Note: Descriptions are shown in the official language in which they were submitted.
CA 02273259 1999-OS-28
WO 98/28393 PCT/US97/22694
DISHWASHING DETERGENT COMPOSITIONS CONTAINING ORGANIC DIAMINES
Field of the Invention
The present invention relates to detergent compositions containing low
molecular weight organic diamines. More particularly, the invention is
directed to
detergent compositions for hand dishwashing which have improved grease removal
performance and benefits in sudsing. The detergents of this invention also
have
improved low temperature stability properties and superior dissolution, as
well as
improved tough food stain removal, and antibacterial properties. The detergent
compositions of this invention can be in any form, including granular, paste,
gel or
liquid. Highly preferred embodiments are in liquid or gel form.
When formulated into hand dishwashing detergents at a pH of above about 8.0,
the diamines are more effective as replacements for the low-level use of Ca/Mg
ions
as surfactancy boosters long known in the dishwashing art. The diamines
provide
simultaneous benefits in grease cleaning, sudsing, dissolution and low
temperature
stability, without the shortcomings associated with Ca/Mg.
Background of the Invention
Typical commercial hand dishwashing compositions incorporate divalent ions
(Mg, Ca) to ensure adequate grease performance in soft water. However, the
presence of divalent ions in formulas containing anionic, nonionic, or
additional
surfactants (e.g., alkyl dimethyl amine oxide, alkyl ethoxylate, alkanoyl
glucose
amide, alkyl betaines) leads to slower rates of product mixing with water (and
hence
poor flash foam), poor rinsing, and poor low temperature stability properties.
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WO 98/28393 PCT/US97/22694
7
Moreover, preparation of stable dishwashing detergents containing Ca/Mg is
very
difficult due to the precipitation issues associated with Ca and Mg as pH
increases.
U.S. patent no. 4,556,509 teaches diacid salts of diamines. Under these
conditions, we have found that these materials have limitations. Moreover, the
benefits are confined to hardness < 70ppm. U.S. patent no. 4,556,509 also
teaches
the use of C2 spacer, e.g., ethylene diamine diacid salt and ethoxylated
diamines,
both of which severely limit performance in the current development.
It has now been determined that the use of certain organic diamines, as
outlined in detail below, with surfactants in dishcare compositions with pH's
~8.0-12
(measured at 10% solution) leads to improved cleaning of tough food stains and
removal of grease/oil when compared to the use of Mg or Ca ions in
conventional
detergent compositions. Unexpectedly, these organic diamines also improve suds
stability in the presence of soils, esp. soils containing fatty acids and
proteins.
Further, the strong grease removal performance of the diamines discussed
herein allows reduction/elimination of Mg/Ca ions from the formulation while
maintaining benefits in grease performance. The removal of Mg/Ca additionally
leads to improved benefits in dissolution, rinsing and low temperature product
stability.
The diamines of this invention in combination with surfactants also provides
sensory benefits. It has been found that the presence of this composition
produces a
"silky" feel to wash liquor and a feeling of "mildness" to the skin. The
diamines are
also found to produce antibacterial benefits to the wash liquor. However, the
specific compositions presented herein are especially designed for dishwashing
having relatively high pH's, detersive surfactants, and optional enzymes, all
of which
would be undesirable in contact lens cleaners.
It has now been found these benefits are achieved through the use of low
molecular weight organic diamines in higher pH formulations (~8.0-12) across a
broad range of hardness (8 to >1,000 ppm).
Background Art
U.S. patent no. 4,556,509 teaches the use of low molecular weight organic
diamine diacid salts in detergents having a pH range of from about 6 to 8.
JP 63131124-A 88/06/03 describes contact lens cleaner containing diamines
reacted with halogen compounds such as 1,2-dichloroethane.
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WO 98/28393 PCT/US97/22694
Summary of the Invention
The detergent compositions according to the present invention comprise
diamines and surfactants. More specifically, the detergents of this invention
comprise:
a) an effective amount of a low molecular weight (less than about 400 amu,
preferably less than about 200 amu, more preferably less than or equal to
about 150
amu) organic diamine wherein said diamine has a pKl and a pK2, both in the
range
of from about 8.0 to about 11.5; and
b) a detersive effective amount of surfactant;
wherein the detergent composition has a pH (as measured as 10% aqueous
solution) of from about 8.0 to about 12, preferably from about 8.2 to about
12, more
preferably from about 8.5 to about 11; still more preferably from about 8.5 to
about
10.2.
The preferred weight ratios of surfactant to organic diamine range from about
40:1 to about 2:1, more preferably about 10:1 to about 5:1.
Optionally, the detergent compositions may further comprise a reduced level of
Mg/Ca ions as compared to known conventional detergent compositions. To put it
another way, the compositions herein preferably utilize no more than about
1.5%,
more preferably no more than about 0.6%, of available divalent ions,
preferably
selected from calcium and magnesium. Most preferably, the detergent
compositions
herein are substantially free (i.e., less than about 0.1 %) of added divalent
ions.
The surfactants of this invention are selected from anionic or nonionic
surfactants or mixtures thereof. Preferred anionic surfactants for use herein
include
linear alkylbenzene sulfonate, alpha olefin sulfonate, paraffin sulfonates,
methyl
ester sulfonates, alkyl sulfates, alkyl alkoxy sulfate, alkyl sulfonates,
alkyl
alkoxylated sulfates, sarcosinates, alkyl alkoxy carboxylate, and taurinates.
Preferred nonionic surfactants useful herein are selected from the group
consisting of
alkyl dialkyl amine oxide, alkyl ethoxylate, alkanoyl glucose amide,
alkylpolyglucoside, alkyl betaines, and mixtures thereof. In one highly
preferred
embodiment, the anionic surfactants are selected from the group consisting of
alkyl
sulfates, alkyl alkoxy sulfates, and mixtures thereof. In another highly
preferred
embodiment, the nonionic surfactants are selected from the group consisting of
amine oxide, alkyl betaine, alkanoyl glucose amide, and mixtures thereof. If a
mixture of anionic surfactant and nonionic surfactant is used, the weight
ratio of
anionic:nonionic is preferably from about 50:1 to about 1:50, more preferably
from
about 50:1 to about 3:1. Also, when mixtures of anionic and nonionic
surfactants
are present, the hand dishwashing detergent composition herein preferably
further
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WO 98128393 PCT/I1S97/22694
4
comprise protease enzyme, amylase enzyme, or mixtures thereof. Further , these
hand dishwashing detergent embodiments preferably further comprises a
hydrotrope.
Suitable hydrotropes include sodium. potassium, ammonium or water-soluble
substituted ammonium salts of toluene sulfonic acid, naphthalene sulfonic
acid,
cumene sulfonic acid, xylene sulfonic acid.
The detergent will further preferably comprise one or more detersive adjuncts
selected from the following: soil release polymers, dispersants,
polysaccharides,
abrasives, bactericides, tarnish inhibitors, builders, enzymes, dyes, buffers,
antifungal or mildew control agents, insect repellents, perfumes, hydrotropes,
thickeners, processing aids, suds boosters, brighteners, anti-corrosive aids,
stabilizers antioxidants and chelants. Although cationic surfactants may be
optionally present in the detergent compositions herein, preferred embodiments
are
substantially free of cationic surfactant. Moreover, the compositions herein
are
substantially free of halide ions (chloride, fluoride, bromide, or iodide
ions) and
substantially free of urea. By substantially free is meant less than about 1%,
preferably less than about 0.1 %, by weight of total composition, more
preferably 0%
added, of the specific component.
Moreover, the hand dishwashing detergent composition of this invention can
further comprise enzymes preferably selected from the group consisting of
protease,
lipase, amylase, cellulase, and mixtures thereof; more preferably the enzymes
are
selected from protease and amylase.
Furthermore, it is preferred that the diamines used in the present invention
are
substantially free from impurities. That is, by "substantially free" it is
meant that the
diamines are over 95% pure, i.e., preferably 97%, more preferably 99%, still
more
preferably 99.5%, free of impurities. Examples of impurities which may be
present
in commercially supplied diamines include 2-Methyl-1,3-diaminobutane and
alkylhydropyrimidine. Further, it is believed that the diamines should be free
of
oxidation reactants to avoid diamine degradation and ammonia formation.
Additionally, if amine oxide andlor other surfactants are present, the amine
oxide or
surfactant should be hydrogen peroxide-free. The preferred level of hydrogen
peroxide in the amine oxide or surfactant paste of amine oxide is 0-40 ppm,
more
preferably 0-15 ppm. Amine impurities in amine oxide and betaines, if present,
should be minimized to the levels referred above for hydrogen peroxide.
Making the compositions free of hydrogen peroxide is important when the
compositions contain an enzyme. The peroxide can react with the enzyme and
destroy any performance benefits the enzyme adds to the composition. Even
small
amounts of hydrogen peroxide can cause problems with enzyme containing
CA 02273259 2003-08-27
formulations. However, the diamine can react with any peroxide present and act
as
an enzyme stabilizer and prevent the hydrogen peroxide from reacting with the
enzyme. The only draw back of this stabilization of the enzymes by the diamine
is
that the nitrogen compounds produced are believed to cause the malodors which
can
be present in diamine containing compositions. Having the diamine act as an
enzyme stabilizer also prevents the diamine from providing the benefits to the
composition for which it was originally put in to perform, namely, grease
cleaning,
sudsing, dissolution and low temperature stability. Therefore, it is preferred
to
minimize the amount of hydrogen peroxide present as an impurity in the
inventive
compositions either by using components which are substantially free of
hydrogen
peroxide and/or by using non-diamine antioxidants even though the diamine can
act
as an enzyme stabilizer, because of the possible generation of malodorous
compounds and the reduction in the amount of diamine available present to
perform
its primary role. '
It is further preferred that the compositions of the present invention be
"malodor" free. That is, that the odor of the headspace does not generate a
negative
olfactory response from the consumer. This can be achieved in many ways,
including the use of perfumes to mask any undesirable odors, the use of
stabilizers,
such as antioxidants, chelants etc., and/or the use of diamines which are
substantially
free of impurities. It is believed, without wanting to being limited by
theory, that it
is the impurities present in the diamines that are the cause of most of the
malodors in
the compositions of the present invention. These impurities can form during
the
preparation and storage of the diamines. They can also form during the
preparation
and storage of the inventive composition. The use of stabilizers such as
antioxidants
and chelants inhibit and/or prevent the formation of these impurities in the
composition from the time of preparation to ultimate use by the consumer and
beyond. Hence, it is most preferred to remove, suppress and/or prevent the
formation of these malodors by the addition of perfumes, stabilizers and/or
the use
of diamines which are substantially free from impurities.
Moreover, the hand dishwashing detergent composition of this invention can
further comprise baking soda, especially when formulated at a pH of below
about 9.
If present, the baking soda will comprise from about 0.5% to about 5%,
preferably
from about 1% to about 3%, by weight of the total composition.
All parts, percentages and ratios used herein are expressed as percent weight
unless otherwise specified.
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WO 98128393 PCT/US97/22694
6
Detailed Description of the Invention
Definitions - The present detergent compositions comprise an "effective
amount" or a "grease removal-improving amount" of individual components
defined
herein. By an "effective amount" of the diamines herein and adjunct
ingredients
herein is meant an amount which is sufficient to improve, either directionally
or
significantly at the 90% confidence level, the performance of the cleaning
composition against at least some of the target soils and stains. Thus, in a
composition whose targets include certain grease stains, the formulator will
use
sufficient diamine to at Ieast directionally improve cleaning performance
against
such stains. Importantly, in a fully-formulated detergent the diamine can be
used at
levels which provide at least a directional improvement in cleaning
performance
over a wide variety of soils and stains, as will be seen from the examples
presented
hereinafter.
As noted, the diamines are used herein in detergent compositions in
combination with detersive surfactants at levels which are effective for
achieving at
least a directional improvement in cleaning performance. In the context of a
hand
dishwashing 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 length of time the dishware is contacted with the
wash
water.
Since the habits and practices of the users of detergent compositions show
considerable variation, it is satisfactory to include from about 0.25% to
about 15%,
preferably from about 0.5% to about 10%, more preferably from about 0.5% to
about 6%, by weight, of the diamines in such compositions.
In one of its several aspects, this invention provides a means for enhancing
the removal of greasy/oily soils by combining the specific diamines of this
invention
with surfactants. Greasy/oily "everyday "soils are a mixture of triglycerides,
lipids,
complex polysaccharides, fatty acids, inorganic salts and proteinaceous
matter.
Without being limited by theory, it is believed that the strong grease
performance benefits achieved by the organic diamines across a broad range of
hardness (up to about 1,000 ppm expressed as CaC03) reduces the need for
divalent
ions in the hand dishwashing detergent to bolster grease performance in soft
water.
Significantly, the removal of divalent ions from conventional hand dishwashing
formulas leads to benefits in rate of product mixing with water (termed
"dissolution"), flash foam, rinsing, and low temperature stability.
Depending on consumer preferences, the compositions herein may be
formulated at viscosities of over about S0, preferably over about 100
centipoise, and
CA 02273259 2005-O1-25
7
more preferably from about 100 to about 400 centipoise. For European
formulations, the compositions may be formulated at viscosites of up to about
800
centipoise.
Moreover, the superior rate of dissolution achieved by divalent ion reduction
even allows the formulator to make hand dishwashing detergents, especially
compact
formulations, at even significantly higher viscosities (e.g., I,000 centipoise
or
higher) than conventional formulations while maintaining excellent dissolution
and
cleaning performance. This has significant potential advantages for making
compact
products with a higher viscosity while maintaining acceptable dissolution. By
"compact" or "Ultra" is meant detergent formulations with reduced levels of
water
compared to conventional liquid detergents. The level of water is less than
50%,
preferably less than 30% by weight of the detergent compositions. Said
concentrated
products provide advantages to the consumer, who has a product which can be
used
in lower amounts a.nd to the producer, who has lower shipping costs.
Superior grease cleaning and dissolution performance are obtained if the pH
of the detergent is maintained in the range of about 8.0 to about 12. This pH
range is
selected to maximize the in-use content of non-protonated diarnine (at one of
the
nitrogen atoms).
This is unlike the inferior situation that exists at pH less than 8 (see U.S.
4,556,509, Colgate) wherein the diamine is highly protonated and has little or
no
buffer capacity remaining or when using preformed amine salts or quaternized
derivatives.
Diamines - Preferred organic diamines are those in which pKl and pK2 are
in the range of about 8.0 to about 11.5, preferably in the range of about 8.4
to about
1 I, even more preferably from about 8.6 to about 10.75. Preferred materials
for
performance and supply considerations are 1,3 propane diamine (pKl=10.5;
pK2=8.8), 1,6 hexane diamine (pKl=11; pK2=10), 1,3 pentane diamine (Dytek EP)
(pKl=10.5; pK2=8.9), 2-methyl 1,5 pentane diamine (Dytek~ {pKl=11.2;
pK2=10.0). Other preferred materials are the primary/primary diamines with
alkylene spacers ranging from C4 to C8. In general, it is believed that
primary
diamines are preferred over secondary and tertiary diamines.
Definition of pKl and pK2 - As used herein, "pKal" and "pKa2" are
quantities of a type collectively known to those skilled in the art as "pKa"
pKa is
used herein in the same manner as is commonly known to people skilled in the
art of
chemistry. Values referenced herein can be obtained from literature, such as
from
"Critical Stability Constants: Volume 2, Amines" by Smith and Mantel, Plenum
Press, NY and London, 1975. Additional information on pKa's can be obtained
CA 02273259 2003-08-27
8
from relevant company literature. such as information supplied by Dupont. a
supplier of diamines.
As a working definition herein, the pKa of the diamines is specified in an all-
aqueous solution at 25oC and for an ionic strength between 0.1 to 0.5 M. The
pKa is
an equilibrium constant which can change with temperature and ionic strength;
thus,
values reported in the literature are sometimes not in agreement depending on
the
measurement method and conditions. To eliminate ambiguity, the relevant
conditions and/or references used for pKa's of this invention are as defined
herein or
in "Critical Stability Constants: Volume 2, Amines". One typical method of
measurement is the potentiometric titration of the acid with sodium hydroxide
and
determination of the pKa by suitable methods as described and referenced in
"The
Chemist's Ready Reference Handbook" by Shugar and Dean, McGraw Hill, NY,
1990.
It has been determined that substituents and structural modifications that
lower pK 1 and pK2 to below about 8.0 are undesirable and cause losses in
performance. This can include substitutions that lead to ethoxylated diamines,
hydroxy ethyl substituted diamines, diamines with oxygen in the beta (and less
so
gamma) position to the nitrogen in the spacer group (e.g., Jeffamine EDR 148).
In
addition, materials based on ethylene diamine are unsuitable.
The diamines useful herein can be defined by the following structure:
R~\ ~~X~ ~~Y Rs
N A
wherein R1~ are independently selected from H, methyl, -CH3CH2, and ethylene
oxides; Cx and Cy are independently selected from methylene groups or branched
alkyl groups where x+y is from about 3 to about 6; and A is optionally present
and is
selected from electron donating or withdrawing moieties chosen to adjust the
diamine pKa's to the desired range. If A is present, then x and y must both be
1 or
greater.
Examples of preferred diamines include the following:
~N~r~
Dimethyl aminopropyl amine: ~ ;
FitN
1,6-Hexane Diamine:
1,3 propane diamine -
CA 02273259 2003-08-27
~N~~~~2
2-methyl 1,5 pentane diamine - ;
HyN
1,3-pentanediamine, available under the tradename Dytek EP '~ IYNHz
HzN~NH2
1-methyl-diaminopropane - ;
H~/~/~~~-~'N~
Jeffamine EDR 148 - ;
NHZ
CHZCH2NHz
Isophorone diamine - '
CH2NH2
'CHZNHz
1,3-bis(methylamine)-cyclohexane
and mixtures thereof.
When tested as approximately equimolar replacements for Ca/Mg in the near
neutral pH range (7-8), the organic diamines provided only parity grease
cleaning
performance to Ca/Mg. This achievement is not possible through the use of
Ca/Mg
or through the use of organic diamines below pH 8 or through the use of
organic
diamine diacid salts below pH 8.
Anionic Surfactants - The anionic surfactants useful in the present invention
are preferably selected from the group consisting of, linear alkylbenzene
sulfonate,
alpha olefin sulfonate, paraffin sulfonates, methyl ester sulfonates, alkyl
sulfates,
alkyl alkoxy sulfate, alkyl sulfonates, alkyl alkoxy carboxylate, alkyl
alkoxylated
sulfates, sarcosinates, taurinates, and mixtures thereof. An effective amount,
typically from about 0.5% to about 90%, preferably about 5% to about 50%, more
preferably from about 10 to about 30%, weight %, of anionic detersive
surfactant
can be used in the present invention.
CA 02273259 2003-08-27
10
One type of anionic surfactant which can be utilized encompasses alkyl ester
sulfonates. These are desirable because they can be made with renewable, non-
petroleum resources. Preparation of the alkyl ester sulfonate surfactant
component
can be effected according to known methods disclosed in the technical
literature.
For instance, linear esters of Cg-C20 carboxylic acids can be sulfonated with
gaseous S03 according to "The Journal of the American Oil Chemists Society,"
52
( 1975), pp. 323-329. Suitable starting materials would include natural fatty
substances as derived from tallow, palm, and coconut oils, etc.
The prefer ed alkyl ester sulfonate surfactant, especially for laundry
applications, comprises alkyl ester sulfonate surfactants of the structural
formula:
0
R3-CH-C-OR4
S03M
wherein R3 is a Cg-C2p hydrocarbyl, preferably an alkyl, or combination
thereof,
R4 is a C1-C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M
is a
soluble salt-forming ration. Suitable salts include metal salts such as
sodium,
potassium, and lithium salts, and substituted or unsubstituted ammonium salts,
such
as methyl-, dimethyl, -trimethyl, and quaternary ammonium rations, e.g.
tetramethyl-ammonium and dimethyl piperdinium, and rations derived from
alkanolamines, e.g. monoethanol-amine, diethanolamine, and triethanolamine.
Preferably, R3 is C l0-C 16 alkyl, and R4 is methyl, ethyl or isopropyl.
Especially
preferred are the methyl ester sulfonates wherein R3 is C14-C16 alkyl.
Alkyl sulfate surfactants are another type of anionic surfactant of importance
for use herein. In addition to providing excellent overall cleaning ability
when used
in combination with polyhydroxy fatty acid amides (see below), including good
grease/oil cleaning over a wide range of temperatures, wash concentrations,
and
wash times, dissolution of alkyl sulfates can be obtained, as well as improved
formulability in liquid detergent formulations are water soluble salts or
acids of the
formula ROS03M wherein R preferably is a C10-C24 hydrocarbyl, preferably an
alkyl or hydroxyalkyl having a C10-C2p alkyl component, more preferably a C12-
C 1 g alkyl or hydroxyalkyl, and M is H or a ration, e.g., an alkali or
alkaline (Group
IA or Group IIA) metal ration (e.g., sodium, potassium, lithium, magnesium,
calcium), substituted or unsubstituted ammonium rations such as methyl-,
dimethyl-
and trimethyl ammonium and quaternary ammonium rations, e.g., tetramethyl-
ammonium and dimethyl piperdinium, and rations derived from alkanolarnines
such
as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and
the
like. Typically, alkyl chains of C12-16 ~'e Preferred for lower wash
temperatures
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WO 98/28393 PCT/US97/22694
11
(e.g., below about 50°C) and C 16-18 alkyl chains are preferred for
higher wash
temperatures (e.g., above about 50°C).
Alkyl alkoxylated sulfate surfactants are another category of useful anionic
surfactant. These surfactants are water soluble salts or acids typically of
the formula
RO(A)mS03M wherein R is an unsubstituted C 1 p-C24 alkyl or hydroxyalkyl group
having a C 10-C24 alkyl component, preferably a C 12-C20 alkyl or
hydroxyalkyl,
more preferably C 12-C 1 g alkyl or hydroxyalkyl, A is an ethoxy or propoxy
unit, m
is greater than zero, typically between about 0.5 and about 6, more preferably
between about 0.5 and about 3, and M is H or a cation which can be, for
example, a
metal canon (e.g., sodium, potassium, lithium, calcium, magnesium, etc.),
ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as
alkyl propoxylated sulfates are contemplated herein. Specific examples of
substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium
and
quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl
piperidinium and cations derived from alkanolamines, e.g. monoethanolamine,
diethanolamine, and triethanolamine, and mixtures thereof. Exemplary
surfactants
are C 12-C 1 g alkyl polyethoxylate ( 1.0) sulfate, C 12-C 1 g alkyl
polyethoxylate (2.25)
sulfate, C 12-C 1 g alkyl polyethoxylate (3.0) sulfate, and C 12-C 1 g alkyl
polyethoxylate (4.0) sulfate wherein M is conveniently selected from sodium
and
potassium. Surfactants for use herein can be made from natural or synthetic
alcohol
feedstocks. Chain lengths represent average hydrocarbon distributions,
including
branching.
Other Anionic Surfactants - Other anionic surfactants useful for detersive
purposes can also be included in the compositions hereof. These can include
salts
(including, for example, sodium, potassium, ammonium, and substituted ammonium
salts such as mono-, di- and triethanolamine salts) of soap, Cg-C2p linear
alkylbenzenesulphonates, Cg-C22 primary or secondary alkanesulphonates, Cg-C24
olefinsulphonates, sulphonated polycarboxylic acids prepared by sulphonation
of the
pyrolyzed product of alkaline earth metal citrates, e.g., as described in
British patent
specification No. 1,082,179, alkyl glycerol sulfonates, fatty acyl glycerol
sulfonates,
fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates,
paraffin
sulfonates, alkyl phosphates, isothionates such as the acyl isothionates, N-
acyl
taurates, fatty acid amides of methyl tauride, alkyl succinamates and
sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C 12-C 18
monoesters) diesters of sulfosuccinate (especially saturated and unsaturated
C6-C 14
diesters), N-acyl sarcosinates, sulfates of alkylpolysaccharides such as the
sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described below),
CA 02273259 2003-08-27
12
branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those
of the
formula RO(CH2CH20)kCH2C00-M+ wherein R is a Cg-C22 alkyl, k is an
integer from 0 to 10, and M is a soluble salt-forming cation, and fatty acids
esterified with isethionic acid and neutralized with sodium hydroxide. Resin
acids
and hydrogenated resin acids are also suitable, such as rosin, hydrogenated
rosin,
and resin acids and hydrogenated resin acids present in or derived from tall
oil.
Further examples are given in "Surface Active Agents and Detergents" (Vol. I
and II
by Schwartz, Perry and Berch). A variety of such surfactants are also
generally
disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et
al. at
Column 23, line 58 through Column 29, line 23.
Secondary Surfactants - Secondary detersive surfactant can be selected from
the group consisting of nonionics, cationics, ampholytics, zwitterionics, and
mixtures thereof. By selecting the type and amount of detersive surfactant,
along
with other adjunct ingredients disclosed herein, the present detergent
compositions
can be formulated to be used in the context of laundry cleaning or in other
different
cleaning applications, particularly including dishwashing. The particular
surfactants
used can therefore vary widely depending upon the particular end-use
envisioned.
Suitable secondary surfactants are described below.
Nonionic Detergent Surfactants - Suitable nonionic detergent surfactants are
generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December
30,
1975, at column 13, line 14 through coiurnn 16, line 6.
Exemplary, non-limiting classes of useful nonionic surfactants include:
alkyl dialkyl amine oxide, alkyl ethoxylate, alkanoyl glucose amide, alkyl
betaines,
and mixtures thereof.
Other nonionic surfactants for use herein include:
The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl
phenols. In general, the polyethylene oxide condensates are preferred. These
compounds include the condensation products of alkyl phenols having an alkyl
group containing from about 6 to about 12 carbon atoms in either a straight
chain or
branched chain configuration with the alkylene oxide. In a preferred
embodiment,
the ethylene oxide is present in an amount equal to from about 5 to about 25
moles
of ethylene oxide per mole of alkyl phenol. Commercially available nonionic
surfactants of this type include Igepal~ CO-630, marketed by the GAF
Corporation;
and Triton~ X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas
Company. These compounds are commonly referred to as alkyl phenol alkoxylates,
(e.g., alkyl phenol ethoxylates).
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WO 98/28393 PCT/U597I22694
13
The condensation products of aliphatic alcohols with from about 1 to about 2~
moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either
be
straight or branched, primary or secondary, and generally contains from about
8 to
about 22 carbon atoms. Particularly preferred are the condensation products of
alcohols having an alkyl group containing from about 10 to about 20 carbon
atoms
with from about 2 to about 18 moles of ethylene oxide per mole of alcohol.
Examples of commercially available nonionic surfactants of this type include
Tergitol~ 15-S-9 (the condensation product of C 11-C 15 linear secondary
alcohol
with 9 moles ethylene oxide), Tergitol~ 24-L-6 NMW (the condensation product
of
C 12-C 14 primary alcohol with 6 moles ethylene oxide with a narrow molecular
weight distribution), both marketed by Union Carbide Corporation; Neodol~ 45-9
(the condensation product of C 14-C 15 linear alcohol with 9 moles of ethylene
oxide), Neodol~ 23-6.5 (the condensation product of C 12-C 13 linear alcohol
with
6.5 moles of ethylene oxide), Neodol~ 45-7 (the condensation product of C 14-C
1 S
linear alcohol with 7 moles of ethylene oxide), Neodol~ 45-4 (the condensation
product of C 14-C 15 linear alcohol with 4 moles of ethylene oxide), marketed
by
Shell Chemical Company, and Kyro~ EOB (the condensation product of C 13-C 15
alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble
Company.
Other commercially available nonionic surfactants include Dobanol 91-8~
marketed
by Shell Chemical Co. and Genapol UD-080~ marketed by Hoechst. This category
of nonionic surfactant is referred to generally as "alkyl ethoxylates."
The condensation products of ethylene oxide with a hydrophobic base formed
by the condensation of propylene oxide with propylene glycol. The hydrophobic
portion of these compounds preferably has a molecular weight of from about
1500 to
about 1800 and exhibits water insolubility. The addition of polyoxyethylene
moieties to this hydrophobic portion tends to increase the water solubility of
the
molecule as a whole, and the liquid character of the product is retained up to
the
point where the polyoxyethylene content is about 50% of the total weight of
the
condensation product, which corresponds to condensation with up to about 40
moles
of ethylene oxide. Examples of compounds of this type include certain of the
commercially-available Pluronic~ surfactants, marketed by BASF.
The condensation products of ethylene oxide with the product resulting from
the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of
these products consists of the reaction product of ethylenediamine and excess
propylene oxide, and generally has a molecular weight of from about 2500 to
about
3000. This hydrophobic moiety is condensed with ethylene oxide to the extent
that
the condensation product contains from about 40% to about 80% by weight of
CA 02273259 2003-08-27
14
polyoxyethylene and has a molecular weight of from about x,000 to about
11,000.
Examples of this type of nonionic surfactant include certain of the
commercially
available Tetronic~ compounds, marketed by BASF.
Semi-polar nonionic surfactants are a special category of nonionic surfactants
which include water-soluble amine oxides containing one alkyl moiety of from
about 10 to about 18 carbon atoms and 2 moieties selected from the group
consisting
of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3
carbon
atoms; water-soluble phosphine oxides containing one alkyl moiety of from
about 10
to about 18 carbon atoms and 2 moieties selected from the group consisting of
alkyl
groups and hydroxyalkyl groups containing from about 1 to about 3 carbon
atoms;
and water-soluble sulfoxides containing one alkyl moiety of from about 10 to
about
18 carbon atoms and a moiety selected from the group consisting of alkyl and
hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine oxide surfactants
having the formula
O
R3(OR4 N(RS)2
wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures
thereof
containing from about 8 to about 22 carbon atoms; R4 is an alkylene or
hydroxyalkylene group containing from about 2 to about 3 carbon atoms or
mixtures
thereof; x is from 0 to about 3; and each RS is an alkyl or hydroxyalkyl group
containing from about 1 to about 3 carbon atoms or a polyethylene oxide group
containing from about 1 to about 3 ethylene oxide groups. The RS groups can be
attached to each other, e.g., through an oxygen or nitrogen atom, to form a
ring
structure.
These amine oxide surfactants in particular include C 10-C 1 g alkyl dimethyl
amine oxides and Cg-C 12 alkoxy ethyl dihydroxy ethyl amine oxides.
Alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued
January 21, 1986, having a hydrophobic group containing from about 6 to about
30
carbon atoms, preferably from about 10 to about 16 carbon atoms and a
polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about
1.3
to about 10, preferably from about 1.3 to about 3, most preferably from about
1.3 to
about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon
atoms
can be used, e.g., glucose, galactose and galactosyl moieties can be
substituted for
the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-
, 3-, 4-,
etc. positions thus giving a glucose or galactose as opposed to a glucoside or
galactoside.) The intersaccharide bonds can be, e.g., between the one position
of the
CA 02273259 1999-OS-28
WO 98/28393 PCT/US97/22694
additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the
preceding
saccharide units.
Optionally, and less desirably, there can be a polyalkylene-oxide chain
joining
the hydrophobic moiety and the polysaccharide moiety. The preferred
alkyleneoxide
is ethylene oxide. Typical hydrophobic groups include alkyl groups, either
saturated
or unsaturated, branched or unbranched containing from about 8 to about 18,
preferably from about 10 to about 16, carbon atoms. Preferably, the alkyl
group is a
straight chain saturated alkyl group. The alkyl group can contain up to about
3
hydroxy groups and/or the polyalkyleneoxide chain can contain up to about 10,
preferably less than 5, alkyleneoxide moieties. Suitable alkyl polysaccharides
are
octyl, nonyl, decyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl,
heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides,
galactosides,
lactosides, glucoses, fructosides, fructoses and/or galactoses. Suitable
mixtures
include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl
tetra-,
penta-, and hexa-glucosides.
The preferred alkylpolyglycosides have the formula
R20(CnH2n0~(glYcosyI)x
wherein R2 is selected from the group consisting of alkyl, alkyl-phenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl
groups
contain from about 10 to about 18, preferably from about 12 to about 14,
carbon
atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x
is from
about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably
from
about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To
prepare
these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and
then
reacted with glucose, or a source of glucose, to form the glucoside
(attachment at the
1-position). The additional glycosyl units can then be attached between their
1-
position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position,
preferably
predominantly the 2-position.
Fatty acid amide surfactants having the formula:
R6-~N(R7)2
wherein R6 is an alkyl group containing from about 7 to about 21 (preferably
from
about 9 to about 17) carbon atoms and each R7 is selected from the group
consisting
of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H40)xH where x varies
from about 1 to about 3.
Preferred amides are Cg-C20 ammonia amides, monoethanolamides,
diethanolamides, and isopropanolamides.
CA 02273259 2003-08-27
16
Cationic Surfactants - Cationic detersive surfactants can also be included in
detergent compositions of the present invention. Cationic surfactants include
the
ammonium surfactants such as alkyldimethylammonium halogenides, and those
surfactants having the formula:
[R2(OR3)y)[R4(OR3)y)2R5N+X-
wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18
carbon
atoms in the alkyl chain, each R3 is selected from the group consisting of -
CH2CH2-
-CH2CH(CH3)-, -CH2CH(CH20H)-, -CH2CH2CH2-, and mixtures thereof; each
R4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl,
benzyl, ring structures formed by joining the two R4 groups, -
CH2CHOHCHOHCOR6CHOH-CH20H wherein R6 is any hexose or hexose
polymer having a molecular weight less than about 1000, and hydrogen when y is
not O; R5 is the same as R4 or is an alkyl chain wherein the total number of
carbon
atoms of R2 plus R5 is not more than about 18; each y is from 0 to about 10
and the
sum of the y values is from 0 to about 15; and X is any compatible anion.
Other cationic surfactants useful herein are also described in U.S. Patenc
4,228,044, Cambre, issued October 14, 1980.
Other Surfactants - Ampholytic surfactants can be incorporated into the
detergent compositions hereof. These surfactants can be broadly described as
aliphatic derivatives of secondary or tertiary amines, or aliphatic
derivatives of
heterocyclic secondary and tertiary amines in which the aliphatic radical can
be
straight chain or branched. One of the aliphatic substituents contains at
least about 8
carbon atoms, typically from about 8 to about 18 carbon atoms, and at least
one
contains an anionic water-solubilizing group, e.g., carboxy, sulfonate,
sulfate. See
U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at
column
19, lines 18-35 for examples of ampholytic surfactants. Preferred amphoteric
include C 12 -C 1 g alkyl ethoxylates ("AE") including the so-called narrow
peaked
alkyl ethoxylates and C6-C 12 alkyl phenol alkoxylates (especially ethoxylates
and
mixed ethoxy/propoxy), C 12-C 1 g betaines and sulfobetaines ("sultaines"), C
l 0-C 18
amine oxides, and mixtures thereof.
Zwitterionic surfactants can also be incorporated into the detergent
compositions hereof. These surfactants can be broadly described as derivatives
of
secondary and tertiary amines, derivatives of heterocyclic secondary and
tertiary
amines, or derivatives of quaternary ammonium, quaternary phosphonium or
tertiary
sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued
December 30, 1975 at column 19, line 38 through column 22, line 48 for
examples
CA 02273259 1999-OS-28
WO 98128393 PCT/US97/22694
17
of zwitterionic surfactants. Amphoiytic and zwitterionic surfactants are
generally
used in combination with one or more anionic and/or nonionic surfactants.
PolYhvdroxv Fattv Acid Amide Surfactant - The detergent compositions hereof
may also contain an effective amount of polyhydroxy fatty acid amide
surfactant.
By "effective amount" is meant that the formulator of the composition can
select an
amount of polyhydroxy fatty acid amide to be incorporated into the
compositions
that will improve the cleaning performance of the detergent composition. In
general,
for conventional levels, the incorporation of about 1 %, by weight,
polyhydroxy fatty
acid amide will enhance cleaning performance.
The detergent compositions herein will typically comprise about 1 % weight
basis, polyhydroxy fatty acid amide surfactant, preferably from about 3% to
about
30%, of the polyhydroxy fatty acid amide. The polyhydroxy fatty acid amide
surfactant component comprises compounds of the structural formula:
O Rl
R~-C-N-Z
wherein: Rl is H, Cl-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a
mixture thereof, preferably C 1-C4 alkyl, more preferably C 1 or C2 alkyl,
most
preferably C 1 alkyl (i.e., methyl); and R2 is a CS-C31 hydrocarbyl,
preferably
straight chain C~-C 1 g alkyl or alkenyl, more preferably straight chain Cg-C
1 ~ alkyl
or alkenyl, most preferably straight chain C 11-C 1 S alkyl or alkenyl, or
mixtures
thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain
with
at least 3 hydroxyls directly connected to the chain, or an alkoxylated
derivative
(preferably ethoxylated or propoxylated) thereof. Z preferably will be derived
from
a reducing sugar in a reductive amination reaction; more preferably Z will be
a
glycityl. Suitable reducing sugars include glucose, fructose, maltose,
lactose,
galactose, mannose, and xylose. As raw materials, high dextrose corn syrup,
high
fructose corn syrup, and high maltose corn syrup can be utilized as well as
the
individual sugars listed above. These corn syrups may yield a mix of sugar
components for Z. It should be understood that it is by no means intended to
exclude other suitable raw materials. Z preferably will be selected from the
group
consisting of -CH2-(CHOH)n-CH20H, -CH(CH20H)-(CHOH)n-1-CH20H, -CH2-
(CHOH)2(CHOR')(CHOH)-CH20H, and alkoxylated derivatives thereof, where n is
an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic
monosaccharide.
Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH20H.
R' can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-
2-hydroxy ethyl, or N-2-hydroxy propyl.
CA 02273259 2003-08-27
18
R2-CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide,
myristamide, capricamide, palmitamide, tallowamide, etc.
Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl,
1-
deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
Methods for making polyhydroxy fatty acid amides are known in the art. In
general, they can be made by reacting an alkyl amine with a reducing sugar in
a
reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine,
and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or
triglyceride in a condensation/amidation step to form the N-alkyl, N-
polyhydroxy
fatty acid amide product. Processes for making compositions containing
polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent
Specification 809,060, published February 18, 1959, by Thomas Hedley & Co.,
Ltd.,
U.S. Patent 2,965,576, issued December 20, 1960 to E. R. Wilson, and U.S.
Patent
2,703,798, Anthony M. Schwartz, issued March 8, 1955, and U.S. Patent
1,985,424,
issued December 25, 1934 to Piggott .
Builder - The compositions according to the present invention may further
comprise a builder system. Any conventional builder system is suitable for use
herein including aluminosilicate materials, silicates, polycarboxylates and
fatty acids,
materials such as ethylene-diamine tetraacetate, metal ion sequestrants such
as
aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphoric
acid and diethylene triamine pentamethylene-phosphoric acid. Though less
preferred for obvious environmental reasons, phosphate builders can also be
used
herein.
Suitable polycarboxylates builders for use herein include citric acid,
preferably
in the form of a water-soluble salt, derivatives of succinic acid of the
formula R-
CH(COOH)CH2(COOH) wherein R is C10-20 alkyl or alkenyl, preferably C12-16,
or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone
substituents.
Specific examples include lauryl succinate , myristyl succinate, palmityl
succinate 2-
dodecenylsuccinate, 2-tetradecenyl succinate. Succinate builders are
preferably used
in the form of their water-soluble salts, including sodium, potassium,
ammonium and
alkanolanunonium salts.
Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate
monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
Especially for the liquid execution herein, suitable fatty acid builders for
use
herein are saturated or unsaturated C10-18 fatty acids, as well as the
corresponding
soaps. Preferred saturated species have from 12 to 16 carbon atoms in the
alkyl
CA 02273259 2003-08-27
19
chain. The preferred unsaturated fatty acid is oleic acid. Other preferred
builder
system for liquid compositions is based on dodecenyi succinic acid and citric
acid.
Detergency builder salts are normally included in amounts of from 3% to 50%
by weight of the composition preferably from S% to 30% and most usually from
5%
to 25% by weight.
Optional Detergent Ingredients: - Detergent compositions of the present
invention may further comprise one or more enzymes which provide cleaning
performance benefits. Said enzymes include enzymes selected from cellulases,
hemiceUulases, peroxidases, proteases, gluco-amylases, amylases, lipases,
cutinases,
pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases,
ligninases, pullulanases, tannases, pentosanases, malanases,13-glucanases,
arabinosidases or mixtures thereof. A preferred combination is a detergent
composition having a cocktail of conventional applicable enzymes like
protease,
amylase, lipase, cutinase and/or cellulase.
Cellulases - the cellulases usable in the present invention include both
bacterial or fungal cellulase. Suitable cellulases are disclosed in U.S.
Patent
4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from
Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028;
GB-
A-2.095.275 and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by a strain of Humicola
insolens (Humicola grisea var. thermoidea), particularly the Humicola strain
DSM
1800. Other suitable cellulases are cellulases originated from Humicola
insolens
having a molecular weight of about 50KDa, an isoelectric point of 5.5 and
containing
415 amino acids. Especially suitable cellulases are the cellulases having
color care
benefits. Examples of such cellulases are cellulases described in European
patent
No. 0495257.
Peroxidase enzymes are used in combination with oxygen sources, e.g.
percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for
"solution bleaching", i.e. to prevent transfer of dyes or pigments removed
from
substrates during wash operations to other substrates in the wash solution.
Peroxidase enzymes are known in the art, and include, for example, horseradish
peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-
peroxidase.
Peroxidase-containing detergent compositions are disclosed, for example, in
PCT
International Application WO 89/099813 and in European Patent - No . 0 5 40 7
8 4 .
CA 02273259 2003-08-27
Said cellulases and/or peroxidases are normally incorporated in the detergent
composition at levels from 0.0001 % to 2% of active enzyme by weight of the
detergent composition.
Proteolvtic Enzyme - The proteolytic enzyme can be of animal, vegetable or
microorganism (preferred) origin. The proteases for use in the detergent
compositions herein include (but are not limited to) trypsin, subtilisin,
chymotrypsin
and elastase-type proteases. Preferred for use herein are subtilisin-type
proteolytic
enrymes. Particularly preferred is bacterial serine proteolytic enzyme
obtained from
Bacillus subtilis and/or Bacillus licheniformis.
Suitable proteolytic enzymes include Novo Industri A/S Alcalase~ (preferred),
Esperase~~ Savinase~ (Copenhagen, Denmark), Gist-brocades' Maxatase~,
Maxacal~ and Maxapem 15~ (protein engineered Maxacal~) (Delft, Netherlands),
and subtilisin BPN and BPN'(preferred), which are commercially available.
Preferred proteolytic enzymes are also modified bacterial serine proteases,
such as
those made by Genencor International, Inc. (San Francisco, California) which
are
described in European Patent 251,4468, granted December 28, 1994 (particularly
pages 17, 24 and 98) and which are also called herein "Protease B". U.S.
Patent
5,030,378, Venegas, issued July 9, 1991, refers to a modified bacterial serine
proteolytic enzyme (Genencor International) which is called "Protease A"
herein
(same as BPN'). In particular see columns 2 and 3 of U.S. Patent 5,030,378 for
a
complete description, including amino sequence, of Protease A and its
variants.
Other proteases are sold under the tradenames: Primase;~~7urazym;
Opticlear~and
Optimase~referred proteolytic enzymes, then, are selected from the group
consisting of Alcalase ~ (Novo Industri A/S), BPN', Protease A and Protease B
(Genencor), and mixtures thereof. Protease B is most preferred.
Of particular interest for use herein are the proteases described in U.S.
Patent
No. 5,470,733.
Another 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, andlor +274
CA 02273259 2003-08-27
21
according to the numbering of Bacilhts amyloliguefaciens subtilisin, as
described in
WO 95/10615 published April 20, 1995 by Genencor International (A. Baeck et
al.
entitled "Protease-Containing Cleaning Compositions" having U.S. Patent
No. 5,679,630.
Useful proteases are also described in PCT publications: WO 95/30010
published November 9, 1995 by The Procter & Gamble Company; WO 95/30011
published November 9, 1995 by The Procter & Gamble Company; WO 95/29979
published November 9, 1995 by The Procter & Gamble Company.
Protease enzyme may be incorporated into the compositions in accordance
with the invention at a level of from 0.0001% to 2% active enzyme by weight of
the
composition.
Lipase - suitable lipase enzymes include those produced by microorganisms
of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as
disclosed in British Patent 1,372,034. Suitable lipases include those which
show a
positive immunological cross-reaction with the antibody of the lipase,
produced by
the microorganism Pseudomonas fluorescens IAM 1057. This lipase is available
from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase
P
"Amano," hereinafter referred to as "Amano-P". Further suitable Iipases are
lipases
such as M1 Lipase~ and Lipomax~ (Gist-Brocades). Other suitable commercial
lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter
viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan;
Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth
Co., The Netherlands, and lipases ex Pseudomonas gladioli. LIPOLASE~ enzyme
derived from Humicola lanuginosa and commercially available from Novo, see
also
EP 341,947, is a preferred lipase for use herein. Lipase and amylase variants
stabilized against peroxidase enzymes are described in WO 9414951 A to Novo.
See
also WO 9205249 and RD 94359044.
(See also patent application WO 92/05249 viz. wherein the native lipase ex
Htunicola lanuginosa aspartic acid (D) residue at position 96 is changed to
Leucine
(L). According to this nomenclature said substitution of aspartic acid to
Leucine in
position 96 is shown as : D96L.) Preferably the Humicola lanuginosa strain DSM
4106 is used.
In spite of the large number of publications on lipase enzymes, only the
lipase derived from Humicola lanuginosa and produced in Aspergillus oryzae as
host has so far found widespread application as additive for washing products.
It is
CA 02273259 2003-08-27
22
available from Novo Nordisk under the tradename Lipolase~ and Lipolase Ultra~,
as noted above. In order to optimize the stain removal performance of
Lipolase,
Novo Nordisk have made a number of variants. As described in WO 92/05249, the
D96L variant of the native Humicola lanuginosa lipase improves the lard stain
removal efficiency by a factor 4.4 over the wild-type lipase (enzymes compared
in
an amount ranging from 0.075 to 2.5 mg protein per liter). Research Disclosure
No.
35944 published on March 10, 1994, by Novo Nordisk discloses that the lipase
variant (D96L) may be added in an amount corresponding to 0.001-100- mg (5-
500,000 LU/liter) lipase variant per liter of wash liquor.
Also suitable are cutinases [EC 3.1.1.50] which can be considered as a
special kind of lipase, namely lipases which do not require interfacial
activation.
Addition of cutinases to detergent compositions have been described in e.g. WO-
A-
88/09367 (Genencor).
The lipases and/or cutinases are normally incorporated in the detergent
composition at levels from 0.0001 % to 2% of active enzyme by weight of the
detergent composition.
Amylase - Amylases (a and/or 13) can be included for removal of
carbohydrate-based stains. Suitable amylases are Termamyl~ (Novo Nordisk),
Fungamyl~ and BAN~ (Novo Nordisk). The enzymes may be of any suitable
origin, such as vegetable, animal, bacterial, fungal and yeast origin. Amylase
enzymes are normally incorporated in the detergent composition at levels from
0.0001 % to 2%, preferably from about 0.0001 % to about 0.5%, more preferably
from about 0.0005% to about 0.1 %, even more preferably from about 0.001 % to
about 0.05% of active enzyme by weight of the detergent composition.
Amylase enzymes also include those described in W095/26397 and in
WO 96/23873. Other specific amylase
enzymes for use in the detergent compositions of the present invention
therefore
include
(a) 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,
W09512b397.
(b) a-amylases according (a) comprising the amino sequence shown in the SEQ ID
listings in the above cited reference. or an a-amylase being at least 80%
homologous
with the amino acid sequence shown in the SEQ ID listing.
CA 02273259 2003-08-27
23
(c) a-amylases according (a) obtained from an alkalophilic Bacilh~s species,
comprising the following amino sequence in the N-terminal : His-His-Asn-Gly-
Thr-
Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp.
A polypeptide is considered to be X% homologous to the parent amylase if a
comparison of the respective amino acid sequences, performed via algorithms,
such
as the one described by Lipman and Pearson in Science 227, 1985, p. 1435,
reveals
an identity of X%
(d) a-amylases according (a-c) wherein the a-amylase is obtainable from an
alkalophilic Bacillus species; and in particular, from any of the strains NCIB
12289,
NCIB 12512, NCIB 12513 and DSM 935.
In the context of the present invention, the term "obtainable from" is
intended not
only to indicate an amylase produced by a Bacillus strain but also an amylase
encoded by a DNA sequence isolated from such a Bacillus strain and produced in
an
host organism transformed with said DNA sequence.
(e)a-amylase showing positive immunological cross-reactivity with antibodies
raised against an a-amylase having an amino acid sequence corresponding
respectively to those a-amylases in (a-d).
(f) Variants of the following parent a-amylases which (i) have one of the
amino acid
sequences shown in corresponding respectively to those a-amylases in (a-e), or
(ii)
displays at least 80% homology with one or more of said amino acid sequences,
andlor displays immunological cross-reactivity with an antibody raised against
an a-
amylase having one of said amino acid sequences, and/or is encoded by a DNA
sequence which hybridizes with the same probe as a DNA sequence encoding an a-
amylase having one of said amino acid sequence; in which variants
I . at least one amino acid residue of said parent a-amylase has been deleted;
and/or
2. at least one amino acid residue of said parent a-amylase has been replaced
by a
different amino acid residue; and/or
3. at least one amino acid residue has been inserted relative to said parent a-
amylase;
said variant having an a-amylase activity and exhibiting at least one of the
following
properties relative to said parent a-amylase : increased thermostability,
increased
stability towards oxidation, reduced Ca ion dependency, increased stability
and/or a-
amylolytic activity at neutral to relatively high pH values, increased a-
amylolytic
activity at relatively high temperature and increase or decrease of the
isoelectric
point (pI) so as to better match the pI value for a-amylase variant to the pH
of the
medium.
Said variants are described in Wo 96/23873 .
CA 02273259 2003-08-27
24
Other amylases suitable herein include, for example, a-amylases described in
GB 1.296.839 to Novo; RAPIDASE~, International Bio-Synthetics, Inc. and
TER:VIAMYL~, 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 about 60oC; or
alkaline
stability, e.g., at a pH from about 8 to about 11, measured versus the above-
identified reference-point amylase. Stability can be measured using any of the
art-
disclosed technical tests. See, for example, 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 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.
subtilis, or B. stearothermophilus; (b) stability-enhanced amylases as
described by
Genencor International in a paper entitled "Oxidatively Resistant alpha-
Amylases"
presented at the 207th American Chemical Society National Meeting, March 13-17
1994, by C. Mitchinson. Therein it was noted that bleaches in automatic
dishwashing detergents inactivate alpha-amylases but that improved oxidative
stability amylases have been made by Genencor from B. licheniformis NCIB8061.
Methionine (Met} was identified as the most likely residue to be modified. Met
was
substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438
leading to
i
CA 02273259 2003-08-27
specific mutants, particularly important being M 197L and M 197T with the M
197T
variant being the most stable expressed variant. Stability was measured in
CASCADE~ and SUNLIGHT~; (c) particularly preferred amylases herein include
amylase variants having additional modification in the immediate parent as
described in WO 9510603 A and are available from the assignee, Novo, as
DURAMYL~. Other particularly preferred oxidative stability enhanced amylase
include those described in WO 9418314 to Genencor International and WO 9402597
to Novo. Any other oxidative stability-enhanced amylase can be used, for
example
as derived by site-directed mutagenesis from known chimeric, hybrid or simple
mutant parent forms of available amylases. Other preferred enzyme
modifications
are accessible. See WO 9509909 A to Novo.
Various carbohydrase enzymes which impart antimicrobial activity may also
be included in the present invention. Such enzymes include endoglycosidase,
Type
II endoglycosidase and glucosidase as disclosed in U.S. Patent Nos. 5,041,23b,
5,395,541, 5,238,843 and 5,356,803.
Of course, other enzymes having antimicrobial activity may be
employed as well including peroxidases, oxidases and various other enzymes.
Enzyme Stabilizine System - The enzyme-containing compositions herein
may optionally also comprise from about 0.001 % to about 10%, preferably from
about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by
weight of an enzyme stabilizing system. The enzyme stabilizing system can be
any
stabilizing system which is compatible with the detersive enzyme. Such a
system
may be inherently provided by other formulation actives, or be added
separately,
e.g., by the formulator or by a manufacturer of detergent-ready enzymes. Such
stabilizing systems can, for example, comprise calcium ion, boric acid,
propylene
glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and
are
designed to address different stabilization problems depending on the type and
physical form of the detergent composition.
One stabilizing approach is the use of water-soluble sources of calcium and/or
magnesium ions in the finished compositions which provide such ions to the
enzymes. Calcium ions are generally more effective than magnesium ions and are
preferred herein if only one type of cation is being used. Typical detergent
compositions, especially liquids, will comprise from about 1 to about 30,
preferably
from about 2 to about 20, more preferably from about 8 to about 12 millimoles
of
calcium ion.per liter of finished detergent composition, though variation is
possible
depending on factors including the multiplicity, type and levels of enzymes
incorporated. Preferably water-soluble calcium or magnesium salts are
employed,
CA 02273259 1999-OS-28
WO 98/28393 PCT/US97/22694
26
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 and/or
Magnesium
may of course be useful, for example for promoting the grease-cutting action
of
certain types of surfactant.
Another stabilizing approach is by use of borate species. See Severson, U.S.
4,537,706. Borate stabilizers, when used, may be at levels of up to 10% or
more of
the composition though more typically, levels of up to about 3% by weight of
boric
acid or other borate compounds such as borax or orthoborate are suitable for
liquid
detergent use. Substituted boric acids such as phenylboronic acid,
butaneboronic
acid, p-bromophenylboronic acid or the like can be used in place of boric acid
and
reduced levels of total boron in detergent compositions may be possible though
the
use of such substituted boron derivatives.
Stabilizing systems of certain cleaning compositions, for example automatic
dishwashing compositions, may further comprise from 0 to about 10%, preferably
from about 0.01 % to about 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 about 0.5 ppm to
about
1.75 ppm, the available chlorine in the total volume of water that comes in
contact
with the enzyme, for example during dish- or fabric-washing, can be relatively
large;
accordingly, enzyme stability to chlorine in-use is sometimes problematic.
Since
perborate or percarbonate, which have the ability to react with chlorine
bleach, may
present in certain of the instant compositions in amounts accounted for
separately
from the stabilizing system, the use of additional stabilizers against
chlorine, may,
most generally, not be essential, though improved results may be obtainable
from
their use. Suitable chlorine scavenger anions are widely known and readily
available, and, if used, can be salts containing ammonium cations with
sulfite,
bisulfate, thiosulfite, thiosulfate, iodide, etc. Antioxidants such as
carbamate,
ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA)
or
alkali metal salt thereof, monoethanoiamine (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,
CA 02273259 1999-OS-28
WO 98/28393 PCT/US97/22694
27
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.
Perfumes - Perfumes and perfumery ingredients useful in the present
compositions and processes comprise a wide variety of natural and synthetic
chemical ingredients, including, but not limited to, aldehydes, ketones,
esters, and
the like. Also included are various natural extracts and essences which can
comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose
extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine
oil,
cedar, and the like. Finished perfumes can comprise extremely complex mixtures
of
such ingredients. Finished perfumes typically comprise from about 0.01 % to
about
2%, by weight, of the detergent compositions herein, and individual perfumery
ingredients can comprise from about 0.0001 % to about 90% of a 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-tent-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-tetramethyl indane; 1-dodecanal, 4-(4-
hydroxy-
4-methylpentyl)-3-cyclohexene-1-carboxaldehyde; 7-hydroxy-3,7-dimethyl
ocatanal; 10-undecen-1-al; iso-hexenyl cyclohexyl carboxaldehyde; formyl
tricyclodecane; condensation products of hydroxycitronellal and methyl
anthranilate, condensation products of hydroxycitronellal and indol,
condensation
products of phenyl acetaldehyde and indol; 2-methyl-3-(para-tent-butylphenyl)-
propionaldehyde; ethyl vanillin; heliotropin; hexyl cinnamic aldehyde; amyl
CA 02273259 1999-OS-28
WO 98/28393 PCT/US97/22694
28
cinnamic aldehyde; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;
coumarin; decalactone gamma; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic
acid lactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-
benzopyrane; beta-naphthol methyl ether; ambroxane; dodecahydro-3a,6,6,9a-
tetra-
methylnaphtho[2,1b]furan; cedrol, ~-(2,2,3-trimethylcyclopent-3-enyl)-3-
methylpentan-2-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-
ol;
caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenyl acetate;
benzyl
salicylate; cedryl acetate; and para-(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-napthol
methyl
ether; methyl beta-naphthyl ketone; 2-methyl-2-(para-iso-propylphenyl)-
propionaldehyde; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-
2-benzopyrane; dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b)furan; anisalde-
hyde; coumarin; cedrol; vanillin; cyclopentadecanolide; tricyclodecenyl
acetate; and
tricyclodecenyl propionate.
Other perfume materials include essential oils, resinoids, and resins from a
variety of sources including, but not limited to: Peru balsam, Olibanum
resinoid,
styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander and
lavandin.
Still other perfume chemicals include phenyl ethyl alcohol, terpineol,
linalool,
linalyl acetate, geraniol, nerol, 2-(1,1-dimethylethyl)-cyclohexanol acetate,
benzyl
acetate, and eugenol. Carriers such as diethylphthalate can be used in the
finished
perfume compositions.
Polymeric Dispersing Agents - Polymeric dispersing agents can
advantageously be utilized at levels from about 0.1 % to about 7%, by weight,
in the
compositions herein. It is believed, though it is not intended to be limited
by theory,
that polymeric dispersing agents enhance overall detergent performance by
crystal
growth inhibition, particulate soil release peptization, and anti-
redeposition.
Polymeric polycarboxylate materials can be prepared by polymerizing or
copolymerizing suitable unsaturated monomers, preferably in their acid form.
Unsaturated monomeric acids that can be polymerized to form suitable polymeric
polycarboxylates include acrylic acid, malefic acid (or malefic anhydride),
fiunaric
acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic acid. The presence in the polymeric polycarboxylates herein
or
CA 02273259 1999-OS-28
WO 98/28393 PCT/US97/22694
29
monomeric segments, containing no carboxylate radicals such as vinylmethyl
ether,
styrene, ethylene, etc. is suitable provided that such segments do not
constitute more
than about 40% by weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid. Such acrylic acid-based polymers which are useful herein are the water-
soluble salts of polymerized acrylic acid. The average molecular weight of
such
polymers in the acid form preferably ranges from about 2,000 to 10,000, more
preferably from about 4,000 to 7,000 and most preferably from about 4,000 to
5,000.
Water-soluble salts of such acrylic acid polymers can include, for example,
the alkali
metal, ammonium and substituted ammonium salts. Soluble polymers of this type
are known materials. Use of polyacrylates of this type in detergent
compositions has
been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued march 7,
1967.
Acrylic/maleic-based copolymers may also be used as a preferred component
of the dispersing/anti-redeposition agent. Such materials include the water-
soluble
salts of copolymers of acrylic acid and malefic acid. The average molecular
weight
of such copolymers in the acid form preferably ranges from about 2,000 to
100,000,
more preferably from about 5,000 to 75,000, most preferably from about 7,000
to
65,000. The ratio of acrylate to maleate segments in such copolymers will
generally
range from about 30:1 to about 1:1, more preferably from about I0:1 to 2:1.
Water-
soluble salts of such acrylic acid/maleic acid copolymers can include, for
example,
the alkali metal, ammonium and substituted ammonium salts. Soluble
acrylate/maleate copolymers of this type are known materials which are
described in
European Patent Application No. 66915, published December 15, 1982, as well as
in
EP 193,360, published September 3, 1986, which also describes such polymers
comprising hydroxypropylacrylate. Still other useful dispersing agents include
the
maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in
EP
193,360, including, for example, the 45/45/10 terpolymer of
acrylic/maleic/vinyl
alcohol.
Other polymeric materials which can be included are polypropylene glycol
(PPG), propylene glycol (PG), and polyethylene glycol (PEG). PEG can exhibit
dispersing agent performance as well as act as a clay soil removal-
antiredeposition
agent. Typical molecular weight ranges for these purposes range from about 500
to
about 100,000, preferably from about 1,000 to about 50,000, more preferably
from
about 1,500 to about 10,000.
Polyaspartate and polyglutamate dispersing agents may also be used,
especially in conjunction with zeolite builders. Dispersing agents such as
polyaspartate preferably have a molecular weight (avg.) of about 10,000.
i
CA 02273259 2003-08-27
Additionally, 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 I0.0%, typically from 0.1 % to ~%,
preferably from 0.2% to 3.0% by weight, of the composition.
Preferred SRA's typically have hydrophilic segments to hydrophilize the
surface of hydrophobic fibers such as polyester and nylon, and hydrophobic
segments to deposit upon hydrophobic fibers and remain adhered thereto through
completion of washing and rinsing cycles thereby serving as an anchor for the
hydrophilic segments. This can enable stains occurring subsequent to treatment
with
SItA to be more easily cleaned in later washing procedures.
SRA's can include a variety of charged, e.g., anionic or even cationic (see
U.S. 4,956,447), as well as noncharged monomer units and structures may be
linear,
branched or even star-shaped. They may include capping moieties which are
especially effective in controlling molecular weight or altering the physical
or
surface-active properties. Structures and charge distributions may be tailored
for
application to different fiber or textile types and for varied detergent or
detergent
additive products.
Preferred SRA's include oligomeric terephthalate esters, typically prepared
by processes involving at least one transesterification/oligomerization, often
with a
metal catalyst such as a titanium(IV) alkoxide. Such esters may be made using
additional monomers capable of being incorporated into the ester structure
through
one, two, three, four or more positions, without of course forming a densely
crosslinked overall structure.
Suitable SRA's include products as described in U.S. 4,968,451; U.S.
4,711,730; U.S. 4,721,580; U.S. 4,702,857; U.S. 4,877,896; U.S. 3,959,230;
U.S.
3,893,929; U. S. 4,000,093; EP Appl. 0 219 048; U.S. 5,415,807; U.S.
4,201,824;
U.S. 4,240,918; U.S. 4,525,524; U.S. 4,201,824; U.S. 4,579,681; EP 279,134A;
EP
457,205; DE 2,335,044; U.S. 4,240,918; U. S. 4,787,989; U. S. 4,525,524; U.S.
4,877,896;U.S.4,968,451;U.S.4,702,85?;us 5,691,298 and us 4,451,635.
Commercially available examples include SOKALAN HP-22~M
TM
available from BASF, Germany; ZELCOI~~ 126 from Dupont; and MILEASE T
from ICI.
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 WO 90/01815A1.
Chemically, these materials comprise polyaerylates having one ethoxy
side-chain per every 7-8 acrylate units. The side-chains are of the formula
CA 02273259 2003-08-27
31
-(CH2C1-1~0)m(CH2)nCH3 wherein m is 2-3 and n is 6-12. The side-chains are
ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type
structure. The molecular weight can vary, but is typically in the range of
about 2000
to about 50,000. Such alkoxylated polycarboxylates can comprise from about
0.05%
to about 10%, by weight, of the compositions herein.
Another polymer dispersant form use herein includes polyethoxyated-
polyamine polymers (PPP). The preferred polyethoxylated-polyamines useful
herein are generally polyalkyleneamines (PAA's), polyalkyleneimines (PAI's),
preferably polyethyleneamine (PEA's), polyethyleneimines (PEI's). A common
polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are obtained by
reactions involving ammonia and ethylene dichloride, followed by fractional
distillation. The common PIrA's obtained are triethylenetetramine (TETA) and
teraethylenepentamine (TEPA). Above the gentamines, i.e., the hexamines,
heptamines, octamines and possibly nonamines, the cogenerically derived
mixture
does not appear to separate by distillation and can include other materials
such as
cyclic amines and particularly piperazines. There can also be present cyclic
amines
with side chains in which nitrogen atoms appear. See U.S. Patent 2,792,372,
Dickinson, issued May 14, 1957, which describes the preparation of PEA's.
Polyamines can be prepared, for example, by polymerizing ethyleneimine in
the presence of a catalyst such as carbon dioxide, sodium bisulfate, sulfuric
acid,
hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for
preparing these polyamine backbones are disclosed in U.S. Patent 2,182,306,
Ulrich
et al., issued December S, 1939; U.S. Patent 3,033,746, Mayle et al., issued
May 8,
1962; U.S. Patent 2,208,095, Esselmann et al., issued July 16, 1940; U.S.
Patent
2,806,839, Crowther, issued September 17, 1957; and U.S. Patent 2,553,696,
Wilson, issued May 21, 1951.
Additionally, certain alkoxylated (especially ethoxylated) quaternary
polyamine dispersants are useful herein as dispersants. The alkoxylated
quaternary
polyamine dispersants which can be used in the present invention are of the
general
formula:
A A A
Ri-N~ R N~ R N~ Rt (m + 2) X
A R~ m A
where R is selected from linear or branched C2-C12 alkylene, C3-C12
hydroxyalkylene, C4-C 12 dihydroxyaikylene, Cg-C I 2 dialkylarylene,
[(CH2CH2O)qCH2CH2]- and -CH2CH(OH)CH20-
CA 02273259 1999-OS-28
WO 98/28393 PCT/US9'7/22694
32
(CH2CH20)qCH2CH{OH)CH2]- where q is from about 1 to about 100. If present.
Each R1 is independently selected from C 1-C4 alkyl, C7-C 12 alkylaryl, or A.
R1
may be absent on some nitrogens; however, at least three nitrogens must be
quaternized.
A is of the formula:
(CH-CH2-O)nB
R3
where R3 is selected from H or C1-C3 alkyl, n is from about 5 to about 100 and
B is
selected from H, C 1-C4 alkyl, acetyl, or benzoyl; m is from about 0 to about
4, and
X is a water soluble anion.
In preferred embodiments, R is selected from C4 to Cg alkylene, R1 is
selected from C 1-C2 alkyl or C2-C3 hydroxyalkyl, and A is:
(CH-CH2-O)nH
R3
where R3 is selected from H or methyl, and n is from about 10 to about 50; and
m is
1.
In another preferred embodiment R is linear or branched C6, R1 is methyl,
R3 is H, and n is from about 20 to about 50, and m is 1.
The levels of these dispersants used can range from about 0.1 % to about
10%, typically from about 0.4% to about 5%, by weight. These dispersants can
be
synthesized following the methods outline in US. Patent No. 4,664,848, or
other
ways known to those skilled in the art.
Brightener - Any optical brighteners or other brightening or whitening agents
known in the art can be incorporated at levels typically from about 0.01 % to
about
1.2%, by weight, into the detergent compositions herein. Commercial optical
brighteners which may be useful in the present invention can be classified
into
subgroups, which include, but are not necessarily limited to, derivatives of
stilbene,
pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5-
dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous
agents. Examples of such brighteners are disclosed in "The Production and
Application of Fluorescent Brightening Agents", M. Zahradnik, Published by
John
Wiley & Sons, New York (1982).
Specific examples of optical brighteners which are useful in the present
compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on
CA 02273259 2003-08-27
33
TM
December 13. 1988. These brighteners include the PHORWHITE series of
brighteners from Verona. Other brighteners disclosed in this reference
include:
TinopalMUNPA, Tinopal CBS and Tinopal SBM; available from Ciba-Geigy; Artic
White~C 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 bxighteners include 4-methyl-7-
diethyl- amino coumarin; 1,2-bis(benzimidazol-2-yl)ethylene; 1,3-diphenyl-
pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho[1,2-dJoxazole;
and
2-(stilben-4-yl)-2H-naphtho[1,2-dJtriazole. See also U.S. Patent 3,646,015,
issued
February 29, 1972 to Hamilton.
Chelating AAgents - 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
ethylenediaminetetrace-tates, N-hydroxyethylethylenediaminetriacetates,
nitrilo-tri-
acetates, ethylenediamine tetrapro-prionates,
triethylenetetraaminehexacetates,
diethylenetriaminepentaacetates, and ethanoldi-glycines, alkali metal,
ammonium,
and substituted ammonium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as chelating agents in the
compositions of the invention when at lease low levels of total phosphorus are
permitted in detergent compositions, and include ethylenediaminetetrakis
TM
(methylenephosphonates) as DEQUES~f. Preferred, these amino phosphonates to
not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful in the
compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor
et
al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes
such as 1,2-dihydroxy-3,5-disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent
4,704,233, November 3, 1987, to Hartman and Perkins.
CA 02273259 2003-08-27
34
The compositions herein may also contain water-soluble methyl glycine
diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder.
Similarly, the
so called "weak" builders such as citrate can also be used as chelating
agents.
If utilized, these chelating agents will generally comprise from about 0.1 %
to
about IS% by weight of the detergent compositions herein. More preferably, if
utilized, the chelating agents will comprise from about 0.1% to about 3.0% by
weight of such compositions.
Composition pH
Dishwashing compositions of the invention will be subjected to acidic stresses
created by food soils when put to use, i.e., diluted and applied to soiled
dishes. If a
composition with a pH greater than 7 is to be more effective, it preferably
should
contain a buffering agent capable of providing a generally more alkaline pH in
the
composition and in dilute solutions, i.e., about 0.1 % to 0.4% by weight
aqueous
solution, of the composition. The pKa value of this buffering agent should be
about
0.5 to I.0 pH units below the desired pH value of the composition (determined
as
described above). Preferably, the pKa of the buffering agent should be from
about 7
to about 10. Under these conditions the buffering agent most effectively
controls the
pH while using the least amount thereof.
The buffering agent may be an active detergent in its own right, or it may be
a
low molecular weight, organic or inorganic material that is used in this
composition
solely for maintaining an alkaline pH. Preferred buffering agents for
compositions
of this invention are nitrogen-containing materials. Some examples are amino
acids
such as lysine or lower alcohol amines like mono-, di-, and tri-ethanolamine.
Other
preferred nitrogen-containing buffering agents are Tri(hydroxymethyl)amino
methane (HOCH2)3CNH3 (TRIS), 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-
methyl-propanol, 2-amino-2-methyl-1,3-propanol, disodium glutamate, N-methyl
diethanolamide, 1,3-diamino-propanol N,N'-tetra-methyl-1,3-diamino-2-propanol,
N,N-bis(2-hydroxyethyl)glycine (bicine) and N-tris (hydroxymethyl)methyl
glycine
(tricine). Mixtures of any of the above are also acceptable. Useful inorganic
buffers/alkalinity sources include the alkali metal carbonates and alkali
metal
phosphates, e.g., sodium carbonate, sodium polyphosphate. For additional
buffers
see McCutcheon's EMULSIFIERS AND DETERGENTS, North American Edition,
1997, McCutcheon Division, MC Publishing Company Kirk and WO 95/07971
The buffering agent, if used, is present in the compositions of the invention
herein at a level of from about 0.1 % to 15%, preferably from about 1 % to
10%, most
preferably from about 2% to 8%, by weight of the composition.
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WO 98/28393 PCT/US97/22694
Other I~,redients - A wide variety of other ingredients useful in detergent
compositions can be included in the compositions herein, including other
active
ingredients, carriers, hydrotropes, antioxidants, processing aids, dyes or
pigments,
solvents for liquid formulations, solid fillers for bar compositions, etc. If
high
sudsing is desired, suds boosters such as the C 10-C 16 alkanolamides can be
incorporated into the compositions, typically at 1 %-10% levels. The C 10-C 14
monoethanol and diethanol amides illustrate a typical class of such suds
boosters.
Use of such suds boosters with high sudsing adjunct surfactants such as the
amine
oxides, betaines and sultaines noted above is also advantageous.
An antioxidant can be optionally added to the detergent compositions of the
present invention. They can be any conventional antioxidant used in detergent
compositions, such as 2,6-di-tert-butyl-4-methylphenol (BHT), carbamate,
ascorbate, thiosulfate, monoethanolamine(MEA), dietahanolamine,
triethanolamine,
etc. It is preferred that the antioxidant, when present, be present in the
composition
from about 0.001 % to about 5% by weight.
Various detersive ingredients employed in the present compositions
optionally can be further stabilized by absorbing said ingredients onto a
porous
hydrophobic substrate, then coating said substrate with a hydrophobic coating.
Preferably, the detersive ingredient is admixed with a surfactant before being
absorbed into the porous substrate. In use, the detersive ingredient is
released from
the substrate into the aqueous washing liquor, where it performs its intended
detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica
(trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme
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
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
Garners. 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
CA 02273259 2003-08-27
36
about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1.3-
propanediol,
ethylene glycol, glycerine, and 1.2-propanediol) can also be used. The
compositions
may contain from 5% to 90%, typically 10% to 50% of such carriers.
An example of the procedure for making granules of the detergent
compositions herein is as follows: - Linear aklylbenzenesulfonate, sodium
tripolyphosphate, sodium silicate, sodium sulfate perfume, diamine and water
are
added to, heated and mixed via a crutcher. The resulting slurry is spray dried
into a
granular form.
An example of the procedure for making liquid detergent compositions
herein is as follows: - To the free water, citrate and MgCl2 are added and
dissolved.
To this solution amine oxide, betaine, ethanol, hydrotrope and nonionic
surfactant
are added. If free water isn't available, the MgCl2 and citrate are added to
the above
mix then stirred until dissolved. At this point, an acid is added to
neutralize the
formulation. It is preferred that the acid be chosen from organic acids such
as
malefic and citric, however, inorganic mineral acids may be employed as well.
In
preferred embdiments these acids are added to the formulation followed by
diamine
addition. AExS is added last. In formulations without Mg~'~' the procedure is
the
same.
Non-Aqueous Liquid Deterge,~s
The manufacture of liquid detergent compositions which comprise a non-
aqueous carrier medium can be prepared according to the disclosures of U.S.
Patents
4,753,570; 4,767,558; 4,772,413; 4,889,652; 4,892,673; GB-A-2,158,838; GB-A-
2,195,125; GB-A-2,195,649; U.S. 4,988,462; U.S. 5,266,233; EP-A-225,654
(6/16/87); EP-A-510,762 (10/28192); EP-A-540,089 (5/5/93); EP-A-540,090
(5/5/93); U.S. 4,615,820; EP-A-565,017 (10/13/93); EP-A-030,096 {6/10/81).
Such compositions can contain various particulate
detersive ingredients (e.g., bleaching agents, as disclosed hereinabove)
stabty
suspended therein. Such non-aqueous compositions thus comprise a LIQUID
PHASE and, optionally but preferably, a SOLID PHASE, all as described in more
detail hereinafter and in the cited references.
The compositions of this invention can be used to form aqueous washing
solutions for use hand dishwashing. Generally, an effective amount of such
compositions is added to water to form such aqueous cleaning or soaking
solutions.
The aqueous solution so formed is then contacted with the dishware, tableware,
and
cooking utensils.
An effective amount of the detergent compositions herein added to water to
form aqueous cleaning solutions can comprise amounts sufficient to form from
about
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WO 98/28393 PCT/US97/22694
J7
X00 to 20,000 ppm of composition in aqueous solution. More preferably, from
about
800 to 5,000 ppm of the detergent compositions herein will be provided in
aqueous
cleaning liquor.
The following examples are illustrative of the present invention. but are not
meant to limit or otherwise define its scope. All parts, percentages and
ratios used
herein are expressed as percent weight unless otherwise specified.
In the following Examples all levels are quoted as % by weight of the
composition.
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38
EXAMPLE I
The following e
liquid detergent
compositions
are mad
A B C
pH 10% 9 10 10
AS 0 28 25
AES 30 0 0
Amine Oxide 5 3 7
Betaine 3 0 1
Polyhydroxy 0 1.5 0
fatty
acid amide (C14)
Alnonionic 2 0 4
Diamine 1 5 7
Mg++ (as MgCl2)0.25 0 0
Citrate (cit2K3)0.25 0 0
Total (perfumes,(to
dye, water, 100%)
ethanol, etc.)
D E F
pH 10% 9.3 8.5 11
AES 0 15 10
Paraffin Sulfonate20 0 0
Linear Alkyl 5 15 12
Benzene Sulfonate
Betaine 3 1 0
Polyhydroxy 3 0 1
fatty
acid amide (C12)
AE nonionic 0 0 20
DTPA 0 0.2 0
Citrate (as 0.7 0 0
Cit2K3)
Diamine 1 5 7
Mg++ (as MgCl2)1 0 0
Ca++ (as CaXS)2)0 0.5 0
Protease 0.01 0 0.05
Amylase 0 0.05 0.05
Hydrotrope 2 1.5 3
Total (perfumes,(to
dye, water, 100%)
ethanol, etc.)
CA 02273259 2003-08-27
39
The degree of ethoxylation in the AES ranges from 0.6 to about 3.
The diamine is selected from: dimethyl aminopropyl amine; I ,6-hexane
diamine; l,3 propane diamine; 2-methyl 1,5 pentane diamine; 1,3-
pentanediamine;
1-methyl-diaminopropane.
The amylase is selected from: Termamyl~, Fungamyl~; Duramyl~; BAN~.
and the amylases as described in W095/26397.
The lipase is selected from: Amano-P; M1 Lipase~; Lipomax~; Lipolase~~
D96L - lipolytic enzyme variant of the native lipase derived from Humicola
lanuginosa as described in US Serial No. 08/341,826; and the Humicola
lanuginosa
strain DSM 4106.
The protease is selected from: Savinase~; Maxatase~; Maxacal~; Maxapem
IS~; subtilisin BPN and BPN'; Protease B; Protease A; Protease D; Primase~;
Durazym~; Opticlean~;and Optimase~; and Alcalase ~~
Hydrotropes are selected from sodium, potassium, ammonium or water-soluble
substituted ammonium salts of toluene sulfonic acid, naphthalene sulfonic
acid,
cumene sulfonic acid, xylene sulfonic acid.
DTPA is diethylenetriaminepentaacetate chelant.
EXAMPLE II
A B C D
pH 10% 8.5 9 9.0 9.0
AE0.6S 0 0 0 0
AE1S 0 30 0 0
AE1.4S 30 0 27 0
AE2.2S 0 0 0 15
Amine Oxide 5 5 5 3
Betaine 3 3 0 0
AE nonionic 2 2 2 2
Diamine 1 2 4 2
Mg++ (as MgCl2)0.25 0.25 0 0
Ca++ (as CaXS)2)0 0.4 0 0
Total (perfutries,(to 100%)
dye, water,
ethanol, etc.)
CA 02273259 2003-08-27
40
E F G H I J
pH 10% 9.3 8.5 11 10 9 9.2
AES 0 0 0 0 27 0
AES 0 1 ~ 10 27 0 20
Paraffin Sulfonate20 0 0 0 0 0
Linear Alkyl 5 15 12 0 0 0
Benzene Sulfonate
Betaine 3 1 0 2 2 0
Amine Oxide 0 0 0 2 5 7
Polyhydroxy 3 0 1 2 0 0
fatty
acid amide
(C12)
AE nonionic 0 0 20 1 0 2
Hydrotrope 0 0 0 0 0 S
Diamine 1 5 7 4 2 5
Mg++ (as MgCl2)1 0 0 0 0 0
Ca++ (as CaXS)2)0 0.5 0 0 0. I 0.1
Protease 0.1 0 0 0 0.06 0.1
Amylase 0 0.02 0 0.005 0 0.05
Lipase 0 0 0.025 0 0.05 0
DTPA 0 0.3 0 0 0.1 0.1
Citrate (Cit2K3)0.65 0 0 0.3 0 0
Total (perfumes,(to
dye, water, 100%)
ethanol, etc.)
The diamine is selected from: dimethyl aminopropyl amine; 1,6-hexane
diamine; 1,3 propane diamine; 2-methyl 1,5 pentane diamine; 1,3-
Pentanediamine;
1-methyl-diaminopropane.
The amylase is selected from: Termamyl~, Fungamyl~; Duramyl~; BAN~~
and the amylases as described in W095/26397.
The lipase is selected from: Amano-P; M1 Lipase~; Lipomax~; Lipolase~~
D96L - lipolytic enzyme variant of the native lipase derived from Humicola
lanuginosa and the Humicola lanuginosa
strain DSM 4106.
The protease is selected from: Savinase~; Maxatase~; Maxacal~; Maxapem
15~; subtilisin BPN and BPN'; Protease B; Protease A; Protease D; Primase~;
Durazym~; Opticlean~;and Optimase~; and Alcalase ~~
CA 02273259 1999-OS-28
WO 98/28393 PCT/LTS97/22694
41
Hydrotropes are selected from sodium, potassium. ammonium or water-soluble
substituted ammonium salts of toluene sulfonic acid. naphthalene sulfonic
acid,
cumene sulfonic acid, xylene sulfonic acid.
DTPA is diethylenetriaminepentaacetate chelant.
