Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT COMPOSITIONS
FIELD
The present invention relates to a detergent composition comprising a soil
dispersant polymer, a non-AQA surfactant and a bis-alkoxylated quaternary
ammonium (bis-AQA) cationic surfactant.
BACKGROUND
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, 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 different types of soils and stains. While a
review
of the literature would seem to indicate that a wide selection of surfactants
and
surfactant combinations are available to the detergent manufacturer, the
reality is
that many such ingredients are speciality chemicals which are not suitable in
low
unit cost items such as home-use laundry detergents. The fact remains that
most such home-use products such as laundry detergents still mainly comprise
one or more of the conventional ethoxylated nonionic and/or sulfated or
sulfonated anionic surfactants, presumably due to economic considerations and
the need to formulate compositions which function reasonably well with a
variety
of soils and stains and a variety of fabrics.
- The quick and efficient removal of different types of soils and stains such
as body soils, greasyloily soils and certain food stains, can be problematic.
Such
soils comprise a mixture of hydrophobic triglycerides, lipids, complex
polysaccharides, inorganic salts and proteinaceous matter and are thus
notoriously difficult to remove. An additional problem is encountered in the
form
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of lime-soap deposits; the insoluble hardness ion salt (e.g. Ca2+IMg2+) of
fatty
acids derived from the degradation of triglyceride soils. Low levels of
hydrophobic soils, residual stains and lime-soap deposits often remain on the
surface of the fabric after washing. Successive washing and wearing coupled
with limited removal of the soils, stains and deposits in the wash culminates
in a
build-up on the fabric which further entraps particulate dirt leading to
fabric
yellowing. Eventually the fabric takes on a dingy appearance which is
perceived
as unwearable and discarded by the consumer.
The literature suggests that various nitrogen-containing cationic
IO surfactants 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 speciality 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:
IS 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 has been limited by the difficulty
encountered in the large scale manufacture of such compounds. An additional
limitation has been the potential precipitation of anionic active components
of the
20 detergent composition occasioned by their ionic interaction with cationic
surfactants. The aforementioned nonionic and anionic surfactants remain the
major surfactant components in today's laundry compositions.
It has been discovered that certain bis-alkoxylated quaternary ammonium
(bis-AQA) compounds can be used in various detergent compositions to boost
25 detergency performance on a variety of soil and stain types, particularfy
hydrophobic soils and lime-soap deposits, commonly encountered. The bis-AQA
surfactants of the present invention provide substantial benefits to the
formulator,
over cationic surfactants previously known in the art. For example, the bis-
AQA
surfactants used herein provide marked improvement in cleaning of "everyday"
30 greasy/oily hydrophobic soils regularly encountered. Moreover, the bis-AQA
surfactants are compatible with anionic surfactants commonly used in detergent
compositions such as alkyl sulfate and alkyl benzene sulfonate;
incompatibility
with anionic components of the detergent composition has commonly been the
limiting factor in the use of cationic surfactants to date. Low levels (as low
as
35 3 ppm in the laundering liquor) of bis-AQA surfactants gives rise to the
benefits
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described herein. Bis-AQA surfactants can be formulated over a broad pH range
from 5 to 12. The bis-AQA surfactants can be prepared as 30% (wt.) solutions
which are pumpable, and therefore easy to handle in a manufacturing plant. Bis-
AQA surfactants with degrees of ethoxylation above 5 are sometimes present in
a liquid form and can therefore be provided as 100% neat materials. in
addition
to their beneficial handling properties, the availability of bis-AQA
surfactants as
highly concentrated solutions provides a substantial economic advantage in
transportation costs.
Furthermore, it has also been discovered that compositions containing a
soil dispersant polymer and a bis-AQA surfactant can deliver additional
superior
cleaning and whiteness performance versus products containing either
technology alone. Particularly, there is a boost in detergency performance on
claylmud soils as well as soils found on socks. Polymeric dispersants enhance
overall detergency by crystal growth inhibition, particulate soil release
peptization, anti-redeposition and soil soiubilization. Although not wanting
to be
limited by theory, it is believed that benefits of the bis-AQAlsoil dispersant
polymer system are the result of: (1) AQA action on the stain surface to
minimise lime-soap formation and to lift off any calcium soaps present,
thereby
facilitating improved polymer deposition; (2) AQA providing solubilization
deep
into the soil, while the polymer acts as a "grease removal shuttle", stripping
out
the AQA-soiubilized stain components and dispersing them into the wash liquor.
BACKGROUND ART
U.S. Patent 5,441,541, issued August 15, 1995, to A. Mehreteab and F. J.
Loprest, relates to anioniclcationic surtactant mixtures. U.K. 2,040,990,
issued 3
Sept., 1980, to A. P. Murphy, R.J.M. Smith and M. P. Brooks, relates to
ethoxylated cationics in laundry detergents.
None of the existing art provides all of the advantages and benefits of the
present invention.
- SUMMARY
The present invention provides a composition comprising or prepared by
combining a soil dispersant polymer, a non-AQA surfactant and an effective
amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant
of the formula:
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R\ / APR3
\N+ X
R2~ ~A~qRa
wherein R1 is a linear, branched or substituted Cg-C1g alkyl, alkenyl, aryl,
alkanyl, ether or gluycityl ether moiety, R2 is a C1-C3 alkyl moiety, R3 and
R4
can vary independently and are selected from hydrogen, methyl and ethyl, X is
an anion, and A and A' can vary independently and are each C1-C4 alkoxy, p
and q can vary independently and are integers of from 1 to 30, and wherein the
weight ratio of the bis-AQA to the soil dispersant polymer is in the range of
from
about 1:11 to about 1:14.
These and other features, aspects, and advantages of the present
invention will become evident to those skilled in the art from a reading of
the
present disclosure.
DETAILED DESCRIPTION
While the specification concludes with claims particularly pointing and
distinctly claiming the invention, it is believed the present invention will
be better
understood from the following description.
All percentages are by weight of total composition unless specifically
stated otherwise. Ali ratios are weight ratios unless specifically stated
otherwise.
As used herein, "comprising" means that other steps and other ingredients
which
do not affect the end result can be added. This term encompasses the terms
"consisting of and "consisting essentially of."
Ali cited references are incorporated herein by reference in their entireties.
Citation of any reference. is not an admission regarding any determination as
to
its availability as prior art to the claimed invention.
ItI has surprisingly been discovered that compositions containing a soil
dispersant polymer and a bis-AQA surfactant at a particular ratio can deliver
additional superior cleaning and whiteness performance versus products
containing either technology alone. Particularly, there is a boost of
detergency
performance on claylmud soils as well as soils on socks. This surprising
benefit
is evident when the weight ratio of bis-AQA to the soil dispersant polymer is
in
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the range of from about 1:11 to about 1:14, preferably from about 1:12 to
about
1:13.
Soil Dispersant Polymer
The compositions of the present invention comprise a soil dispersant
5 polymer. Soil dispersant polymers are present at levels from 5% to 20%,
preferably from 10% to 15%, more preferably from 13% to 14% by weight, of the
compositions herein. Preferred dispersants for use herein include polymeric
poiycarboxylates.
Polymeric polycarboxylate materials can be prepared by polymerizing or
copoiymerizing 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 40% by weight.
Particularly suitable polymeric polycarboxylates can be derived from
acrylic acid. Such acrylic acid-based polymers which are useful herein are the
water-soluble salts of polymerized acrylic acid. The average molecular weight
of
such polymers in the acid form preferably ranges from 2,000 to 10,000, more
preferably from 4,000 to 7,000 and most preferably from 4,000 to 5,000.
Water-soluble salts of such acrylic.acid polymers can include, for example,
the
alkali metal, ammonium and substituted ammonium salts. Soluble polymers of
this type are known materials. Use of polyacrylates of this type in detergent
compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067,
issued March 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred soil
dispersant polymers. 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 2,000 to 700,000, more
preferably from 5,000 to 75,000, most preferably from 7,000 to 65,000. The
ratio
of acrylate to maleate segments in such copolymers will generally range from
30:1 to 1:1, more preferably from 10:1 to 2:1. Water-soluble salts of such
acrylic
acid/maleic acid copolymers can include, for example, the alkali metal,
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ammonium and substituted ammonium salts. Soluble acrylate/maleate
copolymers of this type are known materials which are described in European
Patent Application No. 66915, published December 15, 1982, as well as in EP
193,360, published September 3, 1986, which also describes such polymers
comprising hydroxypropylacrylate. Still other useful dispersants include the
maleiclacryliclvinyl alcohol terpolymers. Such materials are also disclosed in
EP
193,360, including, for example, the 45145110 terpolymer of
acryliclmaleiclvinyl
alcohol.
Bis-Alkoxylated Quaternary Ammonium (bis-AQA) Cationic Surfactant
The second essential component of the present invention comprises an
effective amount of a bis-AQA surfactant of the formula:
Ri / APR3
N+ X_
R2~ ~ A,qRa
wherein R1 is a linear, branched or substituted alkyl, alkenyl, aryl, alkaryl,
ether,
glycityl ether moiety containing from 8 to 18 carbon atoms, preferably 8 to 16
carbon atoms, most preferably from 8 to14 carbon atoms; R2 is an alkyl group
containing from 1 to 3 carbon atoms, preferably methyl; R3 and R4 can vary
independently and are selected from the group consisiting of hydrogen
(preferred), methyl and ethyl; X- is an anion such as chloride, bromide,
methyl
sulfate, sulfate, sufficient to provide electrical neutrality. A and A' can
vary
independently and are each selected from C1-C4 alkoxy, especially ethoxy,
propoxy, butoxy and mixtures thereof; p is from 1 to 30, preferably 1 to 15,
more
preferably 1 to 8, even more preferably 1 to 4 and q is from 1 to 30,
preferably to
15, more preferably 1 to 8, even more preferably 1 to 4. Most preferably both
p
and q are 1.
Bis-AQA compounds wherein the hydrocarbyl substituent R1 is Cg-C12,
especially Cg-Clp, enhance the rate of dissolution of laundry granules,
especially under cold water conditions, as compared with the higher chain
length
materials. Accordingly, the Cg-C12 bis- AQA surfactants may be preferred by
some formulators. The levels of the bis-AQA surfactants used to prepare
finished laundry detergent compositions can range from 0.3% to 4%, preferably
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from 0.5% to 2%, more preferably from 0.8% to 1.2%, by weight. As stated
previously, the weight ratio of bis-AQA to the soil dispersant polymer is in
the
range of from about 1:11 to about 1:14, preferably from about 1:12 to about
1:13.
The weight ratio of bis-AQA to percarbonate bleach is in the range of from
1:100 to 5:1, preferably from 1:60 to 2:1, most preferably from 1: 20 to 1:1.
The present invention employs an "effective amount" of the bis-AQA
surfactants to improve the performance of cleaning compositions which contain
other optional ingredients. By an "effective amount" of the bis-AQA
surfactants
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 bis-AQA to at least directionally improve cleaning performance
against
such stains. Likewise, in a composition whose targets include clay soil, the
formulator will use sufficient bis-AQA to at least directionally improve
cleaning
performance against such soil.
The bis-AQA surfactants may be used in combination with other 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.
For example, in a top-loading, vertical axis U.S.-type automatic washing
machine using 45 to 83 liters of water in the wash bath, a wash cycle of 10 to
14 minutes and a wash water temperature of 10°C to 50°C, it is
preferred to
include from 2 ppm to 50 ppm, preferably from 5 ppm to 25 ppm, of the bis-AQA
surfactant in the wash liquor. On the basis of usage rates of from 50 ml to
150 ml per wash load, this translates into an in-product concentration (wt.)
of the
bis-AQA surfactant of from 0.1 % to 3.2%, preferably 0.3% to 1.5%, for a heavy-
duty liquid laundry detergent. On the basis of usage rates of from 60 g to 95
g
per wash load, for dense ("compact") granular laundry detergents (density
above
650 gll) this translates into an in-product concentration (wt.) of the bis-AQA
surfactant of from 0.2% to 5.0%, preferably from 0.5% to 2.5%. On the basis of
usage rates of from 80 g to 100 g per load for spray-dried granules (i.e.,
"fluffy";
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density below 650 g/l), this translates into an in-product concentration (wt.)
of the
bis-AQA surfactant of from 0.1 % to 3.5%, preferably from 0.3% to 1.5%.
For example, in a front-loading, horizontal-axis European-type automatic
washing machine using 8 to 15 liters of water in the wash bath, a wash cycle
of
10 to 60 minutes and a wash water temperature of 30°C to 95°C,
it is preferred
to include from 13 ppm to 900 ppm, preferably from 16 ppm to 390 ppm, of the
bis-AQA surfactant in the wash liquor. On the basis of usage rates of from 45
ml
to 270 m! per wash load, this translates into an in-product concentration
(wt.) of
the bis-AQA surfactant of from 0.4% to 2.64%, preferably 0.55% to 1.1 %, for a
heavy-duty liquid laundry detergent. On the basis of usage rates of from 40 g
to
210 g per wash load, for dense ("compact") granular laundry detergents
(density
above 650 g/l) this translates into an in-product concentration (wt.) of the
bis-
AQA surfactant of from 0.5 % to 3.5 %, preferably from 0.7 % to 1.5 %. On the
basis of usage rates of from 140 g to 400 g per load for spray-dried granules
(i.e., "fluffy"; density below 650 g/l), this translates into an in-product
concentration (wt.) of the bis-AQA surfactant of from 0.13% to 1.8%,
preferably
from 0.18% to 0.76%.
For example, in a top-loading, vertical-axis Japanese-type automatic
washing machine using 26 to 52 liters of water in the wash bath, a wash cycle
of
8 to 15 minutes and a wash water temperature of 5°C to 25°C, it
is preferred to
include from 1.67 ppm to 66.67 ppm, preferably from 3 ppm to 6 ppm, of the bis-
AQA surfactant in the wash liquor. On the basis of usage rates of from 20 ml
to
ml per wash load, this translates into an in-product concentration (wt.) of
the
bis-AQA surfactant of from 0.25% to 10%, preferably 1.5% to 2%, for a heavy-
25 duty liquid lauridry detergent. On the basis of usage rates of from 18 g to
35 g
per wash load, for dense ("compact") granular laundry detergents (density
above
650 g/l) this translates into an in-product concentration (wt.) of the bis-AQA
surfactant of from 0.25% to 10%, preferably from 0.5% to1.0%. On the basis of
usage rates of from 30 g to 40 g per load for spray-dried granules (i.e.,
"fluffy";
30 density below 650 gll), this translates into an in-product concentration
(wt.) of the
bis-AQA surfactant of from 0.25% to10%, preferably from 0.5% to 1%.
As can be~ seen from the foregoing, the amount of bis-AQA surfactant
used in a machine-wash laundering context can vary, depending on the habits
and practices of the user, the type of washing machine. In this context,
however,
one heretofore unappreciated advantage of the bis-AQA surfactants is their
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ability to provide at least directional improvements in performance over a
spectrum of soils and stains even when used at relatively low levels with
respect
to the other surtactants (generally avionics or anioniclnonionic mixtures) in
the
finished compositions. This is to be distinguished from other compositions of
the
art wherein various cationic surfactants are used with anionic surfactants at
or
near stoichiometric levels. In general, in the practice of this invention, the
weight
ratio of bis-AQA:anionic surfactant in laundry compositions is in the range
from
1:70 to 1:2, preferably from 1:40 to 1:6, preferably from 1:30 to 1:6, most
preferably 1:15 to 1:8. In laundry compositions which comprise both anionic
and
nonionic surfactants, the weight ratio of bis-AQA:mixed anionic/nonionic is in
the
range from 1:80 to 1:2, preferably 1:50 to 1:8.
Various other cleaning compositions which comprise an anionic
surfactant, an optional nonionic surfactant and specialized surfactants such
as
betaines, sultaines, amine oxides can also be formulated using an effective
15' amount of the bis-AQA surfactants 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
bis-AQA surfactants in such compositions. Again, as in the case of the
granular
and liquid laundry compositions, the weight ratio of the bis-AQA surfactant to
other surfactants present in such compositions is low, i.e., sub-
stoichiometric in
the case of avionics. Preferably, such cleaning compositions comprise bis-
AQAlsurfactanf ratios as noted immediately above for machine-use laundry
compositions.
In contrast with other cationic surfactants known in the art, the bis-
alkoxylated cationics herein have sufficient solubility that they can be used
in
combination with mixed surfactant systems which are quite low in nonionic
surfactants and which contain, for example, alkyl sulfate surfactants. This
can
- be an important consideration for formulators of detergent compositions of
the
type which are conventionally designed for use in top loading automatic
washing
machines, especially of the type used in North America, as well as under
Japanese usage conditions. Typically, such compositions will comprise an
anionic surfactant:nonionic surfactant weight ratio in the range from about
25:1
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to about 1:25, preferably about 20:1 to about 3:1. This can be contrasted with
European-type formulas which typically will comprise anionic:nonionic ratios
in
the range of about 10:1 to 1:10, preferably about 5:1 to about 1:1.
The preferred ethoxylated cationic surfactants herein are available under
5 the trade name ETHOQUAD from Akzo Nobel Chemicals Company.
Alternatively, such materials can be synthesized using a variety of different
reaction schemes (wherein "EO" represents -CH2CH20- units), as follows.
SCHEME 1
R~OH + N H3 H2/Cat/Heat R~ N.H
~H
EXC ES S
Rl N~H + 2 O BASE Cat Rl N-~~O~n~2
n U HEAT
H
RI N-~(EO)nH~2 + CH3C1 HEM R1 N~ ~(EO)nH~2
CH3 C1
SCHEME 2
O
H~N-f(EO)2H12 + ~C~ H~/Cat CH3~N-~(EO)2H)2
H H HEAT
R~Br + CH3'N-[(EO)2HJ2 HEM R~ N~ UEO)2H~2
C H3 Br
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SCHEME 3
H O CH
'N-[(EO)2H]z + ~C\ -Hz/~ 3~N
H H HEAT [(EO)zH]z
R~Br + CH3\N-[(EO)zH]z H~ R~ N~ [(EO)zH]z
CH3 Br
SCHEME 4
O SbClS CAT
CI-CH2CHz-OH + nU --i CI-CH2CH20[EO]n-H
i ~ H HEAT 1 +
R-N~CH3 + 2 CI-CH2CH20[EO]n-H ----~- R N-[CHzCH20[EO]~-i]z
CH3 Cf
An economical reaction scheme is as follows.
SCHEME 5
Rl OS03 Na+- + H-N-[(EO)H]z ~ R1 N-[(EO)H]z
O
R~ N-[~O)H]2 + 2 nU BAfS~E TAT Rt N-[(EO)(EO)nH]2
R~ N-[(EO)(EO)nH]z + CH3C1---> R~ N~ [(EO)(EO)nH]z
CH3 CI
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The following parameters summarize the optional and preferred reaction
conditions of Scheme 5. Step 1 of the reaction is preferably conducted in an
aqueous medium. Reaction temperatures are typically in the range of 140-
200°
C. Reaction pressures are 50-1000 psig. A base catalyst, preferably sodium
hydroxide can be used. The mole ratio of reactants are 2:1 to 1:1 amine to
alkyl
sulfate. The reaction is preferably conducted using Cg-C14 alkyl sulfate,
sodium
salt. The ethoxylation and quaternization steps are carried out using
conventional conditions and reactants.
Under some circumstances reaction Scheme 5 results in products which
are sufficiently soluble in the aqueous reaction medium that gels may form.
While the desired product can be recovered from the gel, an alternate, two-
step
synthesis Scheme 6, hereinafter, may be more desirable in some commercial
circumstances. The first step in Scheme 6 is conducted as in Scheme 5. The
second step (ethoxylation) is preferably conducted using ethylene oxide and an
acid such as HCI which provides the quaternary surfactant. As shown below,
chlorohydrin i.e., chloroethanol, can also be reacted to give the desired
bishydroxyethyl derivative.
For reaction Scheme 6, the following parameters summarize the optional
and preferred reaction conditions for the first step. The first step is
preferably
conducted in an aqueous medium. Reaction temperatures are typically in the
range of 100-230°C. Reaction pressures are 50-1000 psig. A base,
preferably
sodium hydroxide, can be used to react with the HS04-generated during the
reaction, or an excess of the amine can be employed to also react with the
acid.
The mole ratio of amine to alkyl sulfate is typically from 10:1 to 1:1.5;
preferably
from 5:1 to 1:1.1; more preferably from 2:1 to 1:1. In the product recovery
step,
the desired substituted amine is simply allowed to separate as a distinct
phase
from the aqueous reaction medium in which it is insoluble. The second step of
the process is conducted under conventional reaction conditions. Further
ethoxylation and quaternization to provide bis-AQA surfactants are conducted
under standard reaction conditions.
Scheme 7 can optionally be conducted using ethylene oxide under
standard ethoxylation conditions, but without catalyst, to achieve
monoethoxyiation.
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The following illustrates these additional reaction schemes, wherein "EO"
represents the -CH2CH20- unit. In the reactions, either an inorganic base, an
organic base or excess amine reactant is used to neutralize generated HS04.
Scheme 6
H
_ H
R1 OS03 Na+ + H~N-CH2CH2-OH--~ R~ N-CHZCH2-OH
H
I ~CH2CH20H
R NCH2CH20H + CICH2CH20H --~ R~N\
CH2CH20H
Scheme 7
O ~CH2CH20H
R N-CH2CHZOH NUtal st R-N\
EO~H
The following further illustrates several of the above reactions solely for
the convenience of the formulator, but is not intended to be limiting thereof.
Synthesis A
Preparation of N. N-Bis(2-hydroxyethyl)dodecvlamine
To a glass autoclave liner is added 19.96 g of sodium dodecyl sulfate
(0.06921 moles), 14.55 g of diethanolamine (0.1384 moles), 7.6 g of 50 wt.
IS sodium hydroxide solution (0.095 motes) and 72 g of distilled H20. The
glass
liner is sealed into a 500 ml, stainless steel, rocking autoclave and heated
to
160-180°C under 300-400 psig nitrogen for 3-4 hours. The mixture is
cooled to
room temperature and the liquid contents of the glass liner are poured into a
250
ml separatory funnel along with 80 ml of chloroform. The funnel is shaken well
for a few minutes and then the mixture is allowed to separate. The lower
chloroform layer is drained and the chloroform evaporated off to obtain
product.
Synthesis B
Preparation of N N-Bis~2-hydrox~ethyl)dodecylamine
1 Mofe of sodium dodecyl sulfate is reacted with 1 mole of ethanolamine
in the presence of base in the manner described in Synthesis A. The resulting
2
hydroxyethyldodecylamine is recovered and reacted with 1-chloroethanol to
prepare the title compound.
Synthesis C
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Preparation of N,N-Bis(2-hydroxyethyl)dodecylamine
To a glass autoclave liner is added 19.96 g of sodium dodecyl sulfate
(0.06921 moles), 21.378 of ethanolamine (0.3460 moles), 7.6 g of 50 wt.
sodium hydroxide solution (0.095 moles) and 72 g of distilled H20. The glass
liner is sealed into a 500 ml, stainless steel, rocking autoclave and heated
to
160-180°C under 300-400 psig nitrogen for 3-4 hours. The mixture is
cooled to
room temperature and the liquid contents of the glass liner are poured into a
250
ml separatory funnel along with 80 ml of chloroform. The funnel is shaken well
for a few minutes and then allowed mixture to separate. The lower chloroform
layer is drained and the chloroform is evaporated off to obtain product. The
product is then reacted with 1 molar equivalent of ethylene oxide in the
absence
of base catalyst at 120-130°C to produce the desired final product.
The bis-substituted amines prepared in the foregoing Syntheses can be
further ethoxylated in standard fashion. Quaternization with an alkyl halide
to
form the bis-AQA surfactants herein is routine.
According to the foregoing, the following are nonlimiting, specific
illustrations of bis-AQA surfactants used herein. It is to be understood that
the
degree of alkoxyiation noted herein for the bis-AQA surfactants is reported as
an
average, following common practice for conventional ethoxylated nonionic
surfactants. This is because the ethoxylation reactions typically yield
mixtures of
materials with differing degrees of ethoxylation. Thus, it is not uncommon to
report total EO values other than as whole numbers, e.g., "E02.5", "E03.5".
Designation R1 R2 ApR3 q'aR4
bis-AQA-1 C12-C14 CH3 EO EO
(also referred to as
Coco Methyl E02)
bis-AQA-2 C12-C1g CH3 (EO)2 EO
bis-AQA-3 C12-C14 CH3 (EO)2 (EO)2
(Coco Methyl E04)
bis-AQA-4 C12 CHg EO EO
bis-AQA-5 C12-C14 CH3 (EO)2 (EO)3
,.,
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bis-AQA-6 C12-C14 CH3 (EO)2 {EO)3
bis-AQA-7 Cg-C1g CH3 {EO)3 (EO)2
5 bis-AQA-8 C12-C14 CH3 (EO)4 (EO)4
bis-AQA-9 C12-C14 C2H5 (EO)3 (EO)3
bis-AQA-10 C12-C1g C3H7 (EO)3 (EO)4
10
bis-AQA-11 C12-C1g CH3 {propoxy) (EO)3
bis-AQA-12 C'p-C1g C2H5 (iso-propoxy)2
(EO)3
15 bis-AQA-13 C10-C18 CH3 (EOIPO)2 (EQ)3
bis-AQA-14 Cg-C1g CH3 (EO)15* (EO)15*
bis-AQA-15 C1p CH3 EO EO
bis-AQA-16 Cg-C12 CH3 EO EO
bis-AQA-17 Cg-C11 CH3 - EO 3.5
Avg. -
bis-AQA-18 C12 CH3 - EO 3.5
Avg. -
bis-AQA-19 Cg-C14 CH3 (EO)1p (EO)10
bis-AQA-20 C1p C2H5 (EO)2 (EO)3
3a
bis-AQA-21 C12-C14 C2H5 (EO)5 (EO)3
. bis-AQA-22 C12-C1g C3H7 Bu (EO)2
*Ethoxy, optionallyend-capped
with methyl
or ethyl.
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16
Highly preferred bis-AQA compounds for use herein are of the formula;
Ri CH2CHZOH
~N+~ XO
CH3/ 'CH2CH20H
wherein R~ is Cg-C1g hydrocarbyl and mixtures thereof, preferably Cg, C10,
C12, C14 alkyl and mixtures thereof. X is any convenient anion to provide
charge balance, preferably chloride. With reference to the general bis-AQA
structure noted above, since in a preferred compound R1 is derived from
coconut (C12-C14 alkyl) fraction fatty acids, R2 is methyl and ApR3 and A'qR4
are each monoethoxy, this preferred type of compound is referred to herein as
"CocoMeE02" or "bis-AQA-1" in the above list.
Other bis-AQA surfactants useful herein include compounds of the
formula:
R~ /(CH2CH2O)pH
N+ X-
R2~ ~(CH2CH20)qH
wherein R1 is Cg-C1g hydrocarbyl, preferably Cg-C14 alkyl, independently p is
1
to 3 and q is '! to 3, R~ is C1-C3 alkyl, preferably methyl, and X is an
anion,
especially chloride or bromide.
Other compounds of the foregoing type include those wherein the ethoxy
(CH2CH20) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CHg)CH20J
and [CH2CH(CHgOJ units (i-Pr) or n-propoxy units (Pr), or mixtures of EO
and/or
Pr andlor i-Pr units.
A highly preferred bis-AQA compound for use in under built formulations
are of the formula wherein p andlor q are integers in the range of between 10
and 15. This compound is particularly useful in laundry handwash detergent
compositions.
Non-AQA Detersive Surfactants
In addition to the bis-AQA surfactant, the compositions of the present
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17
invention preferably further comprise a non-AQA surfactant. Non-AQA
surfactants may include essentially any anionic, nonionic or additional
cationic
surfactant.
Anionic Surfactant
Nonlimiting exarnpfes of anionic surfactants useful herein typically at
levels from 1 % to 55%, by weight, include the conventional C1 ~-C1 g alkyl
benzene sulfonates ("LAS") and primary ("AS"), branched-chain and random
C10-C20 alkyl sulfates, the C10-C1g 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 7, preferably at least 9, and M is a
water-solubilizing cation, especially sodium, unsaturated sulfates such as
oleyl
sulfate, the C12-C1g alpha-suifonated fatty acid esters, the C10-C18 sulfated
polyglycosides, the C10-C1 g alkyl aikoxy sulfates ("AExS"; especially EO 1-7
ethoxy sulfates), and the C10-C18 alkyl alkoxy carboxylates (especially the EO
1-5 ethoxycarboxylates). The C12-C1g betaines and sulfobetaines ("sultaines"),
C10-C1g amine oxides, can also be included in the overall compositions. C10-
C20 conventional soaps may also be used. If high sudsing is desired, the
branched-chain C10-C16 soaps may be used. Other conventional useful
surfactants are listed in standard texts.
Nonionic Surfactants
Noniimiting examples of nonionic surfactants useful herein typically at
levels from 1 % to 55%, by weight include the alkoxylated alcohols (AE's) and
alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides
{APG's), C1p-C1g glycerol ethers.
More specifically, the condensation products of primary and secondary
aliphatic alcohols with from 1 to 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 8 to 22 carbon atoms. Preferred are the condensation
products of alcohols having an alkyl group containing from 8 to 20 carbon
atoms,
more preferably from 10 to18 carbon atoms, with from 1 to10 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: TergitoITM
15-S-
9 (the condensation product of C1 ~-C15 linear alcohol with 9 moles ethylene
oxide) and TergitoITM 24-L-6 NMW (the condensation product of C12-C14
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18
primary alcohol with 6 moles ethylene oxide with a narrow molecular weight
distribution), both marketed by Union Carbide Corporation; NeodoITM 45-9 (the
condensation product of C14-C15 linear alcohol with 9 moles of ethylene
oxide),
NeodoITM 23-3 (the condensation product of C12-C13 linear alcohol with 3
moles of ethylene oxide), NeodoITM 45-7 (the condensation product of C14-C15
linear alcohol with 7 moles of ethylene oxide) and NeodoITM 45-5 (the
condensation product of C14-C15 linear alcohol with 5 moles of ethylene oxide)
marketed by Shell Chemical Company; KyroTM EOB (the condensation product
of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter &
Gamble Company; and Genapol LA 030 or 050 (the condensation product of
C12-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. The
preferred range of HLB in these AE nonionic surfactants is from 8-11 and most
preferred from 8-10. Condensates with propylene oxide and butylene oxides
may also be used. '
Another class of preferred nonionic surfactants for use herein are the
polyhydroxy fatty acid amide surfactants of the formula.
R2, i -N -Z,
O R~
wherein R1 is H, or C1~ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a
mixture thereof, R2 is C5_31 hYdrocarbyl, and Z is a polyhydroxyhydrocarbyl
having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected
to
the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2
is a
straight C11-15 alkyl or C15_17 alkyl or alkenyl chain such as coconut alkyl
or
mixtures thereof, and Z is derived from a reducing sugar such as glucose,
fructose, maltose, lactose, in a reductive amination reaction. Typical
examples
include the C12-C1g and C12-C14 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, 1986, having a hydrophobic group containing from 6 to 30
carbon atoms, preferably from 10 to 16 carbon atoms, and a polysaccharide,
e.g.
a polyglycoside, hydrophilic group containing from 1.3 to 10, preferably from
1.3
i
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19
to 3, most preferably from 1.3 to 2.7 saccharide units. Any reducing
saccharide
containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and
galactosyl moieties can be substituted for the glucosyl moieties (optionally
the
hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a
glucose or galactose as opposed to a glucoside or gaiactoside). The
intersaccharide bonds can be, e.g., between the one position of the additional
saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding
saccharide units.
The preferred alkyipolyglycosides 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 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3,
preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to 10,
preferably
from 1.3 to 3, most preferably from 1.3 to 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 giycosyl units
2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.
Polyethylene, polypropylene, and poiybutylene 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 6 to 14 carbon atoms, preferably from 8
to
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 2 to 25 moles, more preferably from 3 tol5 moles, of
ethylene oxide per mole of alkyl phenol. Commercially available nonionic
surfactants of this type include IgepaITM CO-630, marketed by the GAF
Corporation; and TritonTM X-45, X-114, X-100 and X-102, all marketed by the
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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
5 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 1500 to 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
10 retained up to the point where the polyoxyethylene content is 50% of the
total
weight of the condensation product, which corresponds to condensation with up
to 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
15 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 2500 to 3000. This hydrophobic moiety is
20 condensed with ethylene oxide to the extent that the condensation product
contains from 40% to 80% by weight of polyoxyethylene and has a molecular
weight of from 5,000 to 11,000. Examples of this type of nonionic surfactant
include certain of the commercially available TetronicTM compounds, marketed
by BASF.
Additional Cationic surfactants
Suitable cationic surfactants are preferably water dispersible compound
having surfactant properties comprising at least one ester (ie -COO-) linkage
and
at least one cationically charged group.
Other suitable cationic surfactants include the quaternary ammonium
surfactants selected from mono C6-C16, preferably Cg-C1p N-alkyl or alkenyl
ammonium surfactants wherein the remaining N positions are substituted by
methyl, hydroxyethyl or hydroxypropyl groups. Other suitable cationic ester
surfactants, including choline ester surfactants, have for example been
disclosed
in US Patents No.s 4228042, 4239660 and 4260529.
............... r ,. ~. ~ ,. .....
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21
Optional Deteraent fnq~redients
The following illustrates various other optional ingredients which may be
used in the compositions of this invention, but is not intended to be limiting
thereof.
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 1 % builder. Liquid formulations typically
comprise 5%
to 50%, more typically 5% to 35% of builder. Granular formulations typically
comprise from 10% to 80%, more typically 15% to 50% builder by weight of the
detergent composition. Lower or higher levels of builders are not excluded.
For
example, certain detergent additive or high-surfactant formulations can be
unbuilt.
Suitable builders herein can be selected from the group consisting of
phosphates and polyphosphates, especially the sodium salts; silicates
including
water-soluble and hydrous solid types and including those having chain-, layer-
,
or three-dimensional- structure as well as amorphous-solid or non-structured-
liquid types; carbonates, bicarbonates, sesquicarbonates and carbonate
minerals other than sodium carbonate or sesquicarbonate; aluminosiiicates;
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
carboxyiates 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 carriers which may be
important
to the engineering of stable surfactant andlor builder-containing detergent
compositions.
Builder mixtures, sometimes termed "builder systems" can be used and
typically comprise two or more conventional builders, optionally complemented
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22
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 60:1 to 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 exempiifed by the tripolyphosphates,
pyrophosphates, glassy polymeric meta-phosphates; and phosphonates.
Suitable silicate builders include alkali metal silicates, particularly those
liquids and solids having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1,
including,
particularly for automatic dishwashing purposes, solid hydrous 2-ratio
silicates
marketed by PQ Corp. under the tradename BRITESIL~, e.g., BRlTESIL 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 b-Na2Si05 morphology silicate marketed by Hoechst and is
preferred especially in granular laundry compositions. See preparative methods
in German DE-A-3,417,649 and DE-A-3,742,043. Other layered silicates, such
as those having the general formula NaMSix02xt1~yH20 wherein M is sodium
or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from
0
to 20, preferably 0, can also or alternately be used herein. Layered silicates
from
Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, as the a, ~ and y
layer-silicate forms. Other silicates may also be useful, such as magnesium
silicate, which can serve as a crispening agent in granules, as a stabilising
agent
for bleaches, and as a component of suds control systems.
Also suitable for use herein are synthesized crystalline ion exchange
materials or hydrates thereof having chain structure and a composition
represented by the following general formula in . an anhydride form:
xM20~ySi02.zM'O wherein M is Na andlor K, M' is Ca andlor Mg; ylx is 0.5 to
2.0 and z/x is 0.005 to 1.0 as taught in U.S. 5,427,711, Sakaguchi et al, June
27,
1995.
Suitable carbonate builders include alkaline earth and alkali metal carbonates
as
disclosed in German Patent Application No. 2,321,001 published on November
15, 1973, although sodium bicarbonate, sodium carbonate, sodium
.....__.",..~,.."-..~. _,................... , .. ,... ,.. .... .....
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23
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)vJ~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 aluminosiiicate
production method is in U.S. 3,985,669, Krummel, et al, October 12, 1976.
Preferred synthetic crystalline aluminosiiicate 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[(AIO2)12(Si02)l2j~xH20 wherein
x is from 20 to 30, especially 27. Dehydrated zeolites (x = 0 - 10) may also
be
used. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in
diameter.
Suitable organic detergent builders include polycarboxylate compounds,
including water-soluble nonsurfactant dicarboxylates and tricarboxylates. More
typically builder polycarboxylates have a plurality of carboxylate groups,
preferably at least 3 carboxyiates. 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, 9964, and Lamberti et al,
U.S.
3,635,830, January 18, 1972; "TMSITDS" 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;
4,158,635; 4,120,874 and 4,102,903.
Other suitable builders are the ether hydroxypolycarboxylates, copolymers
of malefic anhydride with ethylene or vinyl methyl ether; 1, 3, 5-trihydroxy
benzene-2, 4, 6-trisulphonic acid; carboxymethyloxysuccinic acid; the various
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24
alkali metal, ammonium and substituted ammonium salts of polyacetic acids
such as ethylenediamine tetraacetic acid and nitrilotriacetic acid; as well as
meilitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic
acid,
carboxymethyloxysuccinic acid, and soluble salts thereof.
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, hydroxyiminodisuccinate, and methyl glycine diaccetate 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 C5-C20 alkyl and
alkenyl succinic acids and salts thereof. Succinate builders also include:
iaurylsuccinate; myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate
(preferred), 2-pentadecenylsuccinate. Lauryl-succinates are described in
European Patent Application 86200690.5/0,200,263, published November 5,
1986. Fatty acids, e.g., C12-C1 g monocarboxylic acids, can also be
incorporated into the compositions as surfactant/builder materials alone or in
combination with the aforementioned builders, especially citrate andlor the
succinate builders, to provide additional builder activity. Other suitable
potycarboxylates 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.
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Other types of inorganic builder materials which can be used have the
formula (Mx)i Cay (C03)z wherein x and i are integers from 1 to 15, y is an
integer from 1 to 10, z is an integer from 2 to 25, Mi are cations, at least
one of
which is a water-soluble, and the equation Ei = 1-15(xi multiplied by the
valence
5 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
10 present a water-soluble cation selected from the group consisting of
hydrogen,
water-soluble metals, hydrogen, boron, ammonium, silicon, and 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
15 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
20 herein is Na2Ca(C03)2 in any of its crystalline modifications. Suitable
builders
of the above-defined type are further illustrated by, and include, the natural
or
synthetic forms of any one or combinations of the following minerals:
Afghanite,
Andersonite, AshcroftineY, Beyerite, Borcarite, Burbankite, Butschliite,
Cancrinite, Carbocernaite, Carletonite, Davyne, DonnayiteY, Fairchildite,
25 Ferrisurite, F~anzinite, 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.
Bfeach
The compositions described herein may contain a bleach. When present,
such bleaching agents will typically be at levels of from 1 % to 30%, more
typically from 5% to 20%, of the detergent composition, especially for fabric
laundering.
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26
In one preferred aspect the bleaching system contains a hydrogen
peroxide source and a bleach catalyst. The production of the organic
peroxyacid
occurs by an in situ reaction of the bleach activator with a source of
hydrogen
peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate
bleaches. In an alternative preferred aspect a preformed peracid is
incorporated
directly into the composition. Compositions containing mixtures of a hydrogen
peroxide source and bleach activator in combination with a preformed peracid
are also envisaged.
Preferred peroxygen bleaches are perhydrate bleaches. Although the
perhydrate bleach itself has some bleaching capability, a superior bleach
exists
in the peracid formed as a product of the reaction between the hydrogen
peroxide released by the perhydrate and a bleach activator. Preformed peracids
are also envisaged as a preferred peroxygen bleaching species.
Examples of suitable perhydrate salts include perborate, percarbonate;
perphosphate, persulfate and persilicate salts. The preferred perhydrate salts
are
normally the alkali metal salts. The perhydrate salt may be included as the
crystalline solid without additional protection. For certain perhydrate salts
however, the preferred executions of such granular compositions utilize a
coated
form of the material which provides better storage stability for the
perhydrate salt
in the granular product.
Sodium perborate can be in the form of the monohydrate of nominal
formula NaB02H202 or the tetrahydrate NaB02H202.3H20.
Alkali metal percarbonates, particularly sodium percarbonate are
preferred perhydrates for inclusion in compositions in accordance with the
invention. Sodium percarbonate is an addition compound having a formula
corresponding to 2Na2C03.3H202, and is available commercially as a
crystalline solid. Sodium percarbonate, being a hydrogen peroxide addition
compound tends on dissolution to release the hydrogen peroxide quite rapidly
which can increase the tendency for localised high bleach concentrations to
arise. A preferred percarbonate bleach comprises dry particles having an
average particle size in the range from 500 micrometers to 1,000 micrometers,
not more than 10% by weight of said particles being smaller than 200
micrometers and not more than 10% by weight of said particles being larger
than 1,250 micrometers.
..,..... ,. ,. . . ~ ,. f.
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The percarbonate is most preferably incorporated into such compositions
in a coated form which provides in-product stability. A suitable coating
material
providing in product stability comprises mixed salt of a water soluble alkali
metal
sulphate and carbonate. Such coatings together with coating processes have
previously been described in GB-1,466,799, granted to Interox on 9th March
1977. The weight ratio of the mixed salt coating material to percarbonate lies
in
the range from 1:200 to 1:4, more preferably from 1:99 to 1:9, and most
preferably from 1:49 to 1:19. Preferably, the mixed salt is of sodium sulphate
and sodium carbonate which has the general formula Na2S04.n.Na2C03
wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most
preferably n is
from 0.2 to 0.5.
Other coatings which contain silicate (alone or with borate salts or boric
acids or other inorganics), waxes, oils, fatty soaps can also be used
advantageously within the present invention. w
A 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.
Other suitable additional bleaching agents include photoactivated
bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines.
See U.S. Patent 4,033,718, issued Juiy 5, 1977 to Holcombe et al. If used,
detergent compositions will typically contain from 0.025% to 1.25%, by weight,
of
such bleaches, especially sulfonate zinc phthaiocyanine.
Potassium peroxymonopersulfate is another inorganic perhydrate salt of
utility in the compositions herein.
Mixtures of bleaching agents can also be used.
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Bleach Activator
Bleach activators are preferred components where the compositions of
the present invention additionally comprises a peroxygen bleaching agent.
Bleach activators when present are typically at levels of from 0.1 % to 60%,
more
typically from 0.5% to 40% of the bleaching composition comprising the
bleaching agent-plus-bleach activator.
Peroxygen bleaching agents, the perborates, 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 or peracid
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 (NOBS)
and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures
thereof can also be used. See also U.S. 4,634,551 for other typical bleaches
and activators useful herein.
Highly preferred amido-derived bleach activators are those of the
formulae:
R1 N(R5)C(O)R2C(O)L or R1 C(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from 6 to 12 carbon atoms, R2 is an
alkylene containing from 1 to 6 carbon atoms, R5 is H or alkyl, aryl, or
alkaryl
containing from 1 to 10 carbon atoms, and L is any suitable ieaving 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-caproyi)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzene-
sulfonate, {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
l I
C O
I
~C
N
Still another class of preferred bleach activators includes the acyl lactam
activators, especially acyl caprolactams and acyl valerolactams of the
formulae:
O
I!
R6-~-N C H2 C H2~
~C H2-C HZ C H2
O
II
R6-O N-C H2- ~ H2
~C H2-C H2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or aikaryl group containing
from 1 to
12 carbon atoms. Highly preferred lactam activators include benzoyl
caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam,
nonanoyl caprolactam, decanoyl caprolactam, undecenoyi caprolactam, benzoyl
valerolactam, .octanoyl valerolactam, decanoyl vaierolactam, undecenoyl
valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyi valerolactam and
mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October
8, 1985, incorporated herein by reference, which discloses acyl caprolactams,
including benzoyi caprolactam, adsorbed into sodium perborate.
Bleach Catalyst
Bleach catalysts are optional components of the compositions of the
present invention. If desired, the bleaching compounds can be catalyzed by
means of a manganese compound. Such compounds are well known in the art
and include, for example, the manganese-based catalysts disclosed in U.S. Pat.
5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and
European Pat. App. Pub. Nos. 549,271A1, 549,272A1, 544,440A2, and
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544,490A1; Preferred examples of these catalysts include MnlV2(u-O)3(1,4,7-
trimethyl-1,4,7-triazacyclononane)2(PF6)2, Mnlll2(u-O)1(u-OAc)2(1,4,7-
trimethyl-1,4,7-triazacyclononane)2-(C104)2, MnlV4(u-O)6(1,4,7-
triazacyclononane)4(C104)4, MnllIMnlV4(u-O)1(u-OAc)2-{1,4,7-trimethyl-1,4,7-
5 triazacyclononane)2(C104)3, MnIV(1,4,7-trimethyl-1,4,7-triazacyclononane)-
(OCH3)3(PF6), and mixtures thereof. Other metal-based bleach catalysts
include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The
use
of manganese with various complex ligands to enhance bleaching is also
reported in the following United States Patents: 4,728,455; 5,284,944;
I O 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
As a practical matter, and not by way of limitation, the compositions and
processes herein can be adjusted to provide on the order of at least one part
per
ten million of the active bleach catalyst species in the aqueous washing
liquor,
and will preferably provide from 0.1 ppm to 700 ppm, more preferably from 't
15 ppm to 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.
Inorq. Bioinor . Mech., (1983), 2, pages 1-94. The most preferred cobalt
catalyst
useful herein are cobalt pentaamine acetate salts having the formula
20 [Co(NH3)50Ac] Ty, wherein "OAc" represents an acetate moiety and "Ty" is an
anion, and especially cobalt pentaamine acetate chloride, [Co(NH3)50Ac]C12; as
well as [Co(NH3)50Ac](OAc)2; [Co(NH3)50Ac](PF6)2; [Co(NH3)50Ac](S04);
[Co(NH3)50Ac]{BF4)2; and [Co(NH3)50Ac](N03)2 (herein "PAC").
These cobalt catalysts are readily prepared by known procedures, such
25 as taught for eXampie 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,
W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; lnOrQ. Chem., 18, 1497-1502
(1979);
Inora. Chem., 2-11, 2881-2885 {1982); Inor . Chem., 18, 2023-2025 (1979);
Inorg.
30 Synthesis, 173-176 (1960}; and Journal of Physical Chemistry, 56, 22-25
(1952).
As a practical matter, and not by way of limitation, the automatic
dishwashing compositions and cleaning processes herein can be adjusted to
provide on the order of at least one part per hundred million of the active
bleach
catalyst species in the aqueous washing medium, and will preferably provide
from 0.01 ppm to 25 ppm, more preferably from 0.05 ppm to 10 ppm, and most
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31
preferably from 0.1 ppm to 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 0.0005% to 0.2%, more preferably from 0.004% to 0.08%, of
bleach catalyst, especially manganese or cobalt catalysts, by weight of the
cleaning compositions.
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 andlor
stability
optima, thermostability, and stability to active detergents, builders. 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.
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. In practical terms
for
current commercial preparations, typical amounts are up to 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
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32
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-
catalyticaliy
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, 1985. 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 & Gambte .
When desired, a protease having decreased adsorption and increased hydrolysis
is available as described in WO 9507791 to Procter 8~ 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 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, +109,
+126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217,
+218, +222, +260, +265, and/or +274 according to the numbering of Bacillus
amyloliquefaciens subtilisin, as described in the patent applications of A.
Baeck,
et al, entitled "Protease-Containing Cleaning Compositions" having US Serial
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33
No. 08/322,676, and C. Ghosh, et al, "Bleaching Compositions Comprising
Protease Enzymes" having US Serial No. 081322,677, both filed October 13,
1994.
Amylases suitable herein, especially for, but not limited to automatic
S dishwashing purposes, 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 peroxideltetraacetylethylenediamine in
buffered solution at pH 9-10; thermal stability, e.g., at common wash
temperatures such as 60oC; or alkaline stability, e.g., at a pH from 8 to 11,
measured versus the above-identified reference-point amylase. Stability can be
measured using any of the art-disclosed technical tests. See, for example,
references disclosed in WO 9402597. Stability-enhanced amylases can be
obtained from Novo or from Genencor International. One class of highly
preferred amylases herein have the commonality of being derived using site-
directed mutagenesis from one or more of the Bacillus amylases, especially the
Bacillus a-amylases, regardless of whether one, two or multiple amylase
strains
are the immediate precursors. Oxidative stability-enhanced amylases vs. the
above-identified reference amylase are preferred for use, especially in
bleaching,
more preferably oxygen bleaching, as distinct from chlorine bleaching,
detergent
compositions herein. Such preferred amylases include (a) an amylase according
to the hereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as further
illustrated by a mutant in which substitution is made, using alanine or
threonine,
preferably threonine, of the methionine residue located in position 197 of the
B
licheniformis alpha-amylase, known as TERMAMYL~, or the homologous
position variation of a similar parent amylase, such as B. amyloliquefaciens,
B.
subfilis, or B. stearothermophilus; (b) stability-enhanced amylases as
described
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34
by Genencor International in a paper entitled "Oxidatively Resistant alpha-
Amylases" presented at the 207th American Chemical Society National Meeting,
March 13-17 1994, by C. Mitchinson. Therein it was noted that bleaches in
automatic dishwashing detergents inactivate alpha-amylases but that improved
oxidative stability amylases have been made by Genencor from B. licheniformis
NCIB8061. Methionine (Met) was identified as the most likely residue to be
modified. Met was substituted, one at a time, in positions 8, 15, 197, 256,
304,
366 and 438 leading to specific mutants, particularly important being M197L
and
M197T with the M197T 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 Genenco~
IS 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.
Other amylase enzymes include those described in WO 95126397 and in
co-pending application by Novo Nordisk PCTlDK96/00056. Specific amylase
enzymes for use in the detergent compositions of the present invention include
a
-amylases characterized 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, WO 95/26397.) Also included herein are a-amylases which are at
Least 80% homologous with the amino acid sequences shown in the SEQ ID
listings in the references. These enzymes are preferably incorporated into
laundry ~ detergent compositions at a level from 0.00018% to 0.060% pure
enzyme by weight of the total composition, more preferably from 0.00024% to
0.048% pure enzyme by weight of the total composition.
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
,.,,
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Humicola insolens or Humicola strain DSM1800 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-
S 2.247.832. CAREZYME~ and CELLUZYME~ (Novo) are especially useful. See
also WO 9117243 to Novo.
Suitable lipase enzymes for detergent usage include those produced by
microorganisms of the Pseudomonas group, such as Pseudomonas sfutzeri
ATCC 19.154, as disclosed in GB 1,372,034. See also lipases in Japanese
10 Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is
available
from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name
Lipase P "Amano," or "Amano-P." Other suitable commercial lipases include
Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum
var. lipolyficum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacfer
15 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 herein. Lipase and amylase
variants stabilized against peroxidase enzymes are described in WO 9414951 A
20 to Novo. See also WO 9205249 and RD 94359044.
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
25 noted above. ~In order to optimize the stain removal performance of
Lipolase,
Novo Nordisk have made a number of variants. As described in WO 92105249,
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
30 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
0.001-100- mg (5-500,000 LU/liter) lipase variant per liter of wash liquor.
The
present invention provides the benefit of improved whiteness maintenance on
fabrics using low levels of D96L variant in detergent compositions containing
the
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36
bis-AQA surfactants in the manner disclosed herein, especially when the D96L
is
used at levels in the range of 50 LU to 8500 LU per liter of wash solution.
Cutinase enzymes suitable for use herein are described in WO 8809367 A
to Genencor.
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
IS 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. 4,10'1,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes,
March 26, 1985. Enzyme materials useful for liquid detergent formulations, and
their incorporation into such formulations, are disclosed in U.S. 4,261,868,
Hora
et al, April 14, 1981. Enzymes for use in detergents can be stabilised by
various
techniques. Enzyme stabilisation techniques are disclosed and exemplified in
U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586,
October 29, 1986, Venegas. Enzyme stabilisation systems are also described,
for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases,
xylanases and cellulases, is described in WO 9401532 A to Novo.
Enzyme Stabilizing S s
The enzyme-containing compositions herein may optionally also comprise
from 0.001 % to 10%, preferably from 0.005% to 8%, most preferably from
0.01% to 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
,,,
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37
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
andlor 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. 4,537,706. Borate stabilizers, when used, may be at levels of up to 10%
or
more of the composition though more typically, levels of up to about 3% by
weight of boric acid or other borate compounds such as borax or orthoborate
are
suitable for liquid detergent use. Substituted boric acids such as
phenylboronic
acid, butaneboronic acid, p-bromophenyiboronic 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 10%,
preferably from 0.01 % to 6% by weight, of chlorine bleach scavengers, added
to
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 0.5 ppm to
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 percarbonate has the ability to react with chlorine bleach the use of
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38
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, bisuifite, thiosulfite,
thiosuifate,
iodide, etc. Antioxidants such as carbamate, ascorbate, etc., organic amines
such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof,
monoethanolamine (MEA), and mixtures thereof can likewise be used. Likewise,
special enzyme inhibition systems can be incorporated such that different
enzymes have maximum compatibility. Other conventional scavengers such as
bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium
perborate tetrahydrate, sodium perborate monohydrate and sodium
percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate,
citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures
thereof can
be used if desired. In general, since the chlorine scavenger function can be
performed by ingredients separately listed under better recognized functions,
(e.g., hydrogen peroxide sources), there is no absolute requirement to add a
separate chlorine scavenger unless a compound performing that function to the
desired extent is absent from an enzyme-containing embodiment of the
invention; even then, the scavenger is added only for optimum results.
Moreover, the formulator will exercise a chemist's 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%, typically from 0.1 % to 5%,
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
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39
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(I~ aikoxide. 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 SRA's include: a sulfonated product of a substantially linear ester
oligomer comprised of an oligomeric ester backbone of terephthafoyl 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, 1990 to J.J. Scheibel and E.P. Gosselink: such ester
oligomers can be prepared by (a) ethoxylating allyl alcohol, (b) reacting the
product of (a) with dimethyl terephthalate ("DMT') and 1,2-propylene glycol
("PG") in a two-stage transesterification/ oligomerization procedure and (c)
reacting the product of (b) with sodium metabisulfite in water; the nonionic
end-
capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S.
4,791,730, December 8, 1987 to Gosselink et al, for example those produced by
transesterificationloligomerization 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, January 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
compounds of U:S. 4,702,857, October 27, 1987 to Gosselink, for example
produced from DMT, Me-capped PEG and EG andlor 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.
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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-sulfobenzoic acid
monosodium salt, PG and DMT optionally but preferably further comprising
5 added PEG, e.g., PEG 3400.
SRA's also include simple copo(ymeric blocks of ethylene terephthalate or
propylene terephthalate with polyethylene oxide or polypropylene oxide
terephthaiate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to
Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether
cellulosic
10 polymers available as METHOCEL from Dow; and the C1-C4 a(kylcellu(oses 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., C1-Cg vinyl esters,
preferably
polyvinyl acetate), grafted onto polyalkylene oxide backbones. See European
15 Patent Application 0 219 048, published April 22, 1987 by Kud, et al.
Commercially available examples include SOKALAN SRA's such as SOKALAN
HP-22, available from BASF, Germany. Other SRA's are polyesters with repeat
units containing 10-15% by weight of ethylene terephthalate together with 90-
80% by weight of polyoxyethylene terephthalate, derived from a polyoxyethyiene
20 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{EGIPG)5(T)5(SIP)1 which comprises terephthaloyl (T), sulfoisophthaloyl
(SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units and which is
25 preferably terminated with end-caps (CAP), preferably modified
isethionates, as
in an oligomer comprising one sulfoisophthaloyl unit, 5 terephtha(oyl units,
oxyethyieneoxy 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
30 0.5% to 20%, by weight of the oligomer, of a crystallinity-reducing
stabiliser, for
example an anionic surfactant such as linear sodium dodecylbenzenesu(fonate
or a member selected from xylene-, cumene-, and toluene- su(fonates 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,
35 issued May 16, 1995. Suitable monomers for the above SRA include Na 2-(2-
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41
hydroxyethoxy}-ethanesulfonate, DMT, Na- dimethyi 5-sulfoisophthalate, EG and
PG.
Yet another group of preferred SRA's are oiigomeric esters comprising:
(1) a backbone comprising (a) at least one unit selected from the group
consisting of dihydroxysulfonates, polyhydroxy suifonates, 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,
aikoxylated phenolsuifonates, sulfoaroyl derivatives and mixtures thereof.
Preferred of such esters are those of empirical formula:
{(CAP)x(EGIPG)y'(DEG)y"(PEG)y"'(T)z(SIP)z'(SEG)q(B)m}
wherein CAP, EGIPG, 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 trifunctionai 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} ethanesuifonate ("SE3") and its homologs and mixtures thereof and the
products of ethoxylating and suifonating aliyl alcohol. Preferred SRA esters
in
this class include the product of transesterifying and oligomerizing sodium 2-
{2-
(2-hydroxyethoxy)ethoxy}ethanesulfonate. andlor 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)
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42
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.
Additional classes of SRA's include (I) nonionic terephthalates using
diisocyanate coupling agents to link up polymeric ester structures, see U.S.
4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al; (II) SRA's with
carboxylate terminal groups made by adding trimellitic anhydride to known
SRA's
to convert terminal hydroxyl groups to trimellitate esters. With a proper
selection
of catalyst, the trimellitic anhydride forms linkages to the terminals of the
polymer
through an ester of the isolated carboxylic acid of trimellitic anhydride
rather than
by opening of the anhydride linkage. Either nonionic or anionic SRA's may be
used as starting materials as long as they have hydroxyl terminal groups which
may be esterified. See U.S. 4,525,524 Tung et al.; (III) anionic
terephthalate=
based SRA's of the urethane-finked 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.; (u) 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 2,335,044 to Unilever N. V., 1974.
Other
useful SRA's are described in U.S. Patents 4,240,918, 4,787,989, 4,525,524 and
4, 877, 896.
Clay Soil Removal/Anti-redehosition Agents
The compositions of the present invention can also optionally contain
water-soluble ethoxylated amines having clay soil removal and antiredeposition
properties. Granular detergent compositions which contain these compounds
typically contain from 0.01% to 10.0% by weight of the water-soluble
ethoxylates
amines; liquid detergent compositions typically contain 0.01 % to 5%.
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43
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
S disclosed in European Patent Application 111,965, Oh and Gosselink,
published
June 27, 1984. Other clay soil removallantiredeposition agents which can be
used include the ethoxylated amine polymers disclosed in European Patent
Application 111,984, Gosselink, published June 27, 1984; the zwitterionic
polymers disclosed in European Patent Application 112,592, Gosselink,
published July 4, 1984; and the amine oxides disclosed in U.S. Patent
4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or
anti
redeposition agents known in the art can also be utilized in the compositions
herein. See U.S. Patent 4,891,160, VanderMeer, issued January 2, 1990 and
WO 95132272, 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.
Brightener
Any optical brighteners or other brightening or whitening agents known in
the art can be incorporated at levels typicaNy from 0.01 % to 1.2%, by weight,
into
the detergent compositions herein. Commercial optical brighteners which may
be useful in the present invention can be classified into subgroups, which
include, but are not necessarily limited to, derivatives of stilbene,
pyrazoline,
coumarin, carboxylic acid, methinecyanines, 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 8~
Sons, New York (1982).
Specific examples of optical brighteners which are useful in the present
compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on
December 13, 1988. These brighteners include the PHORWHITE series of
brighteners from Verona. Other brighteners disclosed in this reference
include:
Tinopal UNPA, Tinopal CBS and Tinopal SBM; available from Ciba-Geigy; Artic
White CC and Artic White CWD, the 2-(4-styryl-phenyl)-2H-naptho[1,2-
d]triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)-stilbenes; 4,4'-
bis{styryl)bisphenyls; and
the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-
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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
3,64fi,015,
issued February 29, 1972 to Hamilton.
Dye Transfer Inhibiting Agents
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
0.01 % to 10% by weight of the composition, preferably from 0.01 % to 5%, and
more preferably from 0.05% to 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, ethoxytated aiiphatics, aromatics, heterocyclic or
alicyclic
groups or any combination thereof to which the nitrogen of the N-O group can
be
attached or the N-O group is part of these groups. Preferred polyamine N-
oxides
are those wherein R is a heterocyclic group such as pyridine, pyrrole,
imidazole,
pyrrolidine, piperidine and derivatives thereof.
The N-O group can be represented by the following general structures:
O O
~nc-N -~2~~ =N -(Rt )x
(R3)z
wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups
or
combinations thereof; x, y and z are 0 or 9; 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 <fi.
r
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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, polyaikylenes, polyesters,
polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These
5 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
10 appropriate degree of N-oxidation. The polyamine oxides can be obtained in
almost any degree of polymerization. Typically, the average molecular weight
is
within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most
preferred 5,000 to 100,000. This preferred class of materials can be referred
to
as "PVNO".
15 The most preferred polyamine N-oxide useful in the detergent
compositions herein is poly(4-vinyipyridine-N-oxide) which has an average
molecular weight of 50,000 and an amine to amine N-oxide ratio of 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
20 PVPVI has an average molecular weight range from 5,000 to 1,000,000, more
preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000.
(The average molecular weight range is determined by light scattering as
described in Barth, et al., Chemical Analysis, Vol 113. "Modern Methods of
Polymer Characterization", the disclosures of which are incorporated herein by
25 reference.) The PVPVI copolymers typically have a molar ratio of N-
vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from
0.8:1
to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either
linear or branched.
The present invention compositions also may employ a polyvinyl
30 pyrrolidone ("PVP") having an average molecular weight of from 5,000 to
400,000, preferably from 5,000 to 200,000, and more preferably from 5,000 to
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")
35 having an average molecular weight from 500 to 100,000, preferably from
1,000
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to 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in
wash
solutions is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.
The detergent compositions herein may also optionally contain from
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 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:
R2
~N H H N \
N~ N C C N N
/ N H H N \
RZ S~3M S~3M Rl
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-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is
the preferred hydrophilic optical brightener useful in the detergent
compositions
herein.
When in the above formula, 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 5BM-GX by Ciba-Geigy
Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a
cation such as sodium, the brightener is 4,4'-bis[{4-anilino-6-morphilino-s
triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular
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brightener species 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
S when used in combination with the selected polymeric dye transfer inhibiting
agents hereinbefore described. The combination of such selected polymeric
materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners
(e.g.,
Tinopal UNPA-GX, Tinopal 5BM-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 parar»eter 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.
Chelatinq Agents
The detergent compositions herein may also optionally contain one or
more iron and/or manganese chelating agents. Such chelating agents can be
selected from the group consisting of amino carboxylates, amino phosphonates,
polyfunctionally-substituted 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
3S ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,
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nitrilotriacetates, ethylenediamine tetraproprionates, triethyienetetraamine-
hexacetates, 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 least low levels of total phosphorus are
permitted in detergent compositions, and include ethylenediaminetetrakis
(methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates
to not contain alkyl or alkenyl groups with more than 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,SJ 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.
If utilized, these chelating agents will generally comprise from 0.1 % to
15% by weight of the detergent compositions herein. More preferably, if
utilized,
the chelating agents will comprise from 0.1 % to 3.0% by weight of such
compositions.
Suds Supt~ressors
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-tailed "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 Wdey & 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
,,t
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49
typically have hydrocarbyl chains of 10 to 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 C1g-C40 ketones (e.g., stearone), etc. Other
suds inhibitors include N-alkylated amino triazines such as tri- to hexa
alkylmelamines or di- to tetra-alkyidiamine 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 monostearyi alcohol phosphate ester and monostearyl di-alkali metal
(e.g., K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such
as paraffin and haloparaffin can be utilized in liquid form. The liquid
hydrocarbons will be liquid at room temperature and atmospheric pressure, and
will have a pour point in the range of -40°C and 50°C, and a
minimum boiling
point not less than110°C {atmospheric pressure). It is also known to
utilize waxy
hydrocarbons, preferably having a melting point below 100°C. The
hydrocarbons constitute a preferred category of suds suppressor for detergent
compositions. Hydrocarbon suds suppressors are described, for example, in
U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The
hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic
saturated or unsaturated hydrocarbons having from 12 to 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 poiydimethylsiloxane, dispersions or emulsions of
polyorganosiloxane oils or resins, and combinations of poiyorganosiloxane with
silica particles wherein the polyorganosiloxane is chemisorbed or fused onto
the
silica. Silicone suds suppressors are well known in the art and are, for
example,
disclosed in U.S. .Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and
European Patent Application No. 89307851.9, published February 7, 1990, by
Starch, M. S.
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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
5 German Patent Application DOS 2,124,526. Silicone defoamers and suds
controlling agents in granular detergent compositions are disclosed in U.S.
Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et
al,
issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein is a suds
10 suppressing amount of a suds controlling agent consisting essentially of:
(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to
about 1,500 cs. at 25°C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of
siloxane resin composed of (CH3)3Si01~2 units of Si02 units in a
15 ratio of from (CH3)3 Si01~2 units and to Si02 units of from about
0.6: 9 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
20 continuous phase is made up of certain polyethylene glycols or polyethylene
polypropylene glycol copolymers or mixtures thereof (preferred), or
polypropylene glycol. The primary silicone suds suppressor is
branchedlcrosslinked and preferably not linear.
To illustrate this point further, typical liquid laundry detergent
compositions
25 with controlled suds will optionally comprise from about 0.001 to about 1,
preferably from about 0.01 to about 0.7, most preferably from about 0.05 to
about 0.5, weight % of said silicone suds 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
30 compound, (c) a finely divided filler material, and (d) a catalyst to
promote the
reaction of mixture components (a), (b) and (c), to form silanoiates; (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.
35 Similar amounts can be used in granular compositions, gels, etc. See also
U.S.
,,T_
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5'I
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 ai at column 1, fine 46
through
column 4, line 35.
The silicone suds suppressor herein preferably comprises polyethylene
glycol and a copolymer of polyethylene glycollpolypropylene glycol, all having
an
average molecular weight of less than about 1,000, preferably between about
100 and 800. The polyethylene glycol and polyethylenelpolypropylene
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 glycollpolypropylene glycol, preferably PPG 200/PEG 300-.
Preferred is a weight ratio of between about 1:1 and 1:10, most preferably
between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethyiene-
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 L101.
Other suds suppressors useful herein comprise the secondary alcohols
(e.g., 2-alkyl alkanois) and mixtures of such alcohols with silicone oils,
such as
the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The
secondary alcohols include the Cg-C16 alkyl alcohols having a C1-C16 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 or
dishwashing machines, suds should not form to the extent that they either
overflow the washing machine or negatively affect the washing mechanism of the
dishwasher. 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
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52
sufficiently control the suds to result in a low-sudsing laundry or
dishwashing
detergents for use in automatic laundry or dishwashing machines.
The compositions herein will generally comprise from 0% to 10% of suds
suppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and
salts therein, will be present typically in amounts up to 5%, by weight, of
the
detergent composition. Preferably, from 0.5% to 3% of fatty monocarboxylate
suds suppressor is utilized. Silicone suds suppressors are typically utilized
in
amounts up to 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 0.01 % to 1 % of silicone
suds
suppressor is used, more preferably from 0.25% to 0.5%. As used herein, these
weight percentage values include any silica that may be utilized in
combination
with polyorganosiloxane, as well as any optional materials that may be
utilized.
Monostearyl phosphate suds suppressors are generally utilized in amounts
ranging from 0.1 % to 2%, by weight, of the composition. Hydrocarbon suds
suppressors are typically utilized in amounts ranging from 0.01% to 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.
AIkoxYlated Polycarbox~rfates
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 90101815 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 2000 to 50,000. Such alkoxylated polycarboxylates
can
comprise from 0.05% to 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, 1977,
as well as other softener clays known in the art, can optionally be used
typically
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53
at levels of from 0.5% to 10% by weight in the present compositions to provide
fabric softener benefits concurrently with fabric cleaning. Clay softeners can
be
used in combination with amine and cationic softeners as disclosed, for
example,
in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent
4,291,071,
Harris et al, issued September 22, 1981
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. 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. Finished
perfumes
can comprise extremely complex mixtures of such ingredients. Finished
perfumes typically comprise from 0.01 % to 2%, by weight, of the detergent
compositions herein, and individual perfumery ingredients can comprise from
0.0001 % to 90% of a finished perfume composition.
Non-limiting examples of perfume ingredients useful herein include: 7-
acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene; ionone
methyl;
ionone gamma methyl; methyl cedrylone; methyl dihydrojasmonate; methyl
1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl ketone; 7-acetyl-1,1,3,4,4,6-
hexamethyl tetralin; 4-acetyl-6-tert-butyl-1,1-dimethyl indane; para-hydroxy-
phenyl-butanone; benzophenone; methyl beta-naphthyl ketone; 6-acetyl-
1,1,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-1,1,2,6-tetramethyi
indane;
1-dodecanai, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde; 7-
hydroxy-3,7-dimethyl ocatanal; 10-undecen-1-al; iso-hexenyl cyclohexyl
carboxaldehyde; formyl tricyclodecane; condensation products of
hydroxycitroneilal and methyl anthranilate, condensation products of
hydroxycitronellal and indol, condensation products of phenyl acetaldehyde and
indol; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; ethyl vanillin;
heliotropin; hexyl cinnamic aldehyde; amyl cinnamic aldehyde; 2-methyl-2-(para-
iso-propylphenyl)-propionaldehyde; coumarin; decalactone gamma; cyclo-
pentadecanolide; . 16-hydroxy-9-hexadecenoic acid lactone; 1,3,4,6,7,8-
hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane; beta-
naphthol methyl ether; ambroxane; dodecahydro-3a,6,6,9a-tetramethyl-
naphtho[2,1 b]furan; cedrol, 5-(2,2,3-trimethylcyclopent-3-enyl)-3-
methylpentan-2-
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54
ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-oi; caryophyllene
alcohol; tricyciodecenyl propionate; tricyclodecenyl acetate; benzyl
salicylate;
cedryl acetate; and para-(tert-butyl) cyclohexyl acetate.
Particularly preferred perfume materials are those that provide the largest
odor improvements in finished product compositions containing cellulases.
These perfumes include but are not limited to: hexyl cinnamic aldehyde; 2
methyl-3-(para-tert-butylphenyl)-propionaldehyde; 7-acetyl-1,2,3,4,5,6,7,8
octahydro-1,1,6,7-tetramethyl naphthalene; benzyl salicylate; 7-acetyl
1,1,3,4,4,6-hexamethyl tetralin; para-tert-butyl cyclohexyl acetate; methyl
dihydro
jasmonate; beta-napthoi 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-
tetramethyinaphtho[2,1 b]furan; anisaldehyde; coumarin; cedrol; vanillin;
cyclopentadecanolide; tricyclodecenyl acetate; and tricyclodecenyl propionate.
Other perfume materials include essential oils, resinoids, and resins from
a variety of sources including, but not limited to: Peru balsam, Olibanum
resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander
and
lavandin. Still other perfume chemicals include phenyl ethyl alcohol,
terpineol,
linalool, linalyl acetate, geraniol, nerol, 2-(1,1-dimethylethyl)-cyclohexanol
acetate, benzyl acetate, and eugenol. Carriers such as diethylphthalate can be
used in the finished perfume compositions.
Other lngredients
A wide variety of other ingredients useful in detergent compositions can
be included in the compositions herein, including other active ingredients,
carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid
formulations, solid fillers for bar compositions, etc. If high sudsing is
desired,
suds boosters such as the C1p-C16 alkanolamides can be incorporated into the
compositions, typically at 1%-10% levels. The C10-C14 monoethanol and
diethanol amides illustrate a typical class of such suds boosters. Use of such
suds boosters with high sudsing optional 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,
can be added at levels of, typically, 0.1 %-2%, to provide additional suds and
to
enhance grease removal performance.
~.,
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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
5 absorbed into the porous substrate. In use, the detersive ingredient is
released
from the substrate into the aqueous washing liquor, where it performs its
intended detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica
(trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme
10 solution containing 3%-5% of C13-15 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 stirring in silicone oil (various
silicone oil
viscosities in the range of 500-12,500 can be used). The resulting silicone
oil
dispersion is emulsified or otherwise added to the final detergent matrix. By
this
15 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
20 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 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1,3-
propanediol,
ethylene glycol, glycerine, and 1,2-propanediol) can also be used. The
25 compositions may contain from 5% to 90%, typically 10% to 50% of such
carriers.
The detergent compositions herein will preferably be formulated such that,
during use in aqueous cleaning operations, the wash water will have a pH of
between 6.5 and 11, preferably between 7.5 and 10.5. Liquid dishwashing
30 product formulations preferably have a pH between 6.8 and 9Ø Laundry
w 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 welt known to those skilled in the art.
Granules Manufacture
35 Adding the bis-alkoxylated cationics of this invention into a crutcher mix,
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56
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
650 gll) granules ace 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.
EXAMPLES
The following examples further describe and demonstrate the preferred
embodiments within the scope of the present invention. The examples are given
solely for the purpose of illustration, and are not to be construed as
limitations of
the present invention since many variations thereof are possible without
departing from its spirit and scope.
In the following examples, the abbreviated component identifications have
the following meanings:
LAS : Sodium linear C12 alkyl benzene suffonate
C45AS : Sodium C14-C15 linear alkyl sulfate
~ ethylene oxide
C25E9 : A C12_15 branched primary alcohol condensed
with an average of 9 moles of ethylene
oxide
CocoE02 : R1.N+(CH3)(C2H40H)2 with R1 = C12 -
C14
Zeolite A : Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si02)12. 27H20 having a primary
particle size in the range from 0.1 to
10
micrometers
NaSKS-6 : Crystalline layered silicate of formula
S -Na2Si205
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Carbonate : Anhydrous sodium carbonate with a particle
size between 200um and 900~.m
Silicate : Amorphous Sodium Silicate (Si02:Na20;
2.0
ratio)
MA/AA : Copolymer of 4:6 maleic/acrylic acid,
average
molecular weight 11,000.
Protease : Proteolytic enzyme of activity 4KNPUIg
sold by
NOVO Industries AIS under the tradename
Savinase
Cellulase : Cellulytic enzyme of activity 1000
CEVUIg sold
by NOVO Industries A/S under the tradename
Carezyme
Amylase : Amylolytic enzyme of activity 60KNUIg
sold by
NOVO Industries A/S under the tradename
1 S Termamyl 60T
Lipase : Lipolytic enzyme of activity 100kLUlg
sold by
NOVO Industries AIS under the tradename
Lipolase
PB1 : Anhydrous sodium perborate bleach of
nominal formula NaB02.H202
NOES : Nonanoyloxybenzene sulfonate in the
form of
the sodium salt.
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58
In the following Examples all levels are quoted as % by weight of the
composition.
EXAMPLES
I II III
LAS 22.0 20.2 22.2
C45AS 4.0 4.0 3.0
CocoE02 1.2 3.0 2.0
IO C25E9 3.0 3.0 3.0
MA/AA 14.0 20.0 15.0
NaSKS-6 5.0 3.0 4.0
Zeolite A 11.0 7.0 11.0
Silicate 12.0 12.0 12.0
i 5 Carbonate 12.0 12.0 12.0
Protease 0.6 0.6 0.6
Cellulase 0.5 0.5 0.5
Amylase 0.6 0.6 0.6
Lipase 0.3 0.3 0.3
20 NOBS 2.7 2.7 2.7
PB1 2.6 2.6 2.6
Miscellaneous/Others Balance
100
