,7-triazacyclononane)4(CI04)4, MnIIIMnIV4(u-O)1(u-OAc)2_
(1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)3, MnIV(1,4,7-trimethyl-1,4,7-
tri-
azacyclononane)- (OCH3)3(PF6), and mixtures thereof. Other metal-based bleach
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51
catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat.
5,114,6l1.
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;
5,24b,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.
IriOrQ. Bioinorg. Mech., (1983), 2, pages 1-94. The most preferred cobalt
catalyst
useful herein are cobalt pentaamine acetate salts having the formula
[Co(NH3)SOAc) Ty, wherein "OAc" represents an acetate moiety and "Ty" is an
anion, and especially cobalt pentaamine acetate chloride, [Co(NH3)SOAcJCl2; as
well as (Co(NH3)SOAc](OAc)2; [Co(NH3)SOAc](PF6)2; [Co(NH3)SOAc](S04);
[Co(NH3)SOAc)(BF4)2; and (Co(NH3)SOAc](N03)2 (herein "PAC").
These cobalt catalysts are readily prepared by known procedures, such as
taught for example in 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 (
12),
1043-45; The Synthesis and Characterization of Inorganic Compounds, Vd.L.
Jolly
(Prentice-Hall; 1970), pp. 461-3; Inore. Chem., 18, 1497-1502 ( 1979); Inor~.
Chem.,
21, 2881-2885 ( 1982); Inorg~ Chem., I 8, 2023-2025 ( 1979); Inorg. Synthesis,
173-
I 76 ( 1960); and Journal of Ph,~rsical 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
0.01 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 Agents - The compositions of the
present invention can also optionally contain water-soluble ethoxylated amines
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52
having clay soil removal and antiredeposition properties. Granular detergent
compositions which contain these compounds typically contain. from about 0.01
% to
about 10.0% by weight of the water-soluble ethoxylates amines; liquid
detergent
compositions typically contain about 0.0l% 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 111,965, Oh and Gosselink, published June 27,
1984.
Other clay soil removaUantiredeposition agents which can be used include the
ethoxylated amine polymers disclosed in European Patent Application 111,984,
Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in
European Patent Application 1l2,592, Gosselink, published July 4, 1984; and
the
amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22,
l985.
Other clay soil removal and/or anti redeposition agents known in the art can
also bP
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 Dispersing A; ents - 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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S3
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 fonm 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
S,000.
Water-soluble salts of such acrylic acid polymers can include, for example,
the alkali
metal, ammonium and substituted ammonium salts. Soluble polymers of this type
are known materials. Use of polyacrylates of this type in detergent
compositions has
been disclosed, for example, in Diehl, U. S. Patent 3,308,067, issued march 7,
1967.
Acrylic/maleic-based copolymers may also be used as a preferred component
of the dispersing/anti-redeposition agent. Such materials include the water-
soluble
salts of copolymers of acrylic acid and malefic acid. The average molecular
weight
of such copolymers in the acid form preferably ranges from about 2,000 to
l00,000,
more preferably from about S,000 to 7S,000, most preferably from about 7,000
to
65,000. The ratio of acrylate to maleate segments in such copolymers will
generally
range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
Water-
soluble salts of such acrylic acid/maleic acid copolymers can include, for
example,
the alkali metal, ammonium and substituted ammonium salts. Soluble
acrylate/maleate copolymers of this type are known materials which are
described in
European Patent Application No. 669l 5, published December 1 S, 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 4S/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
S0,000, more preferably from about 1,S00 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.
Bri h'g teaser - 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
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54
subgroups, which 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, l988. 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
amino-
coumarins. Specific 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 3,646,0l5, issued February 29,
l972 to Hamilton.
D~ Transfer Inhibitin~A~ - 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, polyamine N-
oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these
agents
typically comprise from about 0.01 % to about I 0% by weight of the
composition,
preferably from about 0.0l % to abs~ut 5%, and more preferably from about
0.05% to
about 2%.
More specifically, the polyamine 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
1; 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.
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The N-O group can be represented by the following general structures:
O O
I I
(Rihc-' -(R2)y; -N-(Rt)x
(R3)z
wherein RI, 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
1,000,000;
more preferred I,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 5,000 to 1,000,000, more preferably
from
5,000 to 200,000, and most preferably from 10,00Q to 20,000. (The average
molecular weight range is determined by light scattering as described in
Barth, et al.,
Chemical Analysis, Vol 113. "Modern Methods of Polymer Characterization", the
disclosures of which are incorporated herein by reference.) The PVPVI
copolymers
typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from I
: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,
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preferably from about 5,000 to about 200,000, and more preferably from about
5,000
to about 50,000. PVP's are known to persons skilled in the detergent field;
see, for
example, EP-A-262,897 and EP-A-256,696, 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
I ,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 I0:1.
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:
R1 R2
N H H N
N N O C C O N-~O N
~N H H N
R2 S03M 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, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M
is a cation 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-LTNPA-GX by Ciba-Geigy Corporation. Tinopal-LJNPA-GX is the preferred
hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, R1 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 disodium salt. This particular brightener species is commercially
marketed
under the tradename Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R I 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
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is 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 IJNPA-
GX, Tinopal SBM-GX andlor 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.
Chelatin~ Agents - The detergent compositions herein may also optionally
contain one or more iron and/or manganese chelating agents. Such chelating
agents
can be selected firom 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
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58
permitted in detergent compositions, and include ethylenediaminetetrakis
(methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to
not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
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-3,5-disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent
4,704,233, 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
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di- to tetra=alkyldiamine chlortriazines formed as products of cyanuric
chloride with
two or three moles of a primary or secondary amine containing 1 to 24 carbon
atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol
phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li)
phosphates and
phosphate esters. The hydrocarbons such as paraffin and haloparaffin can be
utilized
in liquid form. The liquid hydrocarbons will be liquid at roam 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 10Q~C. The hydrocarbons constitute a preferred
category
of suds suppressor for detergent compositions. Hydrocarbon suds suppressors
are
described, for example, in U.S. Patent 4,26S,779, issued May 5, l981 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, 198l to Gandolfo et al and European Patent
Application
No. 893078S 1.9, published February 7, I990, 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 4,6S2,392, 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;
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(ii) from about 5 to about 50 parts per l00 parts by weight of (i) of siloxane
resin composed of (CH3)3Si01/2 units of Si02 units in a ratio of from
(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 100 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-
poiypropylene 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 from about 0.001 to about l,
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 4,983,316, Starch, issued January 8,
1991,
5,288,431, Huber et al., issued February 22, 1994, and U.S. Patents 4,639,489
and
4,749,740, Aizawa et al at column.l, line 46 through column 4, line 35.
The silicone suds suppressor herein preferably comprises polyethylene glycol
and a copolymer of polyethylene glycol/poIypropylene glycol, a11 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
glycol/polypropylene glycol, preferably PPG 2001PEG 300. Preferred is a weight
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ratio of between about 1:1 and l:10, most preferably between 1:3 and 1:6, of
polyethylene glycol:copolymer of polyethylene-polypropylene glycol.
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 1 O I .
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 16 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 12. Mixtures of secondary alcohols are available under the trademark
ISALCHEM 123 from Enichem. 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 0.01% to
about
1 % of silicone suds suppressor is used, more preferably from about 0.2S% 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
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0.01 % to about 5.0%, although higher levels can be used. The alcohol suds
suppressors are typically used at 0.2%-3% by weight of the finished
compositions.
Alkoxylated Polvcarboxylates - Alkoxylated polycarboxylates such as those
prepared from polyacrylates are useful herein to provide additional grease
removal
performance. Such materials are described in WO 91 /08281 and PCT 90/01815 at
p.
4 et seq., incorporated herein by reference. Chemically, these materials
comprise
polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The
side-
chains are of the formula -(CH2CH20)m(CH2)nCH3 wherein m is 2-3 and n is 6-
12. The side-chains are ester-linked to the polyacrylate "backbone" to provide
a
"comb" polymer type structure. The molecular weight can vary, but is typically
in
the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates can
comprise from about 0.0S% 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 4,062,647, Storm and Nirschl, issued
December 13, l977, 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 l, 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 0.01% 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 f nished
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 1,6,10-
trimethyl-2,S,9-cyclododecatrien-1-yl ketone; 7-acetyl-1,1,3,4,4,6-hexamethyl
tetralin; 4-acetyl-6-tent-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-
butanone;
benzophenone; methyl beta-naphthyl ketone; 6-acetyl-l,1,2,3,3,5-hexamethyl
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indane; 5-acetyl-3-isopropyl-I, l,2,6-tetramethyl indane; 1-dodecanal, 4-(4-
hydroxy-
4-methylpentyl)-3-cyclohexene-1-carboxaldehyde; 7-hydroxy-3,7-dimethyl
ocatanal; IO-undecen-1-al; iso-hexenyl cyclohexyl carboxaldehyde; formyl
tricyclodecane; condensation products of hydroxycitronellal and methyl
anthranilate, condensation products of hydroxycitronellal and indol,
condensation
products of phenyl acetaldehyde and indol; 2-methyl-3-(para-tent-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,?,8,8-hexamethylcyclopenta-gamma-2-
benzopyrane; beta-naphthol methyl ether; ambroxane; dodecahydro-3a,6,6,9a-
tetra-
methylnaphtho[2,1 b)furan; cedrol, 5-(2,2,3-trimethylcyclopent-3-enyl)-3-
methylpentan-2-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-
ol;
caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenyl acetate;
benzyl
salicylate; cedryl acetate; and para-(tent-butyl) cyclohexyl acetate. -
Particularly preferred perfume materials are those that provide the largest
odor improvements in f nished product compositions containing cellulases.
These
perfumes include but are not limited to: hexyl cinnamic aIdehyde; 2-methyl-3-
(para-tert-butylphenyl)-propionaldehyde; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-
1,1,6,7-
tetramethyl naphthalene; benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl
tetralin;
para-tert-butyl cyclohexyl acetate; methyl dihydro j asmonate; 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[2,1 b)furan; anisalde-
hyde; 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,
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suds boosters such as the C 10-C 16 alkanolamides can be incorporated inta 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, 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 perfonmance.
Various detersive ingredients employed in the present compositions
optionally can be further stabilized by absorbing said ingredients onto a
porous
hydrophobic substrate, then coating said substrate with a hydrophobic coating.
Preferably, the detersive ingredient is admixed with a surfactant before being
absorbed into the porous substrate. In use, the detersive ingredient is
released from
the substrate into the aqueous washing liquor, where it performs its intended
detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica
(trademark SIPERNAT D 10, DeGussa) is admixed with a proteolytic enzyme
solution containing 3%-5% of C 13_ 15 ethoxylated alcohol (EO 7) nonionic
surfactant. Typically, the enzyme/surfactant solution is 2.5 X the weight of
silica.
The resulting powder is dispersed with stirnng in silicone oil (various
silicone oil
viscosities in the range of S00-12,500 can be used). The resulting silicone
oil
dispersion is emulsified or otherwise added to the final detergent matrix. By
this
means, ingredients such as the aforementioned enzymes, bleaches, bleach
activators,
bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and
hydrolyzable surfactants can be "protected" for use in detergents, including
liquid
laundry detergent compositions.
Liquid detergent compositions can contain water and other solvents as
carriers. Low molecular weight primary or secondary alcohols exemplified by
methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols
are
preferred for solubilizing surfactant, but polyols such as those containing
from 2 to
about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-
propanediol,
ethylene glycol, glycerine, and 1,2-propanediol) can also be used. The
compositions
may contain from 5% to 90%, typically 10% to SO% of such carriers.
The detergent compositions herein will preferably be formulated such that,
during use in aqueous cleaning operations, the wash water will have a pH of
between
about 6.5 and about 11, preferably between about 7.5 and 10.5. Liquid
dishwashing
product formulations preferably have a pH between about 6.8 and about 9Ø
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Laundry products are typically at pH 9-11. 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 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 Deter ents
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 4,753,570;
4,767,558;
4,772,413; 4,889,652; 4,892,673; GB-A-2,1S8,838; GB-A-2,l95,125; GB-A-
2,195,649; U.S. 4,988,462; U.S. 5,266,233; EP-A-22S,654 (6/l6/87); EP-A-
510,762
(l0/28/92); EP-A-540,089 (5/5/93); EP-A-540,090 (5/5/93); U.S. 4,615,820; EP-A-
565,017 (10/13I93); EP-A-030,096 (6110/81), 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 PHASE and, optionally but
preferably, a SOLID PHASE, all as described in more detail hereinafter and in
the
cited references. The AQP 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.
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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.
In the following Examples all levels are quoted as % by weight of the
composition.
EXAMPLES
In the following Examples a11 levels are quoted as % by weight of the
composition.
EXAMPLE I
Ethoxylation and Quaternization of Bis(hexamethylene)triamine - The
ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave
equipped for
temperature measurement and control, pressure measurement, vacuum and inert
gas
purging, sampling, and for introduction of ethylene oxide as a liquid. A ~20
lb. net
cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a
liquid by a
pump to the autoclave with the cylinder placed on a scale so that the weight
change
of the cylinder can be monitored.
A 362 g portion of bis(hexamethylene)triamine (Aldrich, 1.69 moles) is
added to the clean, dry autoclave which has been flushed with nitrogen. The
autoclave is then sealed and pressurized with nitrogen to 2S0 psia. The
nitrogen is
vented back to atmospheric pressure and then repressurized to 200 psia. With
stirring, the autoclave contents are heated to 105~C and 372 g (8.45 moles) of
ethylene oxide is pumped in gradually over about a 2 hour period while
maintaining
the temperature in the 100-110 ~C range. The temperature is maintained for an
additional hour to allow all the ethylene oxide to react. At this point, a
portion of the
reaction product is removed through a bottom valve, leaving 262g (0.602 mol)
of
hydroxyethylated triamine in the reactor which is then cooled to near room
temperature and the reactor is placed under vacuum. Then 65g (0.30 mot) of 25%
sodium methoxide in methanol is added through a valve at the top of the
autoclave
while maintaining vacuum. While stirring vigorously, the temperature is
gradually
raised to 130C~ and held there for about 1 hour to remove all methanol. Then
the
temperature is adjusted to 105C~ and ethylene oxide addition is resumed. An
additional 1457 g (33.1 mol) of ethylene oxide is slowly added while holding
the
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67
temperature in the 100-110C~ range. After this addition, temperature is
maintained
for about 2 hours and another sample is withdrawn corresponding to
ethoxylation of
each original NH to a degree of 12. This process of ethoxylation and
withdrawing of
a sample is repeated two more times to prepare additional samples wherein the
degree of ethoxylation per original NH is 20 and 30. The alkoxide in each
sample is
neutralized by slowly adding the theoretical amount of methanesulfonic acid to
the
samples with good stirring at a temperature above their melting point and
mixing
thoroughly. The degree of ethoxylation of each sample is confirmed by 1 H-NMR
spectroscopy by comparing the size of the resonances of the methylene CH2
peaks at
1.2-1.6 ppm with the -OCH_2 peaks at 3.4-3.8 ppm .
The sample of bis(hexamethylene)triamine ethoxylated to a degree of 30 is
quaternized by dissolving a 100g (0.0l47 mole) portion in 100 ml of
acetonitrile and
adding dimethyl sulfate (Aldrich, 5.56g, 0.044 mol). This reaction mixture is
stirred
at room temperature for 18 hours and then 1 ml of ethanolamine is added and
stirring is continued for an additional 1 hr. to ensure that no residual
dimethyl sulfate
is present. The solvent is then stripped on a rotary evaporator to give the
desired
fully quaternized sample of bis(hexamethylene)triamine ethoxylated to a degree
of
30 on each original NH site. This material is a waxy, tan solid at room
temperature.
The quaternization of the nitrogens is confirmed by 1 H-NMR spectroscopy which
shows disappearance of the CH2-N peak at 2.4-2.8 ppm indicating complete
quaternization.
EXAMPLE II
The following liquid detergent compositions are made
Ingredient Example Example Example
a b c
Wt % Wt % Wt%
C12-l5alkyl polyethoxylate 21.4 20.2 --
(1.8) sulfate
C12-l5alkyl polyethoxylate - - 19.0
(2.5) sulfate
Ethanol 3.7 3.6 3.4
Monoethanolamine 1.0 1.0 1.0
C 10 amidopropyldimethyl amine0.5 0.5 --
Propandiol 6.8 6.4 6.2
C12-l3Alky1 polyethoxylate 0.7 0.6 2.0
(9)
C12-14 alkyl glucose amide 2.7 2.5 3.5
C I 2-14 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 ( 1 OOKLU/g) 0.1 0.08 0.04
Amylase (300KNU/g) T 0.2 ~ 0.2 0.1
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Carezyme (SOOOcevu/g) 0.05 0.5 0.3
Protease (32g/L) 0.9 0.8 1.0
Soil Release Polymer* 0.2 0.5 0.3
AQP** 1.0 2.0 1.2
Polyethyleneimine, MW 600 ethoxylated1.0 -- --
(20 moles EO/nitrogen)
Water, perfume, enzymes, suds to l00% 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
** AQP of Example I.
EXAMPLE III
The following liquid detergent compositions are made:
In reg dient Example Examine 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
Propandiol 8.4 8.5 8.5
C12-l3Alkyl polyethoxylate 2.5 2.8 2.7
(6.5)
C 12-14 alkyl glucose amide 3.8 4.2 4.1
C 12-16 fatty ac id 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 ICNU/g) 0.1 0.4 0.l4
Carezyme (5000 cevu/g) 0.8 0.1 0.5
Lipolase Ultra (100 KL,U/g) 0.1 0.2 0.15
AQP* 3.0 3.0 2.0
Polyethyleneimine, MW 1200 -- -- l.00
ethoxylated
(7 moles EO/nitrogen)
Soil Release Polymer** 0.3 0.3 0.3
Water, perfume, enzymes, fluorscentto 100% to 100% to 100%
brightener, stabilizers, suds
suppressor &
other optional ingredients
* AQP of Example I.
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69
** Oligomer of Sodium 2-[2-(2-Hydroxyethoxy)ethoxy]ethanesulfonate, Dimethyl
Terephthalate, Sodium 2-(2,3-Dihydroxypropoxy)ethanesulfonate, Ethylene
Glycol, and Propylene Glycol)
EXAMPLE IV
The following liquid detergent compositions are made
Ingredient Example
a
Wt
C12-l5alkyl polyethoxylate (3) sulfate4.0
C12-15 alkyl sulfate, branched 14.0
Ethanol 2.2
Monoethanolamine 4.5
C8-10 amidopropyldimethylamine 1.3
Propandiol 9.0
C13-lSAIkyI polyethoxylate (4.0) 4.5
C12-14 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 ( 1 OOKLU/g) 0.1
Endolase (3000 cevu/g) 0.2
AQP* 1.3
PEI 600-E20* * 1.3
Soil Release Polymer*** 0.2
Water, perfume, enzymes, fluorscentto 100%
brightener,
stabilizers, suds suppressor & other
optional
ingredients
* * AQP of Example I.
** Ethoxylated polyethyleneimine E20 having an average MW 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)
