Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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HYDROPHILIC INDEX FOR AQUEOUS, LIQUID LAUNDRY DETERGENT
COMPOSITIONS CONTAINING LAS
t0
TECH:1ICAL FIELD
The present invention relates to stable, aqueous heavy duty liquid laundry
detergent
compositions comprising linear alkyl benzene sulfonate and other surfactants,
and fatty acids.
The surfactant system is selected by calculating an optimal Hydrophilic Index,
which results in
l5 detergent compositions that provide superior cleaning benefits.
BACKGROUND OF THE INVENTION
The art is replete with examples of laundry detergent compositions that have
good cleaning
properties. Although many of these are liquids, the formulation of liquid
detergent compositions
?tl presrnt numerous problems to the formulator, including how to optimize the
surfactant system to
achirve optimal cleaning.
:lttempts to formulate liquid iaundn~ detergent compositions in the past have.
included.the
use of vanuus surfactants and combinations of surfactants. Formulators have
typically relied on
experimental methods for determining the optimal surfactant system. The
procedure of
2~ formulating various detergent compositions and testing the results is labor
intensive, expensive
and inexact. This problem is compounded by the large number a different
surfactants that are
available to detergent formulators.
Therefore. there is a continuing need for reliable and inexpensive methods to
formulate an
optimal surfactant system for use in a heavy duty liquid laundry detergent
composition. The
30 method should relieve the formulator of excessive experimentation with
various surfactant
combinations. h4oreover, the method should result in a surfactant system that
provides superior
cleaning benefits. The method should work for both structured and unstructured
aqueous, heavy
duty liquid detergent compositions. The compositions and methods of this
invention meet these
needs.
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SUMMARY OF THE INVENTION
The present invention encompasses a heavy duty liquid laundry detergent
compositions
comprising a surfactant system, wherein the surfactant system comprises from
about 0.1% to
about 20%, preferably from about 0.5% to about 19%, and more preferably from
about 1% to
about 18%, by weight of the surfactant system of an alkyl benzene sulfonate
surfactant. The
surfactant system has a Hydrophilic Index, HIC, of from about 8.0 to about
9.2, preferably from
about 8.2 to about 9.1, and more preferably from about 8.4 to about 9Ø The
Hydrophilic Index
can be calculated as follows:
HIC = ~y (weight % of surfactant y in the surfactant system) x (HISy).
HISy is calculated for each of the surfactants in the surfactant system as
follows:
HISy = 20 x (the molecular.weight of the hydrophilic portion of surfactant
component y)
/ (the molecular weight of surfactant component y).
Preferably the surfactant system comprises surfactants selected from the group
consisting of non-
soap anionic, nonionic, cationic, amphoteric, amine, poly hydroxy fatty acid
amines and mixtures
thereof, and the detergent composition preferably comprises no additional
surfactants beyond
those in the surfactant system. The surfactant system should comprise from 10%
to about 40%,
preferably from about 12% to about 35%, and most preferably from about 15% to
about 32%, by
weight of the composition.
The compositions of the present invention also preferably comprise specific
enzymes and
fatty acids. Specifically, the present heavy duty liquid laundry detergent
compositions preferably
comprise a detersive amount of an enzyme selected from the group consisting of
alkaline
protease, mannanase, a-amylase variants, and mixtures thereof, preferably the
enzyme is present
in an amount of from about 0.0001 % to about 1.5%, more preferably from about
0.00018% to
about 1.0%, and most preferably from about 0.00024% to about 0.5%, by weight
of the detergent
composition of the pure enzyme. And the present compositions preferably
further comprise from
about 5% to about 20% by weight of the composition of a fatty acid.
In addition to the essential surfactant system and the preferred enzymes and
fatty acids,
the detergent compositions of this invention preferably additionally comprise
adjunct ingredients
selected from the group consisting of non-citrate builders, optical
brighteners, soil release
polymers, dye transfer inhibitors, polymeric dispersing agents, additional
enzymes, suds
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suppressers, dyes, perfumes, colorants, filler salts, hydrotropes,
antiredeposition agents,
antifading agent, chelants, dye fixative agents, prill/fuzzing reducing
agents, and mixtures
thereof.
It has now been unexpectedly found that aqueous, heavy duty liquid detergent
compositions containing a surfactants system, which comprises linear alkyl
benzene sulfonate in
a specific range and has a Hydrophilic Index in a specific range, have
superior cleaning benefits
when compared to compositions having a Hydrophilic Index or linear alkyl
benzene sulfonate
outside the ranges claimed herein. Moreover, the Hydrophilic Index provides an
inexpensive,
quick and reliable method for formulators to optimize a surfactant system that
contains linear
alkyl benzene sulfonate and at least one other surfactant. The compositions
and methods defined
herein are applicable to both structured and unstructured aqueous, heavy duty
liquid detergent
compositions.
All percentages, ratios and proportions herein are by weight, unless otherwise
specified.
All temperatures are in degrees Celsius (o C) unless otherwise specified. All
documents cited
are in relevant part, incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the present invention, it has now been found that a stable,
aqueous
heavy duty liquid detergent composition is surprisingly formed when a
surfactant system is used
that comprises linear alkyl benzene sulfonate in a specific percentage of the
overall surfactant
system. The surfactant system should be selected to be within the Hydrophilic
Index of the
present claims. While the Hydrophilic Index is defined above, and exemplified
in the Example
section below, a more thorough background may be helpful for the formulator.
It is well known that surfactant molecules have a hydrophilic portion
(sometimes referred
to as the "head") and a hydrophobic portion (sometimes referred to as the
"tail"). The
Hydrophilic Index of the present invention is determined from the percent, by
weight, of each
surfactant that is hydrophilic. Those skilled in the art of detergent
formulation will know which
portions of a surfactant molecule are hydrophilic and which are hydrophobic.
And examples of
how to calculate this Index for some of the most common surfactants are given
in Example I
below.
The Hydrophilic Index for a surfactant molecule is referred to herein as HIS.
The
Hydrophilic Index for any given surfactant system can be summing the weight
averaged HIS for
each surfactant in the surfactant system. The weight averaged HIS can be
calculated by
multiplying the HIS of each surfactant in the system by the weight percent of
the surfactant
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relative to the surfactant system. The Hydrophilic Index for a surfactant
system is referred to
herein as HIC. Examples of the HIC calculation for compositions according to
the present
invention, and for comparative compositions outside of the present claims, can
be found in
Example II below.
Anionic Surfactants
The surfactant systems of the present invention comprise linear alkyl benzene
sulphonates and may also comprise other anionic surfactants such as, alkyl
sulfates, alkyl
polyethoxylate sulfates and mixtures thereof. The detergent compositions of
the present
invention may contain other non-soap anionic surfactants.
Generally speaking, anionic surfactants useful herein are disclosed in U.S.
Patent No.
4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent No.
3,919,678, Laughlin et al,
issued December 30, 1975, both incorporated herein by reference.
Useful anionic surfactants include the water-soluble salts, particularly the
alkali metal,
ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium)
salts,
of organic sulfuric reaction products having in their molecular structure an
alkyl group
containing from about 10 to about 20 carbon atoms and a sulfonic acid or
sulfuric acid ester
group. (Included in the term "alkyl" is the alkyl portion of aryl groups.)
Examples of this group
of synthetic surfactants are the alkyl sulfates, especially those obtained by
sulfating the higher
alcohols (Cg-C1 g carbon atoms) such as those produced by reducing the
glycerides of tallow or
coconut oil.
Other anionic surfactants herein are the water-soluble salts of alkyl phenol
ethylene oxide
ether sulfates containing from about 1 to about 4 units of ethylene oxide per
molecule and from
about 8 to about 12 carbon atoms in the alkyl group.
Other useful anionic surfactants herein include the water-soluble salts of
esters of a-
sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty
acid group and
from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-
acyloxy-alkane-1-
sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and
from about 9 to
about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin
sulfonates containing
from about 12 to 24 carbon atoms; and b-alkyloxy alkane sulfonates containing
from about 1 to 3
carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the
alkane moiety.
The alkyl polyethoxylate sulfates usefule herein are of the formula
RO(C2H40)xS03-M+
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wherein R is an alkyl chain having from about 10 to about 22 carbon atoms,
saturated or
unsaturated, M is a cation which makes the compound water-soluble, especially
an alkali metal,
ammonium or substituted ammonium cation, and x averages from about 0.5 to
about 15.
Preferred alkyl sulfate surfactants are the non-ethoxylated C12-15 Primary and
secondary
alkyl sulfates. Under cold water washing conditions, i.e., less than abut
65°F (18.3°C), it is
preferred that there be a mixture of such ethoxylated and non-ethoxylated
alkyl sulfates.
Nonionic Surfactants
Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent
3,929,678,
Laughlin et al., issued December 30, 1975, and U.S. Patent No. 4,285,841,
Barrat et al, issued
August 25, 1981. Exemplary, non-limiting classes of useful nonionic
surfactants include: Cg-
C 1 g alkyl ethoxylates ("AE"), with EO about 1-22, including the so-called
narrow peaked alkyl
ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and
mixed
ethoxy/propoxy), alkyl dialkyl amine oxide, alkanoyl glucose amide, and
mixtures thereof.
If nonionic surfactants are used, the compositions of the present invention
will preferably
contain up to about 10%, preferably from 0% to about 5%, more preferably from
0% to about
3%, by weight of an nonionic surfactant. Preferred are the ethoxylated
alcohols and ethoxylated
alkyl phenols of the formula R(OC2H4)nOH, wherein R is selected from the group
consisting of
aliphatic hydrocarbon radicals containing from about 8 to about 1 S carbon
atoms and alkyl
phenyl radicals in which the alkyl groups contain from about 8 to about 12
carbon atoms, and the
average value of n is from about 5 to about 15. 'These surfactants are more
fully described in
U.S. Patent No. 4,284,532, Leikhim et al, issued August 18, 1981. Particularly
preferred are
ethoxylated alcohols having an average of from about 10 to abut 15 carbon
atoms in the alcohol
and an average degree of ethoxylation of from about 6 to about 12 moles of
ethylene oxide per
mole of alcohol.
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
34 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.
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These compounds are commonly referred to as alkyl phenol alkoxylates, (e.g.,
alkyl phenol
ethoxylates).
The condensation products of aliphatic alcohols with from about 1 to about 25
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 I O 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 C11-C15 linear secondary
alcohol with 9
moles ethylene oxide), Tergitol~ 24-L-6 NMW (the condensation product of C 12-
C 14 Pri~rY
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 C14-
C15 linear
alcohol with 9 moles of ethylene oxide), Neodol~ 23-6.5 (the condensation
product of C12-C13
linear alcohol with 6.5 moles of ethylene oxide), Neodol~ 45-7 (the
condensation product of
CI4-CI5 linear alcohol with 7 moles of ethylene oxide), Neodol~ 45-4 (the
condensation
product of C 14-C I S linear alcohol with 4 moles of ethylene oxide), marketed
by Shell Chemical
Company, and Kyro~ EOB (the condensation product of C13-C15 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
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ethylene oxide to the extent that the condensation product contains from about
40% to about 80%
by weight of polyoxyethylene and has a molecular weight of from about 5,000 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 ~ s
( )x (R )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-C12 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
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intersaccharide bonds can be, e.g., between the one position of the additional
saccharide units
and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
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
1 S R20(CnH2n0)t(glYcosyl)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:
O
~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, dietha-
nolamides, and
isopropanolamides.
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Cationic and Ampl:oteric Surfactants
Non-quaternary, cationic detersive surfactants can also be included in
detergent
compositions of the present invention. Cationic surfactants useful herein are
described in U.S.
Patent 4,228,044, Cambre, issued October 14, 1980.
S 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 C12 -CIg alkyl
ethoxylates ("AE")
including the so-called narrow peaked alkyl ethoxylates and C6-CI2 alkyl
phenol alkoxylates
(especially ethoxylates and mixed ethoxy/propoxy), C12-CIg betaines and
sulfobetaines
("sultaines"), C 10-C I g amine oxides, and mixtures thereof.
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Polyl:ydroxy Fatty Acid Amide Surfactant
The detergent compositions hereof may also contain polyhydroxy fatty acid
amide
surfactant. The polyhydroxy fatty acid amide surfactant component comprises
compounds of the
structural formula:
O Rt
R2-C-~ -
wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a
mixture thereof,
preferably C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1
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 15 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.
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
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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, each of which is incorporated herein by reference.
Amine Surfactants
Suitable amine surfactants for use herein include detersive amines according
to the
formula:
R3
R~-X-(CH2)~
I
Ra
wherein R1 is a C6-C12 alkyl group; n is from about 2 to about 4, X is a
bridging group which is
selected from NH, CONH, COO, or O or X can be absent; and R3 and R4 are
individually
selected from H, C1-C4 alkyl, or (CH2-CH2-O(RS)) wherein RS is H or methyl.
Preferred amines include the following:
R 1-(CH2)2-NH2
R1-O-(CH2)3-NH2
R1-C(O)-NH-(CH2)3-IV(CH3)2
H2CH(OH)Rs
R' I
CH2CH(OH)Rs
wherein R1 is a C6-C12 alkyl group and RS is H or CH3.
In a highly preferred embodiment, the amine is described by the formula:
R1-C(O)-NH-(CH2)3-N(CH3)2
wherein R1 is Cg-C12 alkyl.
Particularly preferred amines include those selected from the group consisting
of octyl
amine, hexyl amine, decyl amine, dodecyl amine, Cg-C12 bis(hydroxyethyl)amine,
Cg-C12
bis(hydroxyisopropyl)amine, and Cg-C12 amido-propyl dimethyl amine, and
mixtures.
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If utilized the detersive amines comprise from about 0.1 % to about 10%,
preferably from
about 0.5% to about 5%, by weight of the composition.
Quaternary Ammonium Surfactants
From about 1% to about 6% of a quaternary ammonium surfactant having the
formula
~ R1
a
N X
/ \
R3 R2
wherein R1 and R2 are individually selected from the group consisting of C1-C4
alkyl, C1-C4
hydroxy alkyl, benzyl, and -(C2H40)xH where x has a value from about 2 to
about 5; X is an
anion; and (1) R3 and R4 are each a C6-C14 alkyl or (2) R3 is a C6-Clg alkyl,
and R4 is selected
from the group consisting of C 1-C 10 alkyl, C 1-C 10 hydroxy alkyl, benzyl,
and -(C2H40)xH
where x has a value from 2 to 5;
Preferred quaternary ammonium surfactants are the chloride, bromide, and
methylsulfate
salts. Examples of preferred mono-long chain alkyl quaternary ammonium
surfactants are those
wherein R1, R2, and R4 are each methyl and R3 is a Cg-C16 alkyl; or wherein R3
is Cg-lg alkyl
and R1, R2, and R4 are selected from methyl and hydroxy-alkyl moieties. Lauryl
trimethyl
ammonium chloride, myristyl trimethyl ammonium chloride, palmityl trimethyl
ammonium
chloride, coconut Mmethylammonium chloride, coconut trimethylammonium
methylsulfate,
coconut dimethyl-monohydroxyethyl-ammonium chloride, coconut dimethyl-
monohydroxyethylammonium methylsulfate, steryl dimethyl-monohydroxy-
ethylammonium
chloride, steryl dimethylmonohydroxy-ethylammonium methylsulfate, di- C 12-C
14 alkyl
dimethyl ammonium chloride, and mixtures thereof are particularly preferred.
ADOGEN 412T"',
a lauryl trimethyl ammonium chloride commercially available from Witco, is
also preferred.
Even more highly preferred are the lauryl trimethyl ammonium chloride and
myristyl trimethyl
ammonium chloride.
Alkoxylated quaternary ammonium (AQA) surfactants useful in the present
invention are
of the general formula:
R\ /ApRa
\N+~ ~ X
R3
R
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R~ /APR3
N+ X_
R2~ ~A~qRa
11
wherein RI is an alkyl or alkenyl moiety containing from about 8 to about 18
carbon atoms,
preferably 10 to about 16 carbon atoms, most preferably from about 10 to about
14 carbon atoms;
R2 and R3~ are each independently alkyl groups containing from one to about
three carbon atoms,
preferably methyl; R3 and R4 can vary independently and are selected from
hydrogen
(preferred), methyl and ethyl, X- is an anion such as chloride, bromide,
methylsulfate, sulfate, or
the like, to provide electrical neutrality; A is selected from CI-C4 aikoxy,
especially ethoxy (i.e.,
-CH2CH20-), propoxy, butoxy and mixtures thereof; and for formula I, p is from
2 to about 30,
preferably 2 to about 15, most preferably 2 to about 8; and for formula II, p
is from I to about 30,
preferably 1 to about 4 and q is from 1 to about 30, preferably I to about 4,
and most preferably
both p and q are 1.
Other quaternary surfactants include the ammonium surfactants such as
alkyldimethylammonium halogenides, and those surfactants having the formula:
[R2(OR3)y~ [R4(OR3)y)2RS~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 CI-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; RS is
the same as R4 or is an alkyl chain wherein the total number of carbon atoms
of R2 plus RS 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.
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Non Surfactant Components
Fatty Acids
For the purposes of calculating the Hydrophilic Index of this invention, fatty
acids are
not considered a surfactant. Fatty acids are, however, preferred for use in
the present
compositions. Especially preferred is rapeseed fatty acid. Other suitable
fatty acids include
saturated and/or unsaturated fatty acids obtained from natural sources or
synthetically prepared.
Examples of fatty acids include capric, lauric, myristic, palmitic, stearic,
arachidic, and behenic
acid. Other fatty acids include palmitoleic, oleic, linoleic, linolenic, and
ricinoleic acid. The
fatty acid is preferably present at from about 2% to about 15% by weight of
the composition.
Electrolytes
Without being limited by theory, it is believed that the presence of
electrolytes acts to
control the viscosity of the liquid compositions. Thus, the liquid nature of
the compositions
herein are affected by the choice of surfactants and by the amount of
electrolytes present. In
preferred embodiments herein, the compositions will further comprise from 0%
to about 10%,
more preferably from about 2% to about 6%, even more preferably from about 3%
to about 5%,
of a suitable electrolyte or acid equivalent thereof. Sodium citrate is a
highly preferred
electrolyte for use herein.
The compositions herein may optionally contain from about 0% to about 10%, by
weight,
of solvents and hydrotropes. Without being limited by theory, it is believed
that the presence of
solvents and hydrotropes can affect the structured versus isotropic nature of
the compositions;
By "solvent" is meant the commonly used solvents in the detergent industry,
including alkyl
monoalcohol, di-, and tri-alcohols, ethylene glycol, propylene glycol,
propanediol, ethanediol,
glycerine, etc. By "hydrotrope" is meant the commonly used hydrotropes in the
detergent
industry, including short chain surfactants that help solubilize other
surfactants. Other examples
of hydrotropes include cumene, xylene, or toluene sulfonate, urea, Cg or
shorter chain alkyl
carboxylates, and Cg or shorter chain alkyl sulfate and ethoxylated sulfates.
Modified polyamine
The compositions herein may comprise at least about 0.05%, preferably from
about
0.05% to about 3%, by weight, of a water-soluble or dispersible, modified
polyamine agent, said
agent comprising a polyamine backbone corresponding to the formula:
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B RZ ~2)2
UR2)2 Nlw fR'-~JX LR'-~Jy LR'-~JZ
wherein each R1 is independently C2-CS alkylene, alkenylene or arylene; each
R2 is
independently H, or a moiety of formula OH[(CH2)x0]n, wherein x is from about
1 to about 8
and n is from about 10 to about 50; w is 0 or I; x+y+z is from about 5 to
about 30; and B
represents a continuation of this structure by branching; and wherein said
polyamine before
alkylation has an average molecular weight of from about 300 to about 1,200.
In preferred embodiments, R1 is C2-C4 alkylene, more preferably ethylene; R2
is
OH[CH2CH20]n, wherein n is from about 15 to about 30, more preferably n is
about 20. The
average Molecular Weight of the polyamine before alkylation is from about 300
to about 1200,
more preferably from about 500 to about 900, still more preferably from about
600 to about 700,
even more preferably from about 600 to about 650.
In another preferred embodiment, R1 is C2-C4 alkylene, more preferably
ethylene; R2 is
OH[CH2CH20]n, wherein n is from about 10 to about 20, more preferably n is
about 1 S. The
average Molecular Weight of the polyamine before alkylation is from about 100
to about 300,
I S more preferably from about 150 to about 250, even more preferably from
about 180 to about 200.
Polyamide-Polyaneines
The liquid compositions of the present invention preferably comprise from
about 0.1 % to
8% by the weight of the composition of certain polyamide-polyamines. More
preferably, such
polyamide-polyamine materials will comprise from about 0.5% to 4% by weight of
the
compositions herein. Most preferably, these polyamide-polyamines will comprise
from about
1% to 3% by weight of the composition.
The polyamide-polyamine materials used in this invention are those which have
repeating,
substituted amido-amine units which correspond to the general Structural
Formula No. I as
follows:
O O R+
~-C-R1-C-NH-R2-N-R;-NH~-
Structural Formula No. I
In Structural Formula No. I, R1, R2 and RS are each independently CIA,
alkylene, C1~
alkarylene or arylene. It is also possible to eliminate R1 entirely so that
the polyamide-
polyamine is derived from oxalic acid.
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Also in Structural Formula No. I, R3 is H, epichlorohydrin, an azetidinium
group, an
epoxypropyl group or a dimethylaminohydroxypropyl group, and R4 can be H, C 1
~ alkyl, C 1 ~
alkaryl, or aryl. R4 may also be any of the foregoing groups condensed with C
l.,q alkylene
oxide.
R1 is preferably butylene, and R2 and RS are preferably ethylene. R3 is
preferably
epichlorohydrin. R4 is preferably H.
'The polyamide-polyamine materials useful herein can be prepared by reacting
polyamines
such as diethylenetriamine, triethylenetetraarnine, tetraethylenepentamine or
dipropylenetriamine
with C2-C12 dicarboxylic acids such as oxalic, succinic, glutaric, adipic and
diglycolic acids.
Such materials may then be further derivatized by reaction with, for example,
epichlorohydrin.
Preparation of such materials is described in greater detail in Keim, U.S.
Patent 2,296,116, Issued
February 23, 1960; Keim, U.S. Patent 2,296,154, Issued February 23, 1960 and
Keim, U.S.
Patent 3,332,901, Issued July 25, 1967.
The polyamide-polyamine agents preferred for use herein are commercially
marketed by
Hercules, Inc. under the tradename Kymene~ . Especially useful are Kymene
557H~ and
Kymene 557LX~ which are epichlorohydrin adducts of polyamide-polyamines which
are the
reaction products of diethylenetriamine and adipic acid. Other suitable
materials are those
marketed by Hercules under the tradenames Reten~ and Delsette~~ and by Sandoz
under the
tradename Cartaretin~~ These polyamide-polyamine materials are marketed in the
form of
aqueous suspensions of the polymeric material containing, for example, about
12.5% by weight
of solids.
Polyetl:oxylated Polyamine Polymers
Another polymer dispersant form use herein includes polyethoxyated-polyamine
polymers (PPP). The preferred polyethoxylated-polyamines useful herein are
generally
polyalkyleneamines (FAA'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 PEA's obtained are triethylenetetramine
(TETA) and
teraethylenepentamine (TEPA). Above the pentamines, i.e., the hexamines,
heptamines,
octamines and possibly nonamines, the cogenerically derived mixture does not
appear to separate
by distillation and can include other materials such as cyclic amines and
particularly piperazines.
There can also be present cyclic amines with side chains in which nitrogen
atoms appear. See
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U.S. Patent 2,792,372, Dickinson, issued May 14, 1957, which describes the
preparation of
PEA's.
Polyethoxylated polyamines can be prepared, for example, by polymerizing
ethyleneimine
in the presence of a catalyst such as carbon dioxide, sodium bisulfate,
sulfuric acid, hydrogen
peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing
these polyamine
backbones are disclosed in U.S. Patent 2,182,306, Ulrich et al., issued
December 5, 1939; U.S.
Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent 2,208,095,
Esselmann et al.,
issued July 16, 1940; U.S. Patent 2,806,839, Crowther, issued September 17,
1957; and U.S.
Patent 2,553,696, Wilson, issued May 21, 1951
Optionally, but preferred polyethoxyated-polyamine polymers useful for this
invention are
alkoxylated quaternary diamines of the general formula:
A A
Ri-NO I~-N~ R~ 2X0
A
where R is selected from linear or branched C2-C12 alkylene, C3-C12
hydroxyalkylene, C4-C12
dihydroxyalkylene, Cg-C 12 dialkylarylene, [(CH2CH20)qCH2CH2]- and -
CH2CH(OH)CH20-
(CH2CH20)qCH2CH(OH)CH2]- where q is from about 1 to about 100. Each Rl is
independently selected from C1-C4 alkyl, C7-C12 alkylaryl, or A. A is of the
formula:
(CH-CH2-O)nB
R3
where R3 is selected from H or C1-C3 alkyl, n is from about S to about 100,
and B is selected
from H, C1-C4 alkyl, acetyl, or benzoyl; X is a water soluble anion.
In preferred embodiments, R is selected from C4 to Cg alkylene, Rl is selected
from C1-
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 S0.
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.
Additional alkoxyIated quaternary polyamine dispersants which can be used in
the present
invention are of the general formula:
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A A A
RI-N~ R N~ R N~ R1 (m + 2) X~
A R~ m A
where R is selected from linear or branched C2-C12 alkylene, C3-C12
hydroxyalkylene, C4-C12
dihydroxyalkylene, Cg-C12 dialkylarylene, [(CH2CH20)qCH2CH2]- and -
CH2CH(OH)CH20-
(CH2CH20)qCH2CH(OH)CH2]- where q is from about 1 to about 100. If present,
Each Rl is
independently selected from C1-C4 alkyl, C~-C12 alkylaryl, or A. Rl 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 Cl-C3 alkyl, n is from about 5 to about 100 and
B is selected
from H, C1-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 C1-
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 polyethoxyated-polyamine polymers used can range from
about 0.1% to
about 10%, typically from about 0.4% to about 5%, by weight. These
polyethoxyated-polyamine
polymers can be synthesized following the methods outline in U.S. Patent No.
4,664,848, or
other ways known to those skilled in the art.
Enzymes
Suitable enzymes include proteases, amylases, lipases, cellulases,
peroxidases, and
mixtures thereof of any suitable origin, such as vegetable, animal, bacterial,
fungal and yeast
origin. Preferred selections are influenced by factors such as pH-activity
and/or stability optima,
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thermostability, and stability to active bleach, detergents, builders and the
like. In this respect
bacterial or fungal enzymes are preferred, such as bacterial amylases and
proteases, and fungal
cellulases.
Enzymes are normally incorporated into detergent or detergent additive
compositions at
levels sufficient to provide a "cleaning-effective amount". The term "cleaning
effective amount"
refers to any amount capable of producing a cleaning, stain removal, soil
removal, whitening,
deodorizing, or freshness improving effect on substrates such as dishware and
the like.
"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain
removing or
otherwise beneficial effect in a laundry, hard surface cleaning or personal
care detergent
composition.
In practical terms for current commercial preparations, the compositions
herein may
preferably the enzyme is present in an amount of from about 0.0001% to about
1.5%, more
preferably from about 0.00018% to about 1.0%, and most preferably from about
0.00024% to
about 0.5%, by weight of the detergent composition of the pure enzyme.
Protease enzymes are
usually present in such commercial preparations at levels sufficient to
provide from 0.005 to 0.1
Anson units (AU) of activity per gram of composition.
A range of enzyme materials and means for their incorporation into synthetic
detergent
compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor
International,
WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al.
Enzymes are
further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S.
4,507,219, Hughes,
March 26, 1985. Enzyme materials useful for liquid detergent formulations, and
their
incorporation into such formulations, are disclosed in U.S. 4,261,868, Hora et
al, April 14, 1981.
Enzymes for use in detergents can be stabilized by various techniques. Enzyme
stabilization
techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971,
Gedge et al, EP
199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization
systems are also
described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving
proteases,
xylanases and cellulases, is described in WO 9401532 A to Novo.
i) Mannanase
A preferred element of the detergent compositions of the present invention is
a
mannanase enzyme. Encompassed in the present invention are the following three
mannans-
degrading enzymes : EC 3.2.1.25 : (3-mannosidase, EC 3.2.1.78 : Endo-1,4-(3-
mannosidase,
referred therein after as "mannanase" and EC 3.2.1.100 : 1,4-(3-mannobiosidase
(IIJPAC
Classification- Enzyme nomenclature, 1992 ISBN 0-12-227165-3 Academic Press).
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More preferably, the detergent compositions of the present invention comprise
a ~3-1,4-
Mannosidase (E.C. 3.2.1.78) referred to as Mannanase. The term "mannanase" or
"galactomannanase" denotes a mannanase enzyme defined according to the art as
officially being
named mannan endo-1,4-beta-mannosidase and having the alternative names beta-
mannanase and
endo-1,4-mannanase and catalysing the reaction: random hydrolysis of 1,4-beta-
D- mannosidic
linkages in mannans, galactomannans, glucomannans, and galactoglucomannans.
In particular, Mannanases (EC 3.2.1.78) constitute a group of polysaccharases
which
degrade mannans and denote enzymes which are capable of cleaving polyose
chains contaning
mannose units, i.e. are capable of cleaving glycosidic bonds in mannans,
glucomannans,
galactomannans and galactogluco-mannans. Mannans are polysaccharides having a
backbone
composed of (i-1,4- linked mannose; glucomannans are polysaccharides having a
backbone or
more or less regularly alternating ~3-1,4 linked mannose and glucose;
galactomannans and
galactoglucomannans are mannans and glucomannans with a-1,6 linked galactose
sidebranches.
These compounds may be acetylated.
1 S The degradation of galactomannans and galactoglucomannans is facilitated
by full or
partial removal of the galactose sidebranches. Further the degradation of the
acetylated mannans,
glucomannans, galactomannans and galactogluco-mannans is facilitated by full
or partial
deacetylation. Acetyl groups can be removed by alkali or by mannan
acetylesterases. The
oligomers which are released from the mannanases or by a combination of
mannanases and a-
galactosidase and/or mannan acetyl esterases can be further degraded to
release free maltose by
~i-mannosidase and/or ~3-glucosidase.
Mannanases have been identified in several Bacillus organisms. For example,
Talbot et
al., Appl. Environ. Microbiol., Vo1.56, No. 11, pp. 3505-3510 (1990) describes
a beta-mannanase
derived from Bacillus stearothermophilus in dimer form having molecular weight
of 162 kDa and
an optimum pH of 5.5-7.5. Mendoza et al., World J. Microbiol. Biotech., Vol.
10, No. 5, pp. 551-
555 ( 1994) describes a beta-mannanase derived from Bacillus subtilis having a
molecular weight
of 38 kDa, an optimum activity at pH 5.0 and SSC and a pI of 4.8. JP-03047076
discloses a beta-
mannanase derived from Bacillus sp., having a molecular weight of 373 kDa
measured by gel
filtration, an optimum pH of 8-10 and a pI of 5.3-5.4. JP-63056289 describes
the production of an
alkaline, thermostable beta-mannanase which hydrolyses beta-1,4-D-
mannopyranoside bonds of
e.g. mannans and produces manno-oligosaccharides. JP-63036774 relates to the
Bacillus
microorganism FERM P-8856 which produces beta-mannanase and beta-mannosidase
at an
alkaline pH. JP-08051975 discloses alkaline beta-mannanases from alkalophilic
Bacillus sp. AM-
001. A purified mannanase from Bacillus amyloliquefaciens useful in the
bleaching of pulp and
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paper and a method of preparation thereof is disclosed in WO 97/11164. WO
91/18974 describes
a hemicellulase such as a glucanase, xylanase or mannanase active at an
extreme pH and
temperature. WO 94/25576 discloses an enzyme from Aspergillus aculeatus, CBS
101.43,
exhibiting mannanase activity which may be useful for degradation or
modification of plant or
algae cell wall material. WO 93/24622 discloses a mannanase isolated from
Trichoderma reseei
useful for bleaching lignocellulosic pulps. An hemicellulase capable of
degrading mannan-
containing hemicellulose is described in W091/18974 and a purified mannanase
from Bacillus
amyloliguefaciens is described in W097/11164.
Preferably, the mannanase enzyme will be an alkaline mannanase as defined
below, more
preferably, a mannanase originating from a bacterial source. Especially, the
laundry detergent
composition of the present invention will comprise an alkaline mannanase
selected from the
mannanase from the strain Bacillus agaradherens NICMB 40482; the mannanase
from Bacillus
subtilises strain 168, gene yght; the mannanase from Bacillus sp. I633 and/or
the mannanase from
Bacillus sp. AAI12. Most preferred mannanase for the inclusion in the
detergent compositions of
the present invention is the mannanase enzyme originating from Bacillus sp.
I633 as described in
the co-pending application No. PA 1998 01340.
The terms "alkaline mannanase enzyme" is meant to encompass an enzyme having
an
enzymatic activity of at least 10%, preferably at least 25%, more preferably
at least 40% of its
maximum activity at a given pH ranging from 7 to 12, preferably 7.5 to 10.5.
The alkaline mannanase from Bacillus agaradherens NICMB 40482 is described in
the
co-pending U.S. patent application serial No. 09/111,256. More specifically,
this mannanase is:
i) a polypeptide produced by Bacillus agaradherens, NCIMB 40482; or
ii) a polypeptide comprising an amino acid sequence as shown in positions 32-
343
of SEQ 1D N0:2 as shown in U.S. patent application serial No. 09/111,256; or
iii) an analogue of the polypeptide defined in i) or ii) which is at least 70%
homologous with said polypeptide, or is derived from said polypeptide by
substitution, deletion or addition of one or several amino acids, or is
immunologically reactive with a polyclonal antibody raised against said
polypeptide in purified form.
Also encompassed is the corresponding isolated polypeptide having mannanase
activity selected
from the group consisting of:
(a) polynucleotide molecules encoding a polypeptide having mannanase activity
and
comprising a sequence of nucleotides as shown in SEQ 1D NO: 1 from
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nucleotide 97 to nucleotide 1029 as shown in U.S. patent application serial
No.
09/111,256;
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having mannanase
activity
that is at least 70% identical to the amino acid sequence of SEQ ID NO: 2 from
amino acid residue 32 to amino acid residue 343 as shown in U.S. patent
application serial No. 09/111,256;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d).
The plasmid pSJ1678 comprising the polynucleotide molecule (the DNA sequence)
encoding said mannanase has been transformed into a strain of the Escherichia
coli which was
deposited by the inventors according to the Budapest Treaty on the
International Recognition of
the Deposit of Microorganisms for the Purposes of Patent Procedure at the
Deutsche Sammlung
von MilQOOrganismen and Zellkulturen GmbH, Mascheroder Weg lb, D-38124
Braunschweig,
1 S Federal Republic of Germany, on 18 May 1998 under the deposition number
DSM 12180.
A second more preferred enzyme is the mannanase from the Bacillus subtilis
strain 168,
which is described in the co-pending U.S. patent application serial No.
09/095,163. More
specifically, this mannanase is:
i) is encoded by the coding part of the DNA sequence shown in SED ID No. S
shown in the U.S. patent application serial No. 09/095,163 or an analogue of
said
sequence; and/or
ii) a polypeptide comprising an amino acid sequence as shown SEQ )D N0:6 shown
in the U.S. patent application serial No. 09/095,163; or
iii) an analogue of the polypeptide defined in ii) which is at least 70%
homologous
with said polypeptide, or is derived from said polypeptide by substitution,
deletion or addition of one or several amino acids, or is immunologically
reactive
with a polyclonal antibody raised against said polypeptide in purified form.
Also encompassed in the corresponding isolated polypeptide having mannanase
activity selected
from the group consisting of:
(a) polynucleotide molecules encoding a polypeptide having mannanase activity
and
comprising a sequence of nucleotides as shown in SEQ )D NO:S as shown in the
U.S. patent application serial No. 09/095,163
(b) species homologs of (a);
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(c) polynucleotide molecules that encode a polypeptide having mannanase
activity
that is at least 70% identical to the amino acid sequence of SEQ m NO: 6 as
shown in the U.S. patent application serial No. 09/095,163;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d).
A third more preferred mannanase is described in the co-pending Danish patent
application No. PA 1998 01340. More specifically, this mannanase is:
i) a polypeptide produced by Bacillus sp. I633;
ii) a polypeptide comprising an amino acid sequence as shown in positions 33-
340
of SEQ ID N0:2 as shown in the Danish application No. PA 1998 01340; or
iii) an analogue of the polypeptide defined in i) or ii) which is at least 65%
homologous with said polypeptide, is derived from said polypeptide by
substitution, deletion or addition of one or several amino acids, or is
immunologically reactive with a polyclonal antibody raised against said
1 S polypeptide in purified form.
Also encompassed is the corresponding isolated polynucleotide molecule
selected from the group
consisting of
(a) polynucleotide molecules encoding a polypeptide having mannanase activity
and
comprising a sequence of nucleotides as shown in SEQ 1D NO: I from
nucleotide 317 to nucleotide 1243 the Danish application No. PA 1998 01340;
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having mannanase
activity
that is at least 65% identical to the amino acid sequence of SEQ 1D NO: 2 from
amino acid residue 33 to amino acid residue 340 the Danish application No. PA
1998 01340;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d).
The plasmid pBXM3 comprising the polynucleotide molecule (the DNA sequence)
encoding a mannanase of the present invention has been transformed into a
strain of the
Escherichia coli which was deposited by the inventors according to the
Budapest Treaty on the
International Recognition of the Deposit of Microorganisms for the Purposes of
Patent Procedure
at the Deutsche Sammlung von Mikroorganismen and Zellkulturen GmbH,
Mascheroder Weg lb,
D-38124 Braunschweig, Federal Republic of Germany, on 29 May 1998 under the
deposition
number DSM 12197.
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A fourth more preferred mannanase is described in the Danish co-pending patent
application No. PA 1998 01341. More specifically, this mannanase is:
i} a polypeptide produced by Bacillus sp. AAI 12;
ii) a polypeptide comprising an amino acid sequence as shown in positions 25-
362 of
SEQ 1D N0:2as shown in the Danish application No. PA 1998 01341; or
iii) an analogue of the polypeptide defined in i) or ii) which is at least 65%
homologous with said polypeptide, is derived from said polypeptide by
substitution, deletion or addition of one or several amino acids, or is
immunologically reactive with a polyclonal antibody raised against said
polypeptide in purified form.
Also encompassed is the corresponding isolated polynucleotide molecule
selected from the group
consisting of
(a) polynucleotide molecules encoding a polypeptide having mannanase activity
and
comprising a sequence of nucleotides as shown in SEQ 1D NO: 1 from
nucleotide 225 to nucleotide 1236 as shown in the Danish application No. PA
1998 01341;
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having mannanase
activity
that is at least 65% identical to the amino acid sequence of SEQ 1D NO: 2 from
amino acid residue 25 to amino acid residue 362 as shown in the Danish
application No. PA 1998 01341;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b}, (c) or (d).
The plasmid pBXMI comprising the polynucleotide molecule (the DNA sequence)
encoding a mannanase of the present invention has been transformed into a
strain of the
Escherichia coli which was deposited by the inventors according to the
Budapest Treaty on the
International Recognition of the Deposit of Microorganisms for the Purposes of
Patent Procedure
at the Deutsche Sammlung von Mikroorganismen and Zellkulturen GmbH,
Mascheroder Weg lb,
D-38124 Braunschweig, Federal Republic of Germany, on 7 October 1998 under the
deposition
number DSM 12433.
ii) Amylase Variants
The amylase variants used in the present invention include, but are not
limited to, the
amylase enzymes described in WO 95/26397 and in WO 96/23873 (Novo). These
enzymes are
CA 02347695 2001-04-24
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incorporated into cleaning compositions at a level of from about 0.0001%,
preferably from about
O.OOOI8%, more preferably from about 0.00024%, most preferably from about
O.OS% to about
0.1%, preferably to about 0.060%, more preferably to about 0.048% by weight of
the cleaning
compositions of pure enzyme.
S The amylase variants are preferably selected from the group consisting of a-
amylase
variants. Suitable a-amylase variants for use in the present invention
include, but are not limited
to the following a-amylases:
(i) a-amylase characterized by having a specific activity at least 2S% higher
than the
specific activity of Termamyl~ at a temperature range of 2S°C to
SS°C and at a
pH value in the range of 8 to 10, measured by Phadebas~ a-amylase activity
assay; and/or
(ii) a-amylase according to (i) comprising the amino acid sequence shown in
SEQ )D
No. 1 or an a-amylase being at least 80% homologous with the amino acid
sequence shown in SEQ >D No. 1; and/or
(iii) a-amylase according to (i) comprising the amino acid sequence shown in
SEQ
)D No. 2 or an a-amylase being at least 80% homologous with the amino acid
sequence shown in SEQ 1D No. 2; and/or
(iv) a-amylase according to (i) comprising the following amino acid sequence N-
terminal: His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-
Tyr-Leu-Pro-Asn-Asp (SEQ >D No. 3) or an a-amylase being at least 80%
homologous with the amino acid sequence shown (SEQ 1D No. 3) in the N-
terminal; and/or
(v) a-amylase according to (i-iv) wherein the a-amylase is obtainable from an
alkalophilic Bacillus species; and/or
2S (vi) a-amylase according to (v) wherein the amylase is obtainable from any
of the
strains NCIB 12289, NCIB 12S 12, NCIB 12S 13 and DSM 935; and/or
(vii) a-amylase showing positive immunological cross-reactivity with
antibodies
raised against an a-amylase having an amino acid sequence corresponding
respectively to SEQ m No. 1,1D No. 2, or ID No. 3; and/or
(viii) variant of a parent a-amylase, wherein the parent a-amylase (1) has one
of the
amino acid sequences shown in SEQ 1D No. 1,1D No. 2, or m No. 4,
respectively, or (2) displays at least 80% homology with one or more of said
amino acid sequences, and/or displays immunological cross-reactivity with an
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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 sequences,
in which variants: (A) at least one amino acid residue of said parent a-
amylase
has been deleted; and/or (B) at least one amino acid residue of said parent a-
amylase has been replaced by a different amino acid residue; and/or (C) 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 (pn so as to better match the pI value for a-
amylase variant to the pH of the medium.
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%.
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 a host organism
transformed with
the DNA sequence.
iii) Protease
Suitable examples of proteases are the subtilisins which are obtained from
particular
strains of B. subtilis and B. licheniformis. One suitable protease is obtained
from a strain of
Bacillus, having maximum activity throughout the pH range of 8-12, developed
and sold as
ESPERASE~ by Novo Industries A/S of Denmark, hereinafter "Novo". The
preparation of this
enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other
suitable proteases
include ALCALASE~ and SAVINASE~ from Novo and MAXATASE~ from International
Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in
EP 130,756 A,
January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987
and EP 130,756 A,
January 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338
described in WO
9318140 A to Novo. Enzymatic detergents comprising protease, one or more other
enzymes, and
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a reversible protease inhibitor are described in WO 9203529 A to Novo. Other
preferred
proteases include those of WO 9510591 A to Procter & Gamble. When desired, a
protease
having decreased adsorption and increased hydrolysis is available as described
in WO 9507791
to Procter & Gamble. A recombinant trypsin-like protease for detergents
suitable herein is
described in WO 9425583 to Novo.
In more detail, an especially preferred protease, referred to as "Protease D"
is a carbonyl
hydrolase variant having an amino acid sequence not found in nature, which is
derived from a
precursor carbonyl hydrolase by substituting a different amino acid for a
plurality of amino acid
residues at a position in said carbonyl hydrolase equivalent to position +76,
preferably also in
combination with one or more amino acid residue positions equivalent to those
selected from the
group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126,
+128, +135,
+156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265,
and/or +274
according to the numbering of Bacillus amyloliguefaciens subtilisin, as
described in the patent
applications of A. Baeck, et al, entitled "Protease-Containing Cleaning
Compositions" having US
Serial No. 08/322,676, and C. Ghosh, et al, "Bleaching Compositions Comprising
Protease
Enzymes" having US Serial No. 08/322,677, both filed October I3, 1994.
Preferred proteolytic enzymes are also modified bacterial serine proteases,
such as those
described in European Patent Application Serial Number 87 303,761.8, filed
April 28, 1987
(particularly pages 17, 24 and 98), and which is called herein "Protease B",
and in European
Patent Application 199,404, Venegas, published October 29, 1986, which refers
to a modified
bacterial serine proteolytic enzyme which is called "Protease A" herein,
Protease A as disclosed
in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A,
April 28, 1987
and EP 130,756 A, January 9, 1985.
Also preferred proteases are subtilisin enzymes, in particular BPN', that have
been
modified by mutating the various nucleotide sequences that code for the
enzyme, thereby
modifying the amino acid sequence of the enzyme. These modified subtilisin
enzymes have
decreased adsorption to and increased hydrolysis of an insoluble substrate as
compared to the
wild-type subtilisin. Also suitable are mutant genes encoding for such BPN'
variants.
Preferred BPN' variants comprise wild-type amino acid sequence wherein the
wild-type
amino acid sequence at one or more of positions 199, 200, 201, 202, 203, 204,
205, 206, 207,
208, 209, 210, 211, 212, 213, 214, 215, 216, 218, 219 or 220 is substituted;
wherein the BPN'
variant has decreased adsorption to, and increased hydrolysis of, an insoluble
substrate as
compared to the wild-type subtilisin BPN'. Preferably, the positions having a
substituted amino
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acid are 199, 200, 201, 202, 205, 207, 208, 209, 210, 211, 212, or 215; more
preferably, 200,
201, 202, 205 or 207.
Preferred protease enzymes for use according to the present invention also
include the
subtilisin 309 variants. These protease enzymes include several classes of
subtilisin 309 variants.
A. Loop Re ig_on 6 Substitution Variants - These subtilisin 309 variants have
a modified
amino acid sequence of subtilisin 309 wild-type amino acid sequence, wherein
the
modified amino acid sequence comprises a substitution at one or more of
positions
193, 194, 195, 196, 197, 199, 200, 201, 202, 203, 204, 205, 206, 207, 208,
209, 210,
211, 212, 213 or 2I4; whereby the subtilisin 309 variant has decreased
adsorption to,
and increased hydrolysis of, an insoluble substrate as compared to the wild-
type
subtilisin 309. Preferably these proteases have amino acids substituted at
I93, 194,
195, 196, 199, 201, 202, 203, 204, 205, 206 or 209; more preferably 194, 195,
196,
199 or 200.
B. Mufti-LoopJ~ions Substitution Variants - These subtilisin 309 variants may
also be
a modified amino acid sequence of subtilisin 309 wild-type amino acid
sequence,
wherein the modified amino acid sequence comprises a substitution at one or
more
positions in one or more of the first, second, third, fourth, or fifth loop
regions;
whereby the subtilisin 309 variant has decreased adsorption to, and increased
hydrolysis of, an insoluble substrate as compared to the wild-type subtilisin
309.
C. Substitutions at positions other than the loon regions - In addition, one
or more
substitution of wild-type subtilisin 309 may be made at positions other than
positions in the loop regions, for example, at position 74. If the additional
substitution to the subtilisin 309 is mad at position 74 alone, the
substitution is
preferably with Asn, Asp, GIu, Gly, His, Lys, Phe or Pro, preferably His or
Asp.
However modifications can be made to one or more loop positions as well as
position 74, for example residues 97, 99, 101, 102, 105 and 121.
Subtilisin BPN' variants and subtilisin 309 variants are further described in
WO 95/29979,
WO 95/30010 and WO 95/30011, all of which were published November 9, 1995, all
of which
are incorporated herein by reference.
iv) Lipase
Suitable lipase enzymes for detergent usage include those produced by
microorganisms
of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as
disclosed in GB
1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open
Feb. 24, 1978.
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Other 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
lipases are
lipases such as M1 LipaseR and LipomaxR (Gist-Brocades). Other suitable
commercial lipases
include Amano-CES, lipases ex Chromabacter 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 variants stabilized against peroxidase enzymes are described in WO
9414951 A to Novo.
See also WO 9205249 and RD 94359044.
Highly prefer ed lipases are the D96L Iipolytic enzyme variant of the native
lipase derived
from Humicola lanuginosa as described in US Serial No. 08/341,826. (See also
patent
application WO 92/05249 viz. wherein the native lipase ex Humicola Ianuginosa
aspartic acid
(D) residue at position 96 is changed to Leucine (L). According to this
nomenclature said
substitution of aspartic acid to Leucine in position 96 is shown as : D96L.)
Preferably the
Humicola lanuginosa strain DSM 4106 is used.
In spite of the large number of publications on lipase enzymes, only the
lipase derived from
Humicola lanuginosa and produced in Aspergillus oryzae as host has so far
found widespread
application as additive for fabric washing products. It is available from Novo
Nordisk under the
tradename LipolaseTM, as noted above. In order to optimize the stain removal
performance of
Lipolase, Novo Nordisk have made a number of variants. As described in WO
92/05249, the
D96L variant of the native Humicola lanuginosa lipase improves the lard stain
removal
efficiency by a factor 4.4 over the wild-type lipase (enzymes compared in an
amount ranging
from 0.075 to 2.5 mg protein per liter). Research Disclosure No. 35944
published on March 10,
1994, by Novo Nordisk discloses that the lipase variant (D96L) may be added in
an amount
corresponding to 0.001-100- mg (5-500,000 LU/Iiter) lipase variant per liter
of wash liquor.
Lipase enzyme is incorporated into the composition in accordance with the
invention at a
level of from 50 LU to 8500 LU per liter wash solution. Preferably the variant
D96L is present
at a level of from 100 LU to 7500 LU per liter of wash solution. More
preferably at a level of
from 150 LU to 5000 LU per liter of wash solution.
The lipases and/or cutinases are normally incorporated in the detergent
composition at
levels from 0.0001% to 2% of active enzyme by weight of the detergent
composition.
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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).
v) Cellulase
The laundry detergent compositions according to the present invention may
further
comprise at least 0.001% by weight, preferably at least about 0.01%, of a
cellulase enzyme.
However, an effective amount of cellulase enzyme is sufficient for use in the
laundry detergent
compositions described herein. The term "an effective amount" refers to any
amount capable of
producing a cleaning, stain removal, soil removal, whitening, deodorizing, or
freshness
improving effect on substrates such as fabrics, dishware and the like. The
compositions herein
will typically comprise from about 0.05% to about 2%, preferably from about
0.1% to about
1.5% by weight of a commercial enzyme preparation. The cellulase enzymes of
the present
invention are usually present in. such commercial preparations at levels
sufficient to provide from
0.005 to 0.1 Anson units (AU) of activity per gram of composition. Preferably,
the optimum pH
of the enzyme-containing composition is between about 7 and about 9.5.
U. S. Patent No. 4,435,307, Barbesgaard et al, issued March 6, 1984, discloses
cellulase
produced from Humicola insolens. Examples of other suitable cellulases include
those produced
by a strain of Humicola insolens, Humicola grisea var. thermoidea, and
cellulases produced by a
species of Bacillus sp. or Aeromonas sp. Other useful cellulases are those
extracted from the
hepatopancreas of the marine mollusc Dolabella Auricula Solander. Suitable
cellulases are also
disclosed in the following: GB 2,075,028 A (Novo Industri A/S); GB 2,095,275 A
(Kao Soap
Co.,-Ltd.); and Horikoshi et al, U.S. Patent No. 3,844,890 (Rikagaku
Kenkyusho). In addition,
suitable cellulases and methods for their preparation are described in PCT
International
Publication Number WO 91/17243, published November 14, 1991, by Novo Nordisk
A/S.
Cellulases are known iri the art and can be obtained from suppliers under the
tradenames:
Celluzyme~, Endolase~, and Carezyme~.
For industrial production of the cellulases herein it is preferred that
recombinant DNA
techniques be employed. However other techniques involving adjustments of
fermentations or
mutation of the microorganisms involved can be employed to ensure
overproduction of the
desired enzymatic activities. Such methods and techniques are known in the art
and may readily
be carried out by persons skilled in the art.
vi) Other Enzymes
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Peroxidase enzymes may be used in combination with oxygen sources, e.g.,
percarbonate,
perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of
transfer of dyes or
pigments removed from substrates during the wash to other substrates present
in the wash
solution. Known peroxidases include horseradish peroxidase, ligninase, and
haloperoxidases
such as chloro- or bromo-peroxidase. Peroxidase-containing detergent
compositions are
disclosed in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo.
Enzyme Stabilizing System
Enzyme-containing, including but not limited to, liquid compositions, herein
may
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. 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.
See Severson, U.S. 4,537,706 for a review of Borate stabilizers.
Suitable chlorine scavenger anions are widely known and readily available,
and, if used,
can be salts containing ammonium canons with sulfite, bisulfate, thiosulfite,
thiosulfate, iodide,
etc. Antioxidants such as carbamate, ascorbate, etc., organic amines such as
ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof,
monoethanolamine (MEA),
and mixtures thereof can likewise be used. Other conventional scavengers such
as bisulfate,
nitrate, chloride, sources of hydrogen peroxide such as sodium perborate
tetrahydrate, sodium
perborate monohydrate and sodium percarbonate, as well as phosphate, condensed
phosphate,
acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate,
etc., and mixtures thereof
can be used if desired.
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 4%, by weight, of the
detergent
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compositions herein, and individual perfumery ingredients can comprise from
about 0.0001 % to
about 90% of a finished perfume composition.
Material Care Agents
The present compositions may optionally contain as corrosion inhibitors and/or
anti-
tarnish aids one or more material care agents such as silicates. Material care
agents include
bismuth salts, transition metal salts such as those of manganese, certain
types of paraffin,
triazoles, pyrazoles, thiols, mercaptans, aluminium fatty acid salts, and
mixtures thereof and are
preferably incorporated at low levels, e.g., from about 0.01% to about 5% of
the composition. A
preferred paraffin oil is a predominantly branched aliphatic hydrocarbon
comprising from about
to about 50 carbon atoms with a ratio of cyclic to noncyclic hydrocarbons of
about 32 to 68
sold by Wintershall, Salzbergen, Germany as WINOG 70~. Bi(N03)3 may be added.
Other
corrosion inhibitors are illustrated by benzotriazole, thiols including
thionaphtoI and
thioanthranol, and finely divided aluminium fatty acid salts. All such
materials will generally be
15 used judiciously so as to avoid producing spots or films on glassware or
compromising the
bleaching action of the compositions. For this reason, it may be preferred to
formulate without
mercaptan anti-tarnishes which are quite strongly bleach-reactive or common
fatty carboxylic
acids which precipitate with calcium.
20 Chelating Agents
The detergent compositions herein may also optionally contain one or more iron
and/or
manganese chelating agents. Such chelating agents can be selected from the
group consisting of
amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic
chelating agents
and mixtures therein, all as hereinafter defined. Without intending to be
bound by theory, it is
believed that the benefit of these materials is due in part to their
exceptional ability to remove
iron and manganese ions from washing solutions by formation of soluble
chelates.
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetrace-
tates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates,
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 (methylenephosphonates) as DEQUEST.
Preferred, these
amino phosphonates to not contain alkyl or alkenyl groups with more than about
6 carbon atoms.
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Polyfunctionally-substituted aromatic chelating agents are also useful in the
compositions
herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
Preferred compounds
of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-
3,5-
disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate
("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233,
November 3, 1987,
to Hartman and Perkins.
The compositions herein may also contain water-soluble methyl glycine diacetic
acid
(MGDA) salts (or acid form) as a chelant or co-builder useful with, for
example, insoluble
builders such as zeolites, layered silicates and the like.
If utilized, these chelating agents will generally comprise from about 0.1% to
about 15%
by weight of the detergent compositions herein. More preferably, if utilized,
the chelating agents
will comprise from about 0. I % to about 3.0% by weight of such 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, especially in the presence of
zeolite and/or
layered silicate builders. Suitable polymeric dispersing agents include
polymeric
polycarboxylates and polyethylene glycols, although others known in the art
can also be used. It
is believed, though it is not intended to be limited by theory, that polymeric
dispersing agents
enhance overall detergent builder performance, when used in combination with
other builders
(including lower molecular weight polycarboxylates) by crystal growth
inhibition, particulate
soil release peptization, and anti-redeposition.
Polymeric polycarboxylate materials can be prepared by polymerizing or
copolymerizing
suitable unsaturated monomers, preferably in their acid form. Unsaturated
monomeric acids that
can be polymerized to form suitable polymeric polycarboxylates include acrylic
acid, malefic acid
(or malefic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic
acid, citraconic acid
and methylenemalonic acid. The presence in the polymeric polycarboxylates
herein or
monomeric segments, containing no carboxylate radicals such as vinylmethyl
ether, styrene,
ethylene, etc. is suitable provided that such segments do not constitute more
than about 40% by
weight.
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
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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
10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers
can include, for
example, the alkali metal, ammonium and substituted ammonium salts. Soluble
acrylate/maleate
copolymers of this type are known materials which are described in European
Patent Application
No. 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/IO terpoIymer 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.
Alkoxylated polycarboxylates such as those prepared from polyacrylates are
useful
herein to provide additional grease removal performance. Such materials are
described in WO
91/08281 and PCT 90/01815 at p. 4 et seq. Chemically, these materials comprise
polyacrylates
having one ethoxy side-chain per every 7-8 acrylate units. The side-chains are
of the formula
-(CH2CH20)m(CH2)nCH3 wherein m is 2-3 and n is 6-12. The side-chains are ester-
linked to
the polyacrylate "backbone" to provide a "comb" polymer type structure. The
molecular weight
can vary, but is typically in the range of about 2000 to about 50,000. Such
alkoxylated
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polycarboxylates can comprise from about 0.05% to about 10%, by weight, of the
compositions
herein.
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.
Dye Fixative Materials
Optionally but preferred for use herein are selected dye fixative materials
which do not
form precipitates,with anionic surfactant.
The selected dye fixatives useful herein may be in the form of unpolymerized
materials,
oligomers or polymers. Moreover, the preferred dye fixatives useful herein are
cationic. The
dye fixative component of the compositions herein will generally comprise from
about 0.1 % to
5% by the weight of the composition. More preferably, such dye fixative
materials will comprise
from about 0.5% to 4% by weight of the compositions, most preferably from
about 1% to 3%.
1 S Such concentrations should be sufficient to provide from about 10 to 100
ppm of the dye fixative
in the aqueous washing solutions formed from the laundry detergent
compositions herein. More
prefearably from about 20 to 60 ppm of the dye fixative will be delivered to
the aqueous washing
solution, most preferably about 50 ppm.
The non-precipitating dye fixatives useful herein include a number that are
commercially
marketed by CLARIANT Corporation under the Sandofix~, Sandolec~ and Polymer
VRN~
tradenames. These include, for example, Sandofix SWE~, Sandofix WA~, Sandolec
CT~,
Sandolec CS~, Sandolec C 1 ~, Sandolec CF~, Sandolec WA~ and Polymer VRN~.
Other
suitable dye fixatives are marketed by Ciba-Geigy Corporation under the
tradename Cassofix
FRN-300~ and by Hoechst Celanese Corporation under the tradename Tinofix EW~.
Builders
Detergent builders can optionally but preferably be included in the
compositions herein,
for example to assist in controlling mineral, especially Ca and/or Mg,
hardness in wash water or
to assist in the removal of particulate soils from surfaces. Builder level can
vary widely
depending upon end use and physical form of the composition. Built detergents
typically
comprise at least about 1% builder. Liquid formulations typically comprise
about 5% to about
50%; more typically 5% to 35% of builder. Lower or higher levels of builders
are not excluded.
For example, certain detergent additive or high-surfactant formulations can be
unbuilt.
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Suitable builders herein can be selected from the group consisting of
phosphates and
polyphosphates, especially the sodium salts; silicates including water-soluble
and hydrous solid
types and including those having chain-, layer-, or three-dimensional-
structure as well as
amorphous-solid or non-structured-liquid types; carbonates, bicarbonates,
sesquicarbonates and
carbonate minerals other than sodium carbonate or sesquicarbonate;
aluminosilicates; organic
mono-, di-, tri-, and tetracarboxylates especially water-soluble nonsurfactant
carboxylates in
acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or
water-soluble
low molecular weight polymer carboxylates including aliphatic and aromatic
types; and phytic
acid.
Builder mixtures, sometimes termed "builder systems" can be used and typically
comprise
two or more conventional builders, optionally complemented by chelants, pH-
buffers or fillers,
though these latter materials are generally accounted for separately when
describing quantities of
materials herein.
P-containing detergent builders often preferred where permitted by legislation
include, but
1 S are not limited to, the alkali metal, ammonium and alkanolammonium salts
of polyphosphates
exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric meta-
phosphates; and
phosphonates.
Suitable silicate builders include alkali metal silicates, particularly those
liquids and solids
having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1, including, particularly
for automatic
dishwashing purposes, solid hydrous 2-ratio silicates marketed by PQ Coip.
under the tradename
BRITESIL~, e.g., BRTTESIL H20; and layered silicates, e.g., those described in
U.S. 4,664,839,
May 12, 1987, H. P. Rieck. See preparative methods in German DE-A-3,417,649
and DE-A-
3,742,043.
Also suitable for use herein are synthesized crystalline ion exchange
materials or hydrates
thereof as taught in U.S. 5,427,711, Sakaguchi et al, June 27, 1995.
Suitable carbonate builders include alkaline earth and alkali metal carbonates
as disclosed
in German Patent Application No. 2,321,001 published on November 15, 1973.
Aluminosilicate builders are especially useful in granular detergents, but can
also be
incorporated in liquids. Suitable for the present purposes are those having
empirical formula:
[Mz(A102)z(Si02)v]'xH20 wherein z and v are integers of at least 6, the molar
ratio of z to v is
in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
AIuminosilicates can be
crystalline or amorphous, naturally-occurring or synthetically derived. An
aluminosilicate
production method is in U.S. 3,985,669, Krummel, et al, October 12, 1976.
Preferred synthetic
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crystalline aluminosilicate ion exchange materials are available as Zeolite A,
Zeolite P (B),
Zeolite X and, to whatever extent this differs from Zeolite P, the so-called
Zeolite MAP.
Suitable organic detergent builders include polycarboxylate compounds,
including water-
soluble nonsurfactant dicarboxylates and tricarboxylates. More typically
builder
polycarboxylates have a plurality of carboxylate groups, preferably at least 3
carboxylates.
Carboxylate builders can be formulated in acid, partially neutral, neutral or
overbased form.
When in salt form, alkali metals, such as sodium, potassium, and lithium, or
alkanolammonium
salts are preferred. Polycarboxylate builders include the ether
polycarboxylates, such as
oxydisuccinate, see Berg, U.S. 3,128,287, April 7, 1964, and Lamberti et al,
U.S. 3,635,830,
January 18, 1972; "TMS/TDS" builders of U.S. 4,663,071, Bush et al, May 5,
1987; and other
ether carboxylates including cyclic and alicyclic compounds, such as those
described in U.S.
Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other suitable builders are the ether hydroxypolycarboxylates, copolymers of
malefic
anhydride with ethylene or vinyl methyl ether; 1, 3, 5-trihydroxy benzene-2,
4, 6-trisulphonic
acid; carboxymethyloxysuccinic acid; the various alkali metal, ammonium and
substituted
ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid
and nitrilotriacetic
acid; as well as mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-
tricarboxylic acid,
carboxymethyloxysuccinic acid, and soluble salts thereof.
Oxydisuccinates are also especially useful in such compositions and
combinations.
Certain detersive surfactants or their short-chain homologs also have a
builder action. For
unambiguous formula accounting purposes, when they have surfactant capability,
these materials
are summed up as detersive surfactants. Preferred types for builder
functionality are illustrated
by: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed
in U.S.
4,566,984, Bush, January 28, 1986. Succinic acid builders include the CS-C2p
alkyl and alkenyl
succinic acids and salts thereof. Succinate builders also include:
laurylsuccinate,
myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-
pentadecenylsuccinate,
and the like. Lauryl-succinates are described in European Patent Application
86200690.5/0,200,263, published November 5, 1986. Fatty acids, e.g., C I2-C I
g monocarboxylic
acids, can also be incorporated into the compositions as surfactantlbuilder
materials alone or in
combination with the aforementioned builders, especially citrate and/or the
succinate builders, to
provide additional builder activity. Other suitable polycarboxylates are
disclosed in U.S.
4,144,226, Crutchfield et al, March 13, 1979 and in U.S. 3,308,067, Diehl,
March 7, 1967. See
also Diehl, U.S. 3,723,322.
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Other types of inorganic builder materials which can be used have the formula
(Mx)i Cay
(C03)z wherein x and i are integers from 1 to 15, y is an integer from 1 to
10, z is an integer
from 2 to 25, Mi are cations, at least one of which is a water-soluble, and
the equation Ei = 1-
15(xi multiplied by the valence of Mi) + 2y = 2z is satisfied such that the
formula has a neutral or
"balanced" charge. These builders are referred to herein as "Mineral
Builders".
Polymeric Soil Release Agent
Known polymeric soil release agents, hereinafter "SRA" or "SRA's", can
optionally be
employed in the present detergent compositions. If utilized, SRA's will
generally comprise from
0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by
weight, of the
composition.
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.
Suitable SRA's include a sulfonated product of a substantially linear ester
oligomer
comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy
repeat units, for
example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and
E.P. Gosselink.
See U.S. 4,711,730, December 8, 1987 to Gosselink et al, for examples of those
produced by
transesterification/ oligomerization of poly(ethyleneglycol) methyl ether,
DMT, PG and
poly(ethyleneglycol) ("PEG"). Partly- and fully- anionic-end-capped oligomeric
esters of U.S.
4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene
glycol ("EG"), PG,
DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block
polyester
oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink, for
example produced
from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or
PG, Me-
capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially
sulfoaroyl, end-
capped terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado,
Gosselink et al.
SRA's also include simple copolymeric blocks of ethylene terephthalate or
propylene
terephthalate with polyethylene oxide or polypropylene oxide terephthalate,
see U.S. 3,959,230
to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic
derivatives such
as the hydroxyether cellulosic polymers available as METHOCEL from Dow; and
the C1-C4
alkylcelluloses and C4 hydroxyalkyl celluloses; see U.S. 4,000,093, December
28, 1976 to
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Nicol, et al. Suitable SRA's characterised by polyvinyl ester) hydrophobe
segments include
graft copolymers of polyvinyl ester), e.g., CI-C6 vinyl esters, preferably
polyvinyl acetate),
grafted onto polyaIkylene oxide backbones. See European Patent Application 0
219 048,
published April 22, 1987 by Kud, et al. Commercially available examples
include SOKALAN
SRA's such as SOKALAN HP-22, available from BASF, Germany. Other SRA's are
polyesters
with repeat units containing 10-15% by weight of ethylene terephthalate
together with 90-80%
by weight of polyoxyethylene terephthalate, derived from a polyoxyethylene
glycol of average
molecular weight 300-5,000. Commercial examples include ZELCON 5126 from
Dupont and
MILEASE T from ICI.
U.S. 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995.
Suitable
monomers for the above SRA include Na 2-(2-hydroxyethoxy)-ethanesulfonate,
DMT, Na-
dimethyl 5-sulfoisophthalate, EG and PG.
Additional classes of SRA's include ()) nonionic terephthalates using
diisocyanate coupling
agents to link up polymeric ester structures, see U.S. 4,201,824, Violland et
al. and U.S.
4,240,918 Lagasse et al; (II) SRA's with carboxylate tenminal groups made by
adding trirnellitic
anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate
esters. With a
proper selection of catalyst, the trimellitic anhydride forms linkages to the
terminals of the
polymer through an ester of the isolated carboxylic acid of trimellitic
anhydride rather than by
opening of the anhydride linkage. Either nonionic or anionic SRA's may be used
as starting
materials as long as they have hydroxyl terminal groups which may be
esterified. See U.S.
4,525,524 Tung et al.; (III) anionic terephthalate-based SRA's of the urethane-
linked variety, see
U.S. 4,201,824, Violland et al; (IV) polyvinyl caprolactam) and related co-
polymers with
monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate,
including both
nonionic and cationic polymers, see U.S. 4,579,681, Ruppert et al.; (V) graft
copolymers, in
addition to the SOKALAN types from BASF made, by grafting acrylic monomers on
to
sulfonated polyesters; these SRA's assertedly have soil release and anti-
redeposition activity
similar to known cellulose ethers: see EP 279,134 A, 1988, to Rhone-Poulenc
Chemie; (V)7
grafts of vinyl monomers such as acrylic acid and vinyl acetate on to proteins
such as caseins, see
EP 457,205 A to BASF (1991); (VII) polyester-polyamide SRA's prepared by
condensing adipic
acid, caprolactam, and polyethylene glycol, especially for treating polyamide
fabrics, see Bevan
et al, DE 2,335,044 to Unilever N. V., 1974. Other useful SRA's are described
in U.S. Patents
4,240,918, 4,787,989, 4,525,524 and 4,877,896.
Brightener
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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, S- and 6-mernbered-ring heterocycles,
and other
miscellaneous agents. Examples of such brighteners are disclosed in "The
Production and
Application of Fluorescent Brightening Agents", M. Zahradnik, Published by
John Wiley &
Sons, New York ( 1982).
Specific examples of optical brighteners which are useful in the present
compositions are
those identified in U.S. Patent 4,790,856, issued to Wixon on December 13,
1988. These
brighteners include the PHORWHTTE series of brighteners from Verona. Other
brighteners
disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal
SBM; available
from Ciba-Geigy; Artic White CC and Artic White CWD, the 2-(4-styryl-phenyl)-
2H-naptho[1,2-
d]triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)-stilbenes; 4,4'-
bis(styryl)bisphenyls; and the amino-
coumarins. See also U.S. Patent 3,646,015, issued February 29, 1972 to
Hamilton.
Dye Transfer Inhibiting Agents
The compositions of the present invention may also include one or more
materials
effective for inhibiting the transfer of dyes from one fabric to another
during the cleaning
process. Generally, such dye transfer inhibiting agents include polyvinyl
pyrrolidone polymers,
polyamine N-oxide polymers, copolymers of N-vinyl-pyrrolidone and N-
vinylimidazole,
manganese phthalocyanine, peroxidases, and mixtures thereof. Preferred
polyamine N-oxides
are those wherein R is a heterocyclic group such as pyridine, pyrrole,
imidazole, pyrroIidine,
piperidine and derivatives thereof. If used, these agents typically comprise
from about 0.01% to
about 10% by weight of the composition, preferably from about 0.01% to about
5%, and more
preferably from about 0.05% to about 2%.
The N-O group can be represented by the following general structures:
The most preferred polyamine N-oxide useful in the detergent compositions
herein is
poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about
50,000 and an
amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as
a class
as "PVPVI") are also preferred for use herein. Preferably the PVPVI has an
average molecular
weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000,
and most
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preferably from 10,000 to 20,000. (The average molecular weight range is
determined by light
scattering as described in Barth, et al., Chemical Analysis, Vol 113. "Modern
Methods of
Polymer Characterization", the disclosures of which are incorporated herein by
reference.) The
PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-
vinylpyrrolidone from
1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1
to 0.4:1. These
copolymers can be either linear or branched.
The present invention compositions also may employ a poly-vinyl-pyrrolidone
("PVP")
having an average molecular weight of from about 5,000 to about 400,000,
preferably from about
5,000 to about 200,000, and more preferably from about 5,000 to about 50,000.
PVP's are known
to persons skilled in the detergent field; see, for example, EP-A-262,897 and
EP-A-256,696,
incorporated herein by reference. Compositions containing PVP can also contain
polyethylene
glycol ("PEG") having an average molecular weight from about 500 to about
100,000, preferably
from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm
basis delivered
in wash solutions is from about 2:1 to about 50:1, and more preferably from
about 3:1 to about
10:1.
The detergent compositions herein may also optionally contain from about
0.005% to 5%
by weight of certain types of hydrophilic optical brighteners which also
provide a dye transfer
inhibition action. If used, the compositions herein will preferably comprise
from about 0.01% to
1% by weight of such optical brighteners.
Particular brightener species, commercially marketed under the tradenames
Tinopal-
UNPA-GX, Tinopal AMS-GX, and Tinopal SBM-GX by Ciba-Geigy Corporation, are
also
included. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener
useful in the
detergent compositions herein.
Suds Suppressors
Suds suppression can be of particular importance in the so-called "high
concentration
cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-
loading European-
style washing machines.
A wide variety of materials may be used as suds suppressors, and suds
suppressors are well
known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia
of Chemical
Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc.,
1979). One
category of suds suppressor of particular interest encompasses monacarboxylic
fatty acid and
soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to
Wayne St. John.
The monocarboxylic fatty acids and salts thereof used as suds suppressor
typically have
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hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon
atoms. Suitable
salts include the alkali metal salts such as sodium, potassium, and lithium
salts, and ammonium
and alkanolammonium salts.
The detergent compositions herein may also contain non-surfactant suds
suppressers.
These include, for example: high molecular weight hydrocarbons such as
paraffin, fatty acid
esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent
alcohols, aliphatic Clg-C40
ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino
triazines such as
tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed
as products of
cyanuric chloride with two or three moles of a primary or secondary amine
containing 1 to 24
carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl
alcohol
phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li)
phosphates and phosphate
esters. The hydrocarbons such as paraffin and haloparaffin can be utilized in
liquid form.
Hydrocarbon suds suppressers are described, for example, in U.S. Patent
4,265,779, issued May
5, 1981 to Gandolfo et al.
Another preferred category of non-surfactant suds suppressers comprises
silicone suds
suppressers. This category includes the use of polyorganosiloxane oils, such
as polydimethyl-
siloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and
combinations of
polyorganosiloxane with silica particles wherein the polyorganosiloxane is
chemisorbed or fused
onto the silica. Silicone suds suppressers are well known in the art and are,
for example,
disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and
European Patent
Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
Other silicone suds suppressers are disclosed in U.S. Patent 3,455,839 which
relates to
compositions and processes for defoaming aqueous solutions by incorporating
therein small
amounts of polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described, for instance, in
German Patent
Application DOS 2,124,526. Silicone defoamers and suds controlling agents in
granular
detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et
al, and in U.S. Patent
4,652,392, Baginski et al, issued March 24, 1987.
Other suds suppressers useful herein comprise the secondary alcohols (e.g., 2-
alkyl
alkanols) and mixtures of such alcohols with silicone oils, such as the
silicones disclosed in U.S.
4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the C6-C16
alkyl
alcohols having a Cl-C16 chain. A preferred alcohol is 2-butyl octanol, which
is available from
Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are
available under the
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trademark ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise
mixtures
of alcohol + silicone at a weight ratio of 1:5 to 5:1.
Alkoxylated Polycarboxylates
Alkoxylated polycarboxylates such as those prepared from polyacrylates are
useful
herein to provide additional grease removal performance. Such materials are
described in WO
91/08281 and PCT 90/01815 at p. 4 et seq., incorporated herein by reference.
Chemically, these
materials comprise polyacrylates having one ethoxy side-chain per every 7-8
acrylate units. The
side-chains are of the formula -(CH2CH20)m(CH2)nCH3 wherein m is 2-3 and n is
6-12. The
side-chains are ester-linked to the polyacrylate "backbone" to provide a
"comb" polymer type
structure. The molecular weight can vary, but is typically in the range of
about 2000 to about
50,000. Such alkoxylated polycarboxylates can comprise from about 0.05% to
about 10%, by
weight, of the compositions herein.
Fabric Softeners
Various through-the-wash fabric softeners, especially the impalpable smectite
clays of
U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as
other softener
clays known in the art, can optionally be used typically at levels of from
about 0.5% to about
10% by weight in the present compositions to provide fabric softener benefits
concurrently with
fabric cleaning. Clay softeners can be used in combination with amine and
cationic softeners as
disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983
and U.S. Patent
4,291,071, Harris et al, issued September 22, 1981.
Method of Using the Composition
The compositions of this invention can be used to form aqueous washing
solutions for
use in the laundering of fabrics. Generally, an effective amount of such
compositions is added to
water, preferably in a conventional fabric laundering automatic washing
machine, to form such
aqueous laundering solutions. The aqueous washing solution so formed is then
contacted,
preferably under agitation, with the fabrics to be laundered therewith.
An effective amount of the liquid detergent compositions herein added to water
to form
aqueous laundering solutions can comprise amounts sufficient to form from
about 500 to 7,000
ppm of composition in aqueous solution. More preferably, from about 800 to
3,000 ppm of the
detergent compositions herein will be provided in aqueous washing solution.
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EXAMPLES
AE = Alcohol Ethoxylate
APA = Amino Propyl Amine
AS = Alkyl Sulfate
#EO = the average number of ethoxylation units per surfactant molecule
FA = Fatty Acid
CMG = N-Cocoyl N-Methyl Glucamine
LAS = Linear Alkyl Benzene Sulfonate
LTAC = Lauryl Trimethyl Ammonium Chloride
MEA = Monoethanolamine
Polymer A = tetraethylenepentaamine with an average degree of ethoxylation of
15
RPS = Rapeseed
TMSfTDS = a mixture of tartrate monosuccinate and tartrate disuccinate
S = Sulfate
EXAMPLE I
Table I illustrates how the Hydrophilic Index is calculated for various
surfactants that are
commonly used in laundry detergents. In the following table "Cn" is the
average chain length of
the surfactant molecule, and "phobe" represents the molecular weight of the
hydrophobic portion
of the surfactant molecule. Likewise, "phil" is the molecular weight of the
hydrophilic portion of
the surfactant molecule. "Total" is the sum of the phobe and the phil, that
is, the average
molecular weight of the surfactant molecule. "WF phil" is the weight fraction
of the philic
portion, that is, the molecular weight of the philic portion divided by the
total molecular weight.
The "HLS" is the WF phil multiplied by 20. For ionic surfactants the HIS value
is calculated for
the surfactant ion only, i.e, the counterion is ignored.
TABLE I
Surfactants #EO Cn hobe hil total WF HI
hil
Nonionics
AE 23-3 3 12.5 176 149 325 .459 9.17
AE 23-5 5 12.5 176 237 413 .574 11.48
AE 23-6.5 6.5 12.5 176 303 479 .633 12.65
AE 23-9 9 12.5 176 413 589 .701 14.02
AE 24-7 7 13 183 325 508 .640 12.80
CMG 13 183 238 421 .565 11.31
Avionics
anions
C25AS 0 13.5 190 96 286 .336 6.71
C25AE3.OS 3 13.5 190 228 418 .546 10.91
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C25AE1.8S 1.813.5 190 175.2365.2.480 9.59
C 11.BLAS 0 11.8 242.2 80 322.2.248 4.97
C45E1.OS 1 14.5 204 140 344 .407 8.14
C45E2.25S 2.2514.5 204 195 399 .489 9.77
C45E3.OS 3 14.5 204 228 432 .528 10.56
Cationics
cations
C10 APA 10 141 101 242 .417 8.35
LC8-10 APA 9 127 101 228 .443 8.86
EXAMPLE II
The following compositions are intended to illustrate the importance of the
Hydrophilic
Index according to the present invention. Compositions A and B in Table II A,
are made
according to the present invention. Compositions C through J, in Tables II C
and II D, are
compositions outside the limits of this invention and are presented for
comparative purposes
only. Compositions A and B have generally superior cleaning benefits when
compared to prior
compositions that are outside the limits of the present invention.
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TABLE II A
SurfactantsHI A B
Avionics
C25AE1.8S 9.59 20.5
C11.8LAS 4.97 6 3
C45E1.OS 8.14 22.5
Nonionics
AE23-9 14.02 2 3
Cationics
C 1 OAPA 8.3 1.5 1.5
S
Total 30 30
Surfactant
of Surf. 20.0010.00
As LAS
HI 8.90 8.42
Builders
Citric 2.5 2.5
Acid
C12-14FA 5
C12-18FA 3.5
RPS FA 6.5 5
Total _ I
14 1
l
TABLE II B
SurfactantsHI C D E F G
Avionics
C 11.8LAS 4.97 7.2 8.43 I 9.86 6.25
1
C45E2.25S 9.77 10.8 8.43 10.2513.8 10.27
Nonionics
AE23-6.5 12.656.5 3.37 4.1 8.1
AE23-9 14.02 2.22
Cationics
LTAC 5.18 1.2 0.51
Total 25.7 20.74 25.3525.88 24.62
Surfactant
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of Surf. 28.0240.65 43.39 38.10 25.39
As LAS
HI 8.94 8.17 8.15 8.31 9.50
Builders
TMS/TDS 3.37 4.1
Citric 4 3.37 4.1 7.1 4.5
Acid
C12-14FA 15 2.95 0.6
Total I I 19. ~ 9.698.8 7.1 -7.1
~ ~ I
TABLE H C
SurfactantsHI H I J
Anionics
C25AS 6.71 14
C25AE1.8S 9.59 20.15
C25AE2.SS 10.40 19
C25AE3.OS 10.91 4
Nonionics
AE23-9 14.02 2 0.63
AE24-7 12.80 4.5
CMG 11.31 3.5 2.5 4
Cationics
C10APA 8.35 0.5
C8-lOAPA 8.86 1.3
Total 24.5 23.78 27.8
Surfactant
of Surf. 0.00 0.00 0.00
As LAS
HI 10.839.87 9.06
Builders
Citric 3 3 1
Acid
C12-14FA 2 2
C12-18FA 7.5
RPS FA 3.1
Total 5 5 l
I.6
Compositions A and B, which were made according to the present invention,
included the
additional components listed in Table II D.
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TABLE II D
Additional ComponentsWeight
Coin ositions
R, S and T
DTPA 0.50
mannanase 0.01
rotease 0.88
am lase 0.10
cellulase 0.05
bri htener 0.15
of er A 1.20
ethanol 0.50
1,2- ro anediol 4.00
MEA 0.48
NaOH 7.00
Na2S04 1.75
borax 2.50
suds su ressor 0.06
erfume 0.50
dve 0.02
water and Minors bal.
