Note: Descriptions are shown in the official language in which they were submitted.
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GRANULAR COMPOSITIONS HAVING IMPROVED DISSOLUTION
FIELD
The present invention relates to granular detergent compositions having
is improved dissolution. More particularly, it relates to granular detergent
laundry
compositions containing potassium ions.
BACKGROUND
There is a current trend for commercially available granular detergent
2o compositionsto have higher bulk densities as well as higher active
ingredient
content. Such detergent compositions offer greater convenience to the
consumer and at the same time, reduce the amount of packaging materials
which will ultimately be disposed of.
But for such granular detergent compositions, there are problems of poor
2s dissolution resulting in residue andlor pafially dissolved detergent
clump/gel-like
mass left on fabric, in the washing machine, or in a washing machine dispenser
drawer. This n~idue can vary from fine particles to masses as large as 10 to
100 millimeters in size, and is very undesirable for consumers.
Although not wanting to be limited by theory, several examples are
3o illustrated showing how poor dissolution may occur. For example, when
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consumers first put detergent composition and clothes in the washing machine
prior to the addition of water in the tub, significant residue is left in the
tub or on
the clothes. This residue is formed as the machine is filling with water,
since the
detergent is trapped in the clothes and there is no agitation of the tub
contents.
s Under these conditions, hydration and dissolution occur on the surface of
the
detergent, wherein the detergent forms a hydrated paste, or gel-like mass.
In another example, detergent compositions containing zeolite-built
powders dispense poorly, especially when such compositions are placed in a
dispenser drawer of a washing machine andlor a detergent dosing device. This
io poor dispensing may be caused by the formation of a gel-like mass, which
have
high levels of surfactant, upon contact with water. The gel-like mass prevents
a
proportion of the detergent powder from being solubilized in the wash water,
which reduces the effectiveness of the detergent. These solubility problems
especially occur in conditions having low water pressures andlor lower washing
~s temperatures.
The use of effervescence to promote the dissolution of granular detergent
compositions is well known. The effervescence material is usually a
combination
of an acid, such as citric acid, and an alkaline carbonate, such as sodium
carbonate or sodium bicarbonate. The prior art describes preferred
2o effervescence systems which describes the benefits of having low levels of
acid
in the composition, as well as preferred particle sizes of the acid, in
improving the
dissolution behavior of the detergent.
Separately, the use of low levels of potassium salt in granular laundry
detergent compositions for improved solubility of the detergent composition is
2s also known.
None of the existing art provides all of the advantages and benefits of the
present invention.
SUMMARY
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The present invention is directed to a granular detergent composition
comprising, by weight of the total composition from about 0.1 % to about 20%
of a
particulate acid source and from about 1 % to about 50% of an alkaline
carbonate
source, wherein the particulate acid source and the alkaline carbonate source
s are capable of reacting together to produce a gas; from about 0.05% to about
50% potassium ions; and other detersive ingredients.
These and other features, aspects, and advantages of the present
invention will become evident to those skilled in the art from a reading of
the
present disclosure.
~o
DETAILED DESCRIPTION
While this specification concludes with claims distinctly pointing out and
particularly claiming that which is regarded as the invention, it is believed
that the
invention can be better understood through a careful reading of the following
~s detailed description of the invention.
All percentages and proportions are by weight, all temperatures are
expressed in degrees Celsius (°C), molecular weights are in weight
average,
unless othervvise indicated.
Examples of the invention are set forth hereinafter by way of illustration
2o and are not intended to be in any way limiting of the invention.
All ratios are weight ratios unless specifically stated otherwise.
The term mean particle size refers to the geometric mean of the particle
size distribution on a mass basis. This is typically measured by screening a
sample into a number of fractions (typically, five) on a series of Tyler
sieves. The
2s cumulative mass fraction finer is then plotted on a probit scale (y-axis)
against
the log of the aperture size of the sieves (x-axis). Regression of this data
generates a line whose x-intercept is the log of the geometric mean size.
As used herein, "comprising" means that other steps and other ingredients
which do not affect the end result can be added. This term encompasses the
3o terms "consisting of and "consisting essentially of'.
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Ali cited references are incorporated herein by reference in their entireties.
Citation of any reference is not an admission regarding any determination as
to
its availability as prior art to the claimed invention.
As used herein, the term "alkyl" means a hydrocarbyl moiety which is
s straight or branched, saturated or unsaturated. Unless othenrvise specified,
alkyls are preferably saturated or unsaturated with double bonds, preferably
with
one or finro double bonds.
As used herein, the term "detergent composition" or "detergent" is
intended to designate any of the agents conventionally used for removing soil,
1o such as general household detergents or laundry detergents of the synthetic
or
soap type.
The present invention relates to a granular detergent composition
comprising, by weight of the total composition from about 0.1 % to about 20%
of a
particulate acid source and from about 1 % to about 50% of an alkaline
carbonate
is source, wherein the particulate acid source and the alkaline carbonate
source
are capable of reacting together to produce a gas; from about 0.05% to about
50% potassium ions; and other detersive ingredients.
The granular detergent composition has improved dissolution. Such
compositions should reduce the aggregation, association, or solidification of
the
2o detergent particles in water. As a result, the problems of solid detergent
particlesllumps andlor gel-like masses remaining in the washing machine,
dispensing devices, and on washed clothes is greatly reduced. Although not
wanting to be limited by theory, it is believed that the particulate acid
source
reacting rapidly with the alkaline carbonate source produces a gas and an
2s organic salt, which helps disperse the detergent particles and thereby
improve
the solubility.
Although the addition of low levels of potassium ions or low levels of
effervescence materials in detergent compositions have been used to improve
the dissolution of detergents, the combination of both surprisingly improves
the
3o dissolution of the granular detergent composition, as well as provide a
detergent
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composition with better cleaning performance. This surprising benefit is not
possible when either dissolution improvement technology is used solely. For
example, as the level of potassium ions is increased in the composition, there
is
a point in which the composition can no longer be processed due to the high
s level of potassium ions. Technical constraints met with such compositions
include crutcher mix splitting, or over agglomerating. in addition, high
levels of
potassium ions may also negatively affect the dissolution behavior of the
finished
detergent composition. Furthermore, as the level of effervescence material,
such
as citric acid, is increased in the composition, the pH of the composition in
the
to wash solution will be lowered. Such compositions will negatively affect the
cleaning performance, as well as dissolution behavior, of the detergent
composition. Hence, detergent compositions with improved dissolution was
surprisingly achieved by combining both dissolution improvement technologies.
The granular detergent compositions of the present invention contains a
particulate acid source and an alkaline carbonate source which are capable to
react together to form a gas, potassium ions, and other detersive ingredients.
These, including a more detailed description of other detersive ingredients
are
described in detail below.
A. Particulate Acid Source
2o The composition of the present invention contains a particulate acid
source. The acid source is present in the detergent composition such that it
is
capable of reacting with the alkaline carbonate source to produce a gas.
The acid source may be any suitable organic, mineral or inorganic acid, or
a derivative thereof, or a mixture thereof. The source of acidity may be a
mono-,
bi- or tri-protonic acid. Preferred derivatives include a salt or ester of the
acid.
The source of acidity is preferably non-hygroscopic, in order to improve
storage
stability. Organic acids and their derivatives are preferred. The acid is
preferably
water soluble. Suitable acids include hydroxycarboxylic acids such as malic
acid,
tartaric acid and citric acid, dicarboxylic acids such as oxalic acid, malonic
acid,
3o fumaric, succinic acid and digiycolic acid, sulphamic acid, p-
toluenesulphonic
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acid and anhydrides thereof. Additional specific examples include acrylic
acid,
monosodium phosphate, sodium hydrogen sulfate, boric acid, or a salt or an
ester thereof. Those which are stable solids at normal temperature and are
less
hygroscopic are particularly desirable. Citric acid, fumaric acid, acrylic
acid,
s glutaric acid, succinic acid, adipic acrd, monosodium phosphate, sodium
hydrogen sulfate, boric acid, malic acid, oxalic acid, malonic acid,
diglycolic acid,
sulphamic acid, p-toluenesulphonic acid; and mixtures thereof, are especially
preferred.
The preferred mean particle size of the particulate acid source is about
to 2,000 microns or less, preferably about 1,000 microns or less, more
preferably
from about 150 microns to about 710 microns. In one example, 80% or more of
the acid source has a mean particle size in the range of from about 150
microns
to about 710 microns, with at least about 37% by weight of the acid source
having a mean particle size of about 350 microns or less.
is The acid source is preferably included in the composition at a level of
from
about 0.1 % to about 20%, more preferably from about 0.5% to about 10%, even
more preferably from about 1 % to about 5%, by weight of the composition.
B. Alkaline Carbonate Source
The composition of the present invention contains an alkaline carbonate
2o source. The alkaline carbonate source is present in the detergent
composition
such that it is capable of reacting with the particulate acid source to
produce a
gas. Preferably the gas is carbon dioxide, and therefore, the preferred
alkaline
carbonate source is a carbonate, or a suitable derivative thereof.
Examples of alkaline carbonate sources include alkaline earth and alkali
2s metal carbonates, including sodium carbonate, bicarbonate, sesqui-
carbonate,
and any mixtures thereof. Preferably, part of the alkaline carbonate source
contains a source of potassium ions such as K2C03 and KHC03.
Alkali metal percarbonates, such as sodium percarbonate and potassium
percarbonate, are also examples of alkaline carbonate sources for use in the
3o present invention. !n addition, the alkaline carbonate source may contain
other
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components, such as silicate. Suitable silicates include the water soluble
sodium
silicates with an Si02:Na20 ratio of from 1.0 to 2.8. Alkali metal
persilicates are
also suitable sources of silicate.
The alkaline carbonate source is preferably included in the composition at
s a level of from about 1 % to about 50%, more preferably from about 5% to
about
30%, even more preferably from about 10% to about 25%, by weight of the
composition.
C. Potassium Ion
The detergent compositions comprise from about 0.05% to about 50%,
1o preferably from about 0.5% to about 30%, more preferably from about 1 % to
about 20%, by weight, of potassium ions.
Potassium ions useful herein can be preferably provided from any salt,
builder, electrolyte, or surtactant.
Some of non-limiting examples of the potassium salts useful herein are
1s included the description below, as additional/optional detergent components
in
the section of "Industrial Applicabilityn. Preferable examples of such
potassium
salts can be selected from the group consisting of potassium salt of alkali
builders (e.g. potassium salt of carbonates, potassium salt of silicates),
potassium salt of mid-chain branched surfactants, and mixtures thereof.
2o Of the potassium salts, inorganic potassium salts are preferred, and are
more preferably selected from the group consisting of potassium chloride
(KCI),
potassium carbonate (K2C03), potassium sulfate (KZS04), tetrapotassium
pyrophosphate (K,P20~), tripotassium pyrophosphate (HK3P2Or), dipotassium
pyrophosphate (HzK2P20~), and monopotassium pyrophosphate (H3KP20~),
2s pentapotassium tripolyphosphate (K5P30~°), tetrapotassium
tripolyphosphate
(HK4P30~°), tripotassium tripolyphosphate (HZK3P30~°),
dipotassium
tripolyphosphate (H3K2P$O~°), and monopotassium tripolyphosphate
(H4KP3p~°);
potassium hydroxide (KOH); potassium silicate; potassium citrate, potassium
longer alkyl chain, mid-chain branched surfactant compounds, linear potassium
3o alkylbenzene sulfonate, potassium alkyl sulfate, potassium
alkylpolyethoxylate,
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and mixtures thereof. These are commercially available. Inorganic potassium
salts may be dehydrated (preferably) or hydrated. Of the hydrates, those which
are stable up to about 120°F (48.9°C) are preferred. Potassium
carbonate is
most preferred.
s Also suitable for use herein are salts of film forming polymers as described
in U.S. Pat. No. 4,379,080, Murphy, issued Apr. 5, 1983, column 8, line 44 to
column 10, line 37, incorporated herein, which are either partially or wholly
neutralized with potassium. Particularly preferred are the potassium salts of
copolymers of acrylamide and acrylate having a molecular weight between about
io 4,000 and 20,000.
D. Other Detersive Ingredients
The granular detergent compositions herein can optionally include one or
more detersive ingredients or other materials for assisting or enhancing
cleaning
performance, treatment of the substrate to be cleaned, or to modify the
is aesthetics of the detergent composition (e.g., perfumes, colorants, dyes,
etc.).
The following are illustrative examples of such optional detergent materials.
The
list of components is non-limiting.
1. Detersive Surfactant
The detergent composition optionally comprises a detersive surfactant.
2o Preferably the detergent composition comprises at least about 0.01 % of a
detersive surfactant; more preferably at ~east about 0.1 %; more preferably at
least about 1 %; more preferably still, from about 1 % to about 55%.
In a preferred embodiment of the present invention, the fine surfactant
containing particles have been removed from the composition. Preferably, fine
2s particles below 75 microns, more preferably below 150 microns, even more
preferably below 250 microns, have been removed from the composition.
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Detersive anionic surfactants are a preferable source of potassium ions.
The preferred molar ratio of potassium ions to anionic surfactant is from
about
0.5 to about 30, more preferably from about 1.0 to about 20, even more
preferably from about 2 to about 15.
s (1 ) Anionic Surfactants:
Nonlimiting examples of anionic surfactants useful herein, typically at
levels from about 0.1 % to about 50%, by weight, include the conventional
C11-C1g alkyl benzene sulfonates ("LAS") and primary, branched-chain and
random C10-C20 alkyl sulfates ("AS"), the C10-C1g secondary (2,3) alkyl
sulfates
io of the formula CH3(CH2)x(CHOSOg M+) CH3 and CH3 (CH2)y(CHOS03-M+)
CH2CH3 where x and (y + 1 ) are integers of at least about 7, preferably at
least
about 9, and M is a water-solubilizing ration, especially sodium, unsaturated
sulfates such as oleyl sulfate, the C10-C1g alpha-sulfonated fatty acid
esters, the
C10-C1g sulfated alkyl polyglycosides, the C10-C1g alkyl alkoxy sulfates
is ("AEXS' ; especially EO 1-7 ethoxy sulfates), and C10-C1 g alkyl alkoxy
carboxylates (especially the EO 1-5 ethoxycarboxylates). The C12-C1g betaines
and sulfobetaines ("sultaines"), C10-C1g amine oxides, and the like, can also
be
included in the overall compositions. C10-C20 conventional soaps may also be
used. If high sudsing is desired, the branched-chain C10-C16 soaps may be
20 used. Other conventional useful anionic surfactants are listed in standard
texts.
Other suitable anionic surfactants that can be used are alkyl ester
sulfonate surfactants including linear esters of Cg-C2p carboxylic acids
(i.e., fatty
acids) which are sulfonated with gaseous S03 according to "The Journal of the
American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting
2s materials would include natural fatty substances as derived from tallow,
palm oil,
etc.
Another suitable anionic surfactant are longer alkyl chain, mid-chain
branched surfactant compounds in (a) of the formula:
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Ab_X_B
wherein:
(a) Ab is a hydrophobic C9 to C22 (total carbons in the moiety), preferably
s from about C12 to about C18, mid-chain branched alkyl moiety having: (1) a
longest linear carbon chain attached to the - X - B moiety in the range of
from 8
to 21 carbon atoms; (2) one or more C1 - C3 alkyl moieties branching from this
longest linear carbon chain; (3) at least one of the branching alkyl moieties
is
attached directly to a carbon of the longest linear carbon chain at a position
to within the range of position 2 carbon (counting from carbon #1 which is
attached
to the - X - B moiety) to position w - 2 carbon (the terminal carbon minus 2
carbons, i.e., the third carbon from the end of the longest linear carbon
chain);
and (4) the surfactant composition has an average total number of carbon atoms
in the Ab X moiety in the above formula within the range of greater than 14.5
to
is about 18 (preferably greater than 14.5 to about 17.5, more preferably from
about
to about 17);
b) B is a hydophilic moiety selected from sulfates, sulfonates, amine
oxides, polyoxyalkylene (such as polyoxyethylene and polyoxypropylene),
alkoxyiated sulfates, polyhydroxy moieties, phosphate esters, glycerol
sulfonates,
2o polygluconates, polyphosphate esters, phosphonates, sulfosuccinates,
suifosuccaminates, polyalkoxylated carboxylates, glucamides, taurinates,
sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides,
monoalkanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerol
esters, glycerol ester sulfates, glycerol ethers, glycerol ether sulfates,
2s polyglycerol ethers, polyglycerol ether sulfates, sorbitan esters,
polyalkoxyiated
sorbitan esters, ammonioalkanesulfonates, amidopropyt betaines, alkylated
quats, alkyatedlpolyhydroxyalkylated quats, alkylated quats,
alkylatedlpolyhydroxylated oxypropyl quats, imidazolines, 2-yi-succinates,
sulfonated alkyl esters, and suifonated fatty acids (it is to be noted that
more than
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one hydrophobic moiety may be attached to B, for example as in (Ab-X)2-B to
give dimethyl quatsJ; and
X is selected from -CH2- and -C(O)-.
Other anionic surtactants useful for detersive purposes can also be
s included in the laundry detergent compositions. These can include salts
(including, for example, sodium, potassium, ammonium, and substituted
ammonium salts such as mono-, di- and triethanolamine salts) of soap, Cg-C22
primary of secondary alkanesulfonates, Cg-C24 oleflnsulfonates, sulfonated
polycarboxylic acids prepared by sulfonation of the pyrolyzed product of
alkaline
1o earth metal citrates, e.g., as described in British patent specification
No.
1,082,179, Cg-C24 alkylpolyglycolethersulfates (containing up to 10 moles of
ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates,
fatty
oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin
sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-
acyl
1s taurates, alkyl succinamates and sulfosuccinates, monoesters of
sulfosuccinates
(especially saturated and unsaturated C12-C1 g monoesters) and diesters of
sulfosuccinates (especially saturated and unsaturated Cg-C12 diesters),
sulfates
of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the
nonionic
nonsutfated compounds being described below), and alkyl polyethoxy
2o carboxylates such as those of the formula RO(CH2CH20)k-CH2C00-M+
wherein R is a C8-C22 alkyl, k is an integer from 0 to 10, and M is a soluble
salt-
forming cation. Resin acids and hydrogenated resin acids are also suitable,
such
as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids
present in or derived from tallow oil. Further examples are described in
"Surface
2s Active Agents and Detergents" (Vol. I and II by Schwartz, Peny and Berch).
A
variety of such surtactants are also generally disclosed in U.S. Patent
3,929,678,
issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through
Column 29, line 23 (herein incorporated by reference).
A preferred Bisulfate surfactant has the formula
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A-X-M+
R--
B-Y_M+
where R is an alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester,
amine or
s amide group of chain length C1 to C2g, preferably C3 to C24, most preferably
Cg
to C20, or hydrogen; A and B are independently selected from alkyl,
substituted
alkyl, and alkenyl groups of chain Length C1 to C2g, preferably C1 to C5, most
preferably C1 or C2, or a covalent bond, and A and B in total contain at least
2
atoms; A, B, and R in total contain from 4 to about 31 carbon atoms; X and Y
are
1o anionic groups selected from the group consisting of sulfate and sulfonate,
provided that at least one of X or Y is a sulfate group; and M is a cationic
moiety,
preferably a substituted or unsubstituted ammonium ion, or an alkali or
alkaline
earth metal ion.
The Bisulfate surfactant is typically present at levels of incorporation of
~ s from about 0.1 % to about 50%, preferably from about 0.1 % to about 35%,
most
preferably from about 0.5% to about 15% by weight of the detergent
composition.
When included therein, the laundry detergent compositions typically
comprise from about 0.1 % to about 50%, preferably from about 1 % to about 40%
by weight of an anionic surfactant.
20 (2) Nonionic Surfactants:
Nonlimiting examples of nonionic surfactants useful herein typically at
levels from about 0.1 % to about 50%, by weight include the alkoxylated
alcohols
(AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl
polyglycosides (APG's), C10-C1g glycerol ethers, and the tike.
2s More specifically, the condensation products of primary and secondary
aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide (AE)
are
suitable for use as the nonionic surfactant in the detergent composition. The
alkyl
chain of the aliphatic alcohol can either be straight or branched, primary or
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secondary, and generally contains from about 8 to about 22 carbon atoms.
Examples of commercially available nonionic surtactants of this type
include: TergitoITM 15-S-9 (the condensation product of C11-C15 linear alcohol
with 9 moles ethylene oxide) and TergitoITM 24-L-6 NMW (the condensation
s product of C12-C14 Primary alcohol with 6 moles ethylene oxide with a narrow
molecular weight distribution), both marketed by Union Carbide Corporation;
NeodoITM 45-9 (the condensation product of C14-C15 linear alcohol with 9
moles of ethylene oxide), NeodoITM 23-3 (the condensation product of C12-C13
linear alcohol with 3 moles of ethylene oxide), NeodoITM 45-7 (the
condensation
to product of C14-C15 linear alcohol with 7 moles of ethylene oxide) and
NeodoITM
45-5 (the condensation product of C14-C15 linear alcohol with 5 moles of
ethylene oxide) marketed by Shell Chemical Company; KyroTM EOB (the
condensation product of C13-C15 alcohol with 9 motes ethylene oxide),
marketed by The Procter & Gamble Company; and Genapol LA 030 or 050
Is (the condensation product of C12-C14 alcohol with 3 or 5 moles of ethylene
oxide) marketed by Hoechst.
Another class of preferred nonionic surfactants for use herein are the
polyhydroxy fatty acid amide surfactants of the formula.
R2- i-N -Z
O R~
2o wherein R1 is H, or C1~ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a
mixture thereof, R2 is C5_31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl
having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected
to
the chain, or an alkoxylated derivative thereof. Typical examples include the
C12-C1g and C12-C14 N-methylglucamides. See U.S. 5,194,639 and
2s 5,298,636. N-alkoxy polyhydroxy fatty acid amides can also be used; see
U.S.
5,489, 393.
Also useful as a nonionic surfactant in the detergent composition are the
alkylpolysaccharides such as those disclosed in U.S. Patent 4,565,647,
Llenado,
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14
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 9 .3 to about 3, most preferably from
about
s 1.3 to about 2.7 saccharide units.
Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl
phenols are also suitable for use as the nonionic surfactant of the surfactant
systems of the detergent composition, with the polyethylene oxide condensates
being preferred. These compounds include the condensation products of alkyl
1o phenols having an alkyl group containing from about 6 to about 14 carbon
atoms,
preferably from about 8 ,to about 14 carbon atoms, in either a straight-chain
or
branched-chain configuration with the alkytene oxide. Commercially available
nonionic surfactants of this type include IgepaITM CO-630, marketed by the GAF
Corporation; and TritonT~ X-45, X-114, X-100 and X-102, all marketed by the
1s Rohm ~ Haas Company. These surfactants are commonly referred to as
alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
The condensation products of ethylene oxide with a hydrophobic base
formed by the condensation of propylene oxide with propylene glycol are also
suitable for use as the additional nonionic surfactant in the detergent
2o composition. The hydrophobic portion of these compounds will preferably
have a
molecular weight of from about 1500 to about 1800 and will exhibit water
insolubility. Examples of compounds of this type include certain of the
commercially-available PluronicTM surfactants, marketed by BASF.
Also suitable for use as a nonionic surfactant in the detergent composition,
2s are the condensation products of ethylene oxide with the product resulting
from
the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of
these products consists of the reaction product of ethylenediamine and excess
propylene oxide, and generally has a molecular weight of from about 2500 to
about 3000. This hydrophobic moiety is condensed with ethylene oxide to the
3o extent that the condensation product contains from about 40% to about 80%
by
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weight of polyoxyethyiene and has a molecular weight of from about 5,000 to
about 11,000. Examples of this type of nonionic surfactant include certain of
the
commercially available TetronicTM compounds, marketed by BASF.
Also preferred nonionics are amine oxide surfactants. The detergent
s compositions may comprise amine oxide in accordance with the general formula
I:
R1(EO)x(P~)y(BO)zN(O)(CH2R~)2.qH20 (I).
In general, it can be seen that the structure (I) provides one long-chain
io moiety R1(EO)x(PO)y(BO)z and two short chain moieties, CH2R'. R' is
preferably selected from hydrogen, methyl and -CH20H. In general R1 is a
primary or branched hydrocarbyl moiety which can be saturated or unsaturated,
preferably, R1 is a primary alkyl moiety. When x+y+z = 0, R1 is a hydrocarbyl
moiety having chainlength of from about 8 to about 18. When x+y+z is different
is from 0, R1 may be somewhat longer, having a chainlength in the range C12-
C24
The general formula also encompasses amine oxides wherein x+y+z = 0, R1 =
Cg-Clg, R' = H and q = 0-2, preferably 2. These amine oxides are illustrated
by
C12-14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide,
octadecylamine oxide and their hydrates, especially the dihydrates as
disclosed
2o in U.S. Patents 5,075,501 and 5,071,594, incorporated herein by reference.
(3) Cationic Surfactants;
Nonlimiting examples of cationic surfactants useful herein typically at
levels from about 0.1 % to about 50%, by weight include the choline ester type
quats and alkoxylated quaternary ammonium (AQA) surfactant compounds, and
2s the like.
Cationic surfactants useful as a component of the surfactant system is a
cationic choline ester-type quat surfactant which are preferably water
dispersible
compounds having surfactant properties and comprise at least one ester (i.e.
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16
-COO-) linkage and at least one cationically charged group. Suitable cationic
ester surfactants, including choline ester surfactants, have for example been
disclosed in U.S. Patents Nos. 4,228,042, 4,239,660 and 4,260,529.
Preferred cationic ester surfactants are those having the formula:
s
RS R2
RUCf(C~nClbl a (~'-(CHaam (~--(CH2~N ~ R3 M
wherein R1 is a C5-C31 linear or branched alkyl, alkenyl or alkaryl chain or M-
N+(R6R~R8)(CHZ)s; X and Y, independently, are selected from the group
consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO
io wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO
group; R2, R3, R4, Rg, R7 and R8 are independently selected from the group
consisting of alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl and alkaryl groups
having from 9 to 4 carbon atoms; and R5 is independently H or a C1-C3 alkyl
group; wherein the values of m, n, s and t independently lie in the range of
from 0
is to 8, the value of b lies in the range from 0 to 20, and the values of a, a
and v
independently are either 0 or 1 with the proviso that at least one of a or v
must be
1; and wherein M is a counter anion.
Preferably R2, R3 and R4 are independently selected from CH3 and
-CH2CH20H.
2o Preferably M is selected from the group consisting of halide, methyl
sulfate, sulfate, and nitrate, more preferably methyl sulfate, chloride,
bromide or
iodide.
Particularly preferred choline esters of this type include the stearoyl
chotine ester quaternary methylammonium halides (R1=C17 alkyl), palmitoyl
2s choline ester quaternary methylammonium halides (R1=C15 alkyl), myrtstoyl
choline ester quaternary methylammonium halides (R1=C13 alkyl), lauroyl
choline ester quaternary methylammonium halides (R1=C11 alkyl), cocoyl
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choline ester quaternary methylammonium halides (R1=C11-C13 alkyl), tallowyl
choline ester quaternary methylammonium halides (R1=C15-C17 alkyl), and any
mixtures thereof.
Cationic surfactants useful herein also include alkoxylated quaternary
s ammonium (AQA) surfactant compounds (referred to hereinafter as "AQA
compounds") having the formula:
I ~N+ X -
R2~ ~A,qRa
wherein R1 is a linear or branched alkyl or alkenyl moiety containing from
about
io 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most
preferably from about 10 to about 14 carbon atoms; R2 is an alkyl group
containing from one to 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,
is suffrcient to provide electrical neutrality. A and A' can vary
independently and
are each selected from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH20-),
propoxy, butoxy and mixed ethoxylpropoxy; p is from 0 to about 30, preferably
1
to about 4 and q is from 0 to about 30, preferably 1 to about 4, and most
preferably to about 4; preferably both p and q are 1. See also: EP 2,084,
2o published May 30, 1979, by The Procter & Gamble Company, which describes
cationic surfactants of this type which are also useful herein..
The levels of the AQA surfactants used to prepare finished laundry
detergent compositions can range from about 0.1 % to about 5%, typically from
about 0.45% to about 2.5%, by weight.
2s The preferred bis-ethoxylated cationic surfactants herein are available
under the trade name ETHOQUAD from Akzo Nobel Chemicals Company.
Highly preferred bis-AQA compounds for use herein are of the formula
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18 -
R' CH2CH20H
~N+~ XO
CH3/ 'CH2CHZOH
wherein R1 is C10-C1g hydrocarbyl and mixtures thereof, preferably C10, C12
C14 alkyl and mixtures thereof, and X is any convenient anion to provide
charge
balance, preferably chloride. With reference to the general AQA structure
noted
s above, since in a preferred compound R1 is derived from coconut (C12-C14
alkyl) fraction fatty acids, R2 is methyl and ApR3 and A'qR4 are each
monoethoxy, this preferred type of compound is referred to herein as
"CocoMeE02" or "AQA-1" in the above list.
Other compounds of the foregoing type include those wherein the ethoxy
(CH2CH20) units (EO) are replaced by butoxy (Bu), isopropoxy [CH(CHg)CH20]
and [CH2CH(CH30] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO
andlor
Pr andlor i-Pr units.
Additional cationic surtactants are described, for example, in the
"Surfactant Science Series, Volume 4, Cationic Surfactants" or in the
"Industrial
~s Surfactants Handbook". Classes of useful cationic surtactants described in
these
references include amide quats (i.e., Lexquat AMG & Schercoquat CAS), glycidyl
ether quats (i.e., Cyostat 609), hydroxyalkyl quats (i.e., Dehyquart E),
alkoxypropyl quats (i.e., Tomah Q-17-2), polypropoxy quats (Emcol CC-9),
cyclic
alkylammonium compounds (i.e., pyridinium or imidazolinium quats), and/or
2o benzalkonium quats.
Typical cationic fabric softening components include the water-insoluble
quaternary-ammonium fabric softening actives or their corresponding amine
precursor, the most commonly used having been di-long alkyl chain ammonium
chloride or methyl sulfate.
2s Preferred cationic softeners among these include the following:
1) ditallow dimethylammonium chloride (DTDMAC);
2) dihydrogenated tallow dimethylammonium chloride;
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3) dihydrogenated tallow dimethylammonium methylsulfate;
4) distearyl dimethylammonium chloride;
5) dioieyl dimethylammonium chloride;
6) dipalmityl hydroxyethyl methylammonium chloride;
s 7) stearyl benzyl dimethylammonium chloride;
8) tallow trimethylammonium chloride;
9) hydrogenated tallow trimethylammonium chloride;
10) 012-14 alkyl hydroxyethyl dimethylammonium chloride;
11) 012-18 alkyl dihydroxyethyl methylammonium chloride;
l0 12) di(stearoyloxyethyl) dimethylammonium chloride (DSOEDMAC);
13) di(tallow-o~cy-ethyl) dimethylammonium chloride;
14) ditallow imidazolinium methylsuifate;
15) 1-(2-tallowyiamidoethyl)-2-tallowyl imidazolinium methylsulfate.
Biodegradable quaternary ammonium compounds have been presented
is as alternatives to the traditionally used di-long alkyl chain ammonium
chlorides
and methyl sulfates. Such quaternary ammonium compounds contain long chain
alk(en)yl groups interrupted by functional groups such as carboxy groups. Said
materials and fabric softening compositions containing them are disclosed in
numerous publications such as EP-A-0,040,562, and EP-A-0,239,910.
2o The quaternary ammonium compounds and amine precursors herein have
the formula (I) or (II), below
R3\ R3
R\~~'1~'1 Q_''I' 1 + N -~CH2)n'CH -CH2 X -
Rl X R3 Q
T~ T2
or
Zs (I)
(II)
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wherein Q is selected from -O-C(O)-, -C(O)-O-, -0-C(O)-0-, -NR4-C(O)-,
-C(O)-NR4-;
R1 is (CH2)n-Q-T2 or T3;
R2 is (CH2)m-Q-T4 or T5 or R3;
s R3 is C1-C4 alkyl or C1-C4 hydroxyalkyt or H;
R4 is H or C1-C4 alkyl or C1-C4 hydroxyalkyl;
T1, T2, T3, T4, T5 are independently C 11-C22 alkyl or alkenyl;
n and m are integers from 1 to 4; and
X- is a softener-compatible anion. Non-limiting examples of softener-
compatible
io anions include chloride or methyl sulfate.
The alkyl, or alkenyl, chain T1, T2, T3, T4, T5 must contain at least 11
carbon atoms, preferably at least 1fi carbon atoms. The chain may be straight
or
branched. Tallow is a convenient and inexpensive source of long chain alkyl
and
alkenyl material. The compounds wherein T1, T2, T3, T4, T5 represents the
is mixture of long chain materials typical for tallow are particularfy
preferred.
Specific examples of quaternary ammonium compounds suitable for use in
the aqueous fabric softening compositions herein include
1) N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
2) N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl
2o sulfate;
3) N,N-di(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
4) N,N-di(2-tallowyl-oxy-ethylcarbonyl-oxy-ethyl)-N,N-dimethyl ammonium
chloride;
5) N-(2-tallowyl-oxy-2-ethyl)-N-(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl
2s ammonium
chloride;
fi) N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;
7) N-(2-taliowyl-oxy-2-oxo-ethyl)-N-(tallowyl-N,N-dimethyl-ammonium chloride;
and
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2~
8) 1,2-ditaflowyl-oxy-3-trimethylammoniopropane chloride;
and mixtures of any of the above materials.
Other conventional useful surfactants are listed in standard texts.
2. Builders
s Detergent builders can optionally be included in the detergent
compositions herein to assist in controlling mineral hardness. These builders
can
be preferably added in addition to the particulate acid source, alkaline
carbonate
source, and potassium ion. inorganic as well as organic builders can be used.
Builders are typically used in fabric laundering compositions to assist in the
to removal of particulate soils.
The level of builder can vary widely depending upon the end use of the
composition and its desired physical form. When present, the compositions will
typically comprise at least about 1 % builder. Granular formulations typically
comprise from about 10% to about 80%, more typically from about 15% to about
is 50% by weight, of the detergent builder. Lower or higher levels of builder,
however, are not meant to be excluded.
Inorganic or P-containing detergent builders include, but are not limited to,
the alkali metal, ammonium and alkanolammonium salts of polyphosphates
(exempl~ed by the tripolyphosphates, pyrophosphates, and glassy polymeric
2o mete-phosphates), phosphonates, phytic acid, silicates, carbonates
(including
bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However,
non-phosphate builders are required in some locales. Importantly, the
compositions herein function surprisingly well even in the presence of the so-
called "weak" builders (as compared with phosphates) such as citrate, or in
the
2s so-called "underbuilt" situation that may occur with zeolite or layered
silicate
builders.
Examples of silicate builders are the alkali metal silicates, particularly
those having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and layered
silicates,
such as the layered sodium silicates described in U.S. Patent 4,664,839,
issued
3o May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline
layered
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22 -
silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike
zeolite builders, the Na SKS-6 silicate builder does not contain aluminum.
NaSKS-6 has the delta-Na2Si05 morphology form of layered silicate. SKS-6 is a
highly preferred layered silicate for use herein, but other such layered
silicates,
s such as those having the general formula NaMSix02x+1 ~YH20 wherein M is
sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a
number
from 0 to 20, preferably 0 can be used herein. Other silicates may also be
useful
such as for example magnesium silicate, which can serve as a crispening agent
in granular formulations, as a stabilizing agent for oxygen bleaches, and as a
~ o component of suds control systems.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates as disclosed in German Patent Application No. 2,321,001 published
on November 15, 1973.
Aluminosilicate builders are useful in the detergent composition.
~s Aluminosilicate builders are of great importance in most currently marketed
heavy duty granular detergent compositions. Aluminosilicate builders include
those having the empirical formula:
Mz(zA102)y]~xH20
wherein z and y are integers of at least 8, the molar ratio of z to y is in
the range
2o from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available.
These aluminosiiicates can be crystalline or amorphous in structure and can be
naturally-occurring aluminosilicates or synthetically derived. Preferred
synthetic
crystalline aluminosilicate ion exchange materials useful herein are available
2s under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X.
This
material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be
used herein. Preferably, the aluminosilicate has a mean particle size of about
0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the detergent
so composition include, but are not restricted to, a wide variety of
polycarboxylate
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compounds. As used herein, "polycarboxylate" refers to compounds having a
plurality of carboxylate groups, preferably at least 3 carboxylates.
Polycarboxylate builder can generally be added to the composition in acid
form,
but can also be added in the form of a neutralized salt. When utilized in salt
s form, alkali metals, such as sodium, potassium, and lithium, or
alkanoiammonium
salts are preferred.
Citrate builders, e.g., citric ~ acid and soluble salts thereof (particularly
sodium salt), are polycarboxylate builders of particular importance due to
their
availability from renewable resources and their biodegradability. Citrates can
to also be used in granular compositions, especially in combination with
zeolite
and/or layered silicate builders. Oxydisuccinates are also especially useful
in
such compositions and combinations.
Also suitable in the detergent compositions are the 3,3-dicarboxy-4-oxa
1,6-hexanedioates and the related compounds disclosed in U.S. Patent
is 4,566,984 to Bush, issued January 28, 1986. Useful succinic acid builders
include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A
particularly preferred compound of this type is dodecenylsuccinic acid.
Specific
examples of succinate builders . include: lauryisuccinate, myristylsuccinate,
palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate,
2o and the like.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,
Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl,
issued March 7, 1967. See also U.S. Patent 3,723,322 to Diehl, issued March
27, 1973.
2s Fatty acids, e.g., C12-C1g monocarboxylic acids, can also be incorporated
into the compositions alone, or in combination with the aforesaid builders,
especially citrate andlor the succinate builders, to provide additional
builder
activity. Such use of fatty acids will generally result in a diminution of
sudsing,
which should be taken into account by the formulator.
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In situations where phosphorus-based builders can be used, and
especially in the formulation of solids used for hand-laundering operations,
the
various alkali metal phosphates such as the well-known sodium
tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be
s used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and
other known phosphonates (see, for example, U.S. Patents 3,159,581 to Diehl,
issued December 1, 1964; 3,213,030 to Diehl, issued October 19, 1965;
3,400,148 to Quimby, issued September 3, 1968; 3,422,021 to Roy, issued
January 14, 1969; and 3,422,137 to Quimby, issued January 14, 1969) can also
io be used.
3. Alkoxvlated Potyca oxylates
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..
is 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
20 2000 to about 50,000. Such alkoxylated polycarboxylates can comprise from
about 0.05% to about 10% of the compositions herein.
4. _Bleachina Compounds - Bleaching Agents and Bleach Activators
The detergent compositions herein may optionally contain bleaching
agents or bleaching compositions containing a bleaching agent and one or more
2s bleach activators. When present, bleaching agents will typically be at
levels of
from about 1 % to about 30%, more typically from about 5% to about 20%, of the
detergent composition, especially for fabric laundering. If present, the
amount of
bleach activators will typically be from about 0.1 % to about 60%, more
typically
from about 0.5°~ to about 40% of the bleaching composition comprising
the
3o bleaching agent-plus-bleach activator.
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(1) Oxygen Bleaching Agents:
Preferred detergent compositions comprise, as part or aU of the laundry or
cleaning adjunct materials, an oxygen bleaching agent. Oxygen bleaching
agents useful in the detergent composition can be any of the oxidizing agents
s known for laundry, hard surface cleaning, automatic dishwashing or denture
cleaning purposes. Oxygen bleaches or mixtures thereof are preferred, though
other oxidant bleaches, such as oxygen, an enzymatic hydrogen peroxide
producing system, or hypohalites such as chlorine bleaches like hypochlorite,
may also be used.
Oxygen bleaches deliver "available oxygen" (Av0) or "active oxygen"
which is typically measurable by standard methods such as iodidelthiosulfate
and/or ceric sulfate titration. See the well-known work by Swern, or Kirk
Othmer's Encyclopedia of Chemical Technology under "Bleaching Agents".
When the oxygen bleach is a peroxygen compound, it contains -O-O- linkages
is with one O in each such linkage being "active". Av0 content of such an
oxygen
bleach compound, usually expressed as a percent, is equal to 100 * the number
of active oxygen atoms * (16 I molecular weight of the oxygen bleach
compound).
Preferably, an oxygen bleach will be used herein, since this benefits
2o directly from combination with the transition-metal bleach catalyst. The
oxygen
bleach herein can have any physical form compatible with the intended
application; more particularly, solid-form oxygen bleaches as well as
adjuncts,
promoters or activators are included.
Common oxygen bleaches of the peroxygen type include hydrogen
2s peroxide, inorganic peroxohydrates, organic peroxohydrates and the organic
peroxyacids, including hydrophilic and hydrophobic mono- or di- peroxyacids.
These can be peroxycarboxylic acids, peroxyimidic acids, amidoperoxycarboxylic
acids, or their salts including the calcium, magnesium, or mixed-ration salts.
Peracids of various kinds can be used both in free form and as precursors
known
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as "bleach activators" or "bleach promoters" which, when combined with a
source
of hydrogen peroxide, perhydrolyze to release the corresponding peracid.
Also useful herein as oxygen bleaches are the inorganic peroxides such
as Na202, superoxides such as K02, organic hydroperoxides such as cumene
s hydroperoxide and t-butyl hydroperoxide, and the inorganic peroxoacids and
their
salts such as the peroxosulfuric acid salts, especially the potassium salts of
peroxodisuifuric acid and, more preferably, of peroxomonosulfuric acid
including
the commercial triple-salt form sold as OXONE by DuPont and also ~ any
equivalent commercially available forms such as CUROX from Akzo or CAROAT
io from Degussa. Certain organic peroxides, such as dibenzoyl peroxide, may be
useful, especially as additives rather than as primary oxygen bleach.
Mixed oxygen bleach systems are generally useful, as are mixtures of any
oxygen bleaches with the known bleach activators, organic catalysts, enzymatic
catalysts and mixtures thereof; moreover such mixtures may further include
~s brighteners, photobleaches and dye transfer inhibitors of types well-known
in the
art.
Preferred oxygen bleaches, as noted, include the peroxohydrates,
sometimes known as peroxyhydrates or peroxohydrates. These are organic or,
more commonly, inorganic salts capable of releasing hydrogen peroxide readily.
20 They include types in which hydrogen peroxide is present as a true crystal
hydrate, and types in which hydrogen peroxide is incorporated covalently and
is
released chemically, for example by hydrolysis. Typically, peroxohydrates
deliver
hydrogen peroxide readily enough that it can be extracted in measurable
amounts into the ether phase of an etheNwater mixture. Peroxohydrates are
2s characterized in that they fail to give the Riesenfeld reaction, in
contrast to
certain other oxygen bleach types described hereinafter. Peroxohydrates are
the
most common examples of "hydrogen peroxide source" materials and include the
perborates, percarbonates, perphosphates, and persilicates. Other materials
which serve to produce or release hydrogen peroxide are, of course, useful.
3o Mixtures of two or more peroxohydrates can be used, for example when it is
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27
desired to exploit differential solubility. Suitable peroxohydrates include
sodium
carbonate peroxyhydrate and equivalent commercial "percarbonate" bleaches,
and any of the so-called sodium perborate hydrates, the °tetrahydrate"
and
"monohydrate" being preferred; though sodium pyrophosphate peroxyhydrate
s can be used. Many such peroxohydrates are available in processed forms with
coatings, such as of silicate and/or borate and/or waxy materials and/or
surfactants, or have particle geometries, such as compact spheres, which
improve storage stability. By way of organic peroxohydrates, urea
peroxyhydrate
can also be useful herein.
~o Percarbonate bleach includes, for example, dry particles having an mean
particle size in the range from about 500 micrometers to about 1,000
micrometers, not more than about 10% by weight of said particles being smaller
than about 200 micrometers and not more than about 10% by weight of said
particles being larger than about 1,250 micrometers. Percarbonates and
is perborates are widely available in commerce, for example from FMC, Solvay
and
Tokai Denka.
Salts of any of the peracids mentioned below can also be utilized. Salts
include, for example, sodium and potassium salts. Potassium salts are
especially preferred.
2o Organic pen;arboxylic acids useful herein as the oxygen bleach include
magnesium monoperoxyphthalate hexahydrate, available from Interox, m-chloro
perbenzoic acid and its salts, 4-nonylamino-4-oxoperoxybutyric acid and
diperoxydodecanedioic acid and their salts. Such bleaching agents are
disclosed
in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent
2s Application 740,446, Burns et al, filed June 3, 1985, European Patent
Application
0,133,354, Banks et al, published February 20, 1985, and U.S. Patent
4,412,934,
Chung et ai, issued November 1, 1983. Highly preferred oxygen bleaches also
include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in U.S.
Patent 4,fi34,551, issued January 6, 1987 to Burns et al, and include those
3o having formula HO-O-C(O)-R-Y wherein R is an alkylene or substituted
alkylene
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group containing from 1 to about 22 carbon atoms or a phenylene or substituted
phenylene group, and Y is hydrogen, halogen, alkyl, aryl or -C(O)-OH or -C(O)-
O-OH.
Organic percarboxylic acids usable herein include those containing one,
s two or more peroxy groups, and can be aliphatic or aromatic. When the
organic
percarboxylic acid is aliphatic, the unsubstituted acid suitably has the
linear
formula: HO-O-C(O)-(CH2)n-Y where Y can be, for example, H, CHg, CH2CI,
COOH, or C(O)OOH; and n is an integer from 1 to 20. Branched analogs are
also acceptable. When the organic percarboxylic acid is aromatic, the
to unsubstituted acid suitably has formula: HO-O-C(O)-C6H4-Y wherein Y is
hydrogen, alkyl; alkyhalogen, halogen, or -COOH or -C(O)OOH.
Monoperoxycarboxylic acids useful as oxygen bleach herein are further
illustrated by alkyl percarboxylic acids and aryl percarboxylic acids such as
peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g., peroxy-
alpha
1s naphthoic acid; aliphatic, substituted aliphatic and arylalkyl monoperoxy
acids
such as peroxylauric acid, peroxystea~ic acid, and N,N-
phthaloylaminoperoxycaproic acid (PAP); and fi-octylamino-6-oxo-
peroxyhexanoic acid. Monoperoxycarboxyfic acids can be hydrophilic, such as
peracetic acid, or can be relatively hydrophobic. The hydrophobic types
include
2o those containing a chain of six or more carbon atoms, preferred hydrophobic
types having a linear aliphatic C8-C14 chain optionally substituted by one or
more ether oxygen atoms and/or one or more aromatic moieties positioned such
that the peracid is an aliphatic peracid. More generally, such optional
substitution by ether oxygen atoms and/or aromatic moieties can be applied to
zs any of the peracids or bleach activators herein. Branched-chain peracid
types
and aromatic peracids having one or more C3-C16 linear or branched iong-chain
substituents can also be useful. The peracids can be used in the acid form or
as
any suitable salt with a bleach-stable ration.
Other useful peracids and bleach activators herein are in the family of
3o imidoperacids and imido bleach activators. These include
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29
phthaloylimidoperoxycaproic acid and related arylimido-substituted and
acyloxynitrogen derivatives. For listings of such compounds, preparations and
their incorporation into laundry compositions, see U.S. 5,487,818; U.S.
5,470,988, U.S. 5,466,825; U.S. 5,419,846; U.S. 5,415,796; U.S. 5,391,324;
U.S.
s 5,328,634; U.S. 5,310,934; U.S. 5,279,757; U.S. 5,246,620; U.S. 5,245,075;
U.S.
5,294,362; U.S. 5,423,998; U.S. 5,208,340; U.S. 5,132,431 and U.S. 5,087,385.
A preferred percarboxlic acid useful herein are amide-substituted and have
either of the formulae:
O O O O
R~-~-N-R2-~-L~ R~-N-~-RZ-~-L
K5 K5
or mixtures thereof, wherein R' is alkyl, aryl, or alkaryl containing from
about 1 to
about 14 carbon atoms including both hydrophilic types (short R') and
hydrophobic types (R' is especially from about 8 to about 12), R2 is alkylene,
arylene or alkarylene containing from about 1 to about 14 carbon atoms, R5 is
H,
is or an alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon
atoms, and
L is a leaving group.
Useful diperoxyacids include, for example, 1,12-diperoxydodecanedioic
acid (DPDA); 1,9-diperoxyazelaic acid; diperoxybrassilic acid; diperoxysebasic
acid and diperoxyisophthalic acid; 2-decyldiperoxybutane-1,4-dioic acid; and
4,4'-
2o sulphonylbisperoxybenzoic acid. Owing to structures in which two relatively
hydrophilic groups are disposed at the ends of the molecule, diperoxyacids
have
sometimes been classfied separately from the hydrophilic and hydrophobic
monoperacids, for example as °hydrotropic". Some of the diperacids are
hydrophobic in a quite literal sense, especially when they have a long-chain
2s moiety separating the peroxyacid moieties.
More generally, the terms "hydrophilic" and "hydrophobic" used herein in
connection with any of the oxygen bleaches, especially the peracids, and in
connection with bleach activators, are in the first instance based on whether
a
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given oxygen bleach effectively performs bleaching of fugitive dyes in
solution
thereby preventing fabric graying and discoloration and/or removes more
hydrophilic stains such as tea, wine and grape juice - in this case it is
termed
"hydrophilic". When the oxygen bleach or bleach activator has a significant
stain
s removal, whiteness-improving or cleaning effect on dingy, greasy,
carotenoid, or
other hydrophobic soils, it is termed "hydrophobic". The terms are applicable
also
when referring to peracids or bleach activators used in combination with a
hydrogen peroxide source. The current commercial benchmarks for hydrophilic
performance of oxygen bleach systems are: TAED or peracetic acid, for
1o benchmarking hydrophilic bleaching. NOBS or NAPAA are the corresponding
benchmarks for hydrophobic bleaching. The terms "hydrophilic", "hydrophobic"
and "hydrotropic" with reference to oxygen bleaches including peracids and
here
extended to bleach activator have also been used somewhat more narrowly in
the literature. See especially Kirk Othmer's Encyclopedia of Chemical
1s Technology, Vol. 4., pages 284-285. This reference provides a
chromatographic
retention time and critical micelle concentration-based set of criteria, and
is
useful to identif)r andlor characterize preferred sub-classes of hydrophobic,
hydrophilic and hydrotropic oxygen bleaches and bleach activators that can be
used in the detergent composition.
2o Bleaching agents other than oxygen bleaching agents are also known in
the art and can be utilized herein. One type of non-oxygen bleaching agent of
particular interest includes photoactivated bleaching agents such as the
sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718,
issued July 5, 1977 to Holcombe et al. If used, detergent compositions will
2s typically contain from about 0.025% to about 1.25%, by weight, of such
bleaches,
especiaAy sulfonate zinc phthalocyanine.
(2) Enzymatic sources of hydrogen peroxide
On a different track from the bleach activators illustrated hereinabove,
another suitable hydrogen peroxide generating system is a combination of a C1
3o C4 alkanol oxidase and a C1 -C4 alkanol, especially a combination of
methanol
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31
oxidase (MOX) and ethanol. Such combinations are disclosed in WO 94!03003.
Other enzymatic materials related to bleaching, such as peroxidases,
haloperoxidases, oxidases, superoxide dismutases, catalases and their
enhancers or, more commonly, inhibitors, may be used as optional ingredients
in
s the instant compositions.
(3) Oxygen Transfer Agents and Precursors
Also useful herein are any of the known organic bleach catalysts, oxygen
transfer agents or precursors therefor. These include the compounds
themselves and/or their precursors, for example any suitable ketone for
~o production of dioxiranes andlor any of the hetero-atom containing analogs
of
dioxirane precursors or dioxiranes, such as sulfonimines R1 R2C=NS02R3, see
EP 446 982 A, published 1991 and sulfonyloxaziridines, for example:
O
R~R2C NSOzR3
see EP 446,981 A, published 1991. Preferred examples of such materials
is include hydrophilic or hydrophobic ketones, used especially in conjunction
with
monoperoxysulfates to produce dioxiranes in situ, and/or the imines described
in
U.S. 5;576,282 and references described therein. Oxygen bleaches preferably
used in conjunction with such oxygen transfer agents or precursors include
percarboxylic acids and salts, percarbonic acids and salts, peroxymonosulfuric
2o acid and salts, and mixtures thereof. See also U.S. 5,360,568; U.S.
5,360,569;
and U.S. 5,370,826. In a highly preferred embodiment, the detergent
composition
incorporates a transition-metal bleach catalyst and an organic bleach catalyst
such as one named hereinabove, a primary oxidant such as a hydrogen peroxide
source, and at least one additional detergent, hard-surface cleaner or
automatic
2s dishwashing adjunct. Preferred among such compositions are those which
further include a precursor for a hydrophobic oxygen bleach, such as NOBS.
Although oxygen bleach systems andlor their precursors may be
susceptible to decomposition during storage in the presence of moisture, air
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32
(oxygen andlor carbon dioxide) and trace metals (especially rust or simple
salts
or colloidal oxides of the transition metals) and when subjected to light,
stability
can be improved by adding common sequestrants (chelants) andlor polymeric
dispersants and/or a small amount of antioxidant to the bleach system or
product. See, for example, U.S. 5,545,349. Antioxidants are often added to
detergent ingredients ranging from enzymes to surfactants. Their presence is
not
necessarily inconsistent with use of an oxidant bleach; for example, the
introduction of a phase barrier may be used to stabilize an apparently
incompatible combination of an enzyme and antioxidant, on one hand, and an
to oxygen bleach, on the other. Although commonly known substances can be used
as antioxidants, those that are preferable include phenol-based antioxidants
such
as 3,5-di-tert-butyl-4-hydroxytoluene and 2,5-di-tert-butylhydroquinone; amine-
based antioxidants such as N,N'-Biphenyl-p-phenylenediamine and phenyl-4-
piperizinyl-carbonate; sulfur-based antioxidants such as didodecyl-3,3'-
is thiodipropionate and ditridecy!-3,3'-thiodipropionate; phosphorus-based
antioxidants such as tris(isodecyi)phosphate and triphenylphosphate; and,
natural antioxidants such as L-ascorbic acid, its sodium salts and DL- alpha -
tocopherol. These antioxidants may be used independently or in combinations of
two or more. From among these, 3,5-di-tert-butyl-4-hydroxytoluene, 2,5-di-tert-
2o butylhydroquinone and D,L-alpha -tocopherol are particularly preferable.
When
used, antioxidants are blended into the bleaching composition preferably at a
proportion of 0.01-1.0 wt % of the organic acid peroxide precursor, and
particularly preferably at a proportion of 0.05-0.5 wt %. The hydrogen
peroxide or
peroxide that produces hydrogen peroxide in aqueous solution is blended into
25 the mixture during use preferably at a proportion of 0.5-98 wt %, and
particularly
preferably at a proportion of 1-50 wt %, so that the effective oxygen
concentration is preferably 0.1-3 wt %; and particularly preferably 0.2-2 wt
%. In
addition, the organic acid peroxide precursor is blended into the composition
during use, preferably at a proportion of 0.1-50 wt % and particularly
preferably at
3o a proportion of 0.5-30 wt %. Without intending to be limited by theory,
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33
antioxidants operating to inhibit or shut down free radical mechanisms may be
particularly desirable for controlling fabric damage.
While the combinations of ingredients used with the transition-metal
bleach catalysts can be widely permuted, some particularly preferred
s combinations include:
(a) transition metal bleach catalyst + hydrogen peroxide source alone,
e.g., sodium perborate or percarbonate;
(b) as (a) but with the further addition of a bleach activator selected from
(i) hydrophilic bleach activators, such as TAED;
to (ii) hydrophobic bleach activators, such as NOBS or activators
capable,
on perhydrolysis, of releasing NAPAA or a similar hydrophobic
peracid, and
(iii) mixtures thereof;
is (c) transition metal bleach catalyst + peracid alone, e.g.,
(i) hydrophilic peracid, e.g., peracetic acid;
(ii) hydrophobic peracid, e.g., NAPAA or peroxylauric acid;
(iii) inorganic peracid, e.g., peroxymonosulfuric acid potassium salts;
(d) use (a), (b) or (c) with the further addition of an oxygen transfer agent
20 or
precursor therefor, especially (c) + oxygen transfer agent.
Any of (aj - (d) can be further combined with one or more detersive
surfactants,
especially including mid-chain branched anionic types having superior low-
temperature solubility, such as mid-chain branched sodium alkyl sulfates,
though
2s high-level incorporation of nonionic detersive surfactants is also very
useful,
especially in compact-form heavy-duty granular detergent embodiments;
polymeric dispersants, especially including biodegradable, hydrophobicalty
modified andlor , terpolymeric types; sequestrants, for example certain
penta(methylenephosphonates) or ethyienediamine disuccinate; fluorescent
so whitening agents; enrymes, including those capable of generating hydrogen
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peroxide; photobleaches; andlor dye transfer inhibitors. Conventional
builders,
buffers or alkalis and combinations of multiple cleaning-promoting enzymes,
especially proteases, cellulases, amylases, keratinases, andlor lipases may
also
be added. In such combinations, the transition metal bleach catalyst will
s preferably be at levels in a range suited to provide wash (in-use)
concentrations
of from about 0.1 to about 10 ppm (weight of catalyst); the other components
typically being used at their known levels, which may vary widely.
While there is currently no certain advantage, the transition metal catalysts
can be used in combination with heretofore-disclosed transition metal bleach
or
1o dye transfer inhibition catalysts, such as the Mn or Fe complexes of
triazacyclononanes, the Fe complexes of N,N-bis(pyridin-2-yl-methyl)-
bis(pyridin-
2-yl)methylamine (U.S. 5,580,485) and the like. For example, when the
transition
metal bleach catalyst is one disclosed to be particularly effective for
solution
bleaching and dye transfer inhibition, as is the case for example with certain
1s transition metal complexes of porphyrins, it may be combined with one
better
suited for promoting interfacial bleaching of soiled substrates.
(4) Bleach Activators
Bleach activators useful herein include amides, imides, esters and
anhydrides. Commonly at least one substituted or unsubstituted acyi moiety is
2o present, covalently connected to a leaving group as in the structure R-C(O)-
L. In
one preferred mode of use, bleach activators are combined with a source of
hydrogen peroxide; such as the perborates or percarbonates, in a single
product.
Conveniently, the single product leads to in situ production in aqueous
solution
(i.e., during the washing process) of the percarboxylic acid corresponding to
the
2s bleach activator. The product itself can be hydrous, for example a powder,
provided that water is controlled in amount and mobility such that storage
stability
is acceptable. Alternately, the product can be anhydrous. With respect to the
above bleach activator structure RC(O)L, the atom in the leaving group
connecting to the peracid-forming acyl moiety R(C)O- is most typically O or N.
3o Bleach activators can have non-charged, positively or negatively charged
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peracid-forming moieties andlor nancharged, positively or negatively charged
leaving groups. One or more peracid-forming moieties or leaving-groups can be
present. See, for example, U.S. 5,595,967, U.S. 5,561,235, U.S. 5,560,862 or
the bis-(peroxy-carbonic) system of U.S. 5,534,179. Bleach activators can be
s substituted with electron-donating or electron-releasing moieties either in
the
leaving-group or in the peracid-forming moiety or moieties, changing their
reactivity and making them more or less suited to particular pH or wash
conditions. For example, electron-withdrawing groups such as N02 improve the
efficacy of bleach activators intended for use in mild-pH (e.g., from about
7.5- to
~o about 9.5) wash conditions.
Cationic bleach activators include quaternary carbamate-, quaternary
carbonate-, quaternary ester- and quaternary amide- types, delivering a range
of
cationic peroxyimidic, peroxycarbonic or peroxycarboxylic acids to the wash.
An
analogous but non-cationic palette of bleach activators is available when
is quaternary derivatives are not desired. In more detail, cationic activators
include
quaternary ammonium-substituted activators of WO 96-06915, U.S. 4,751,015
and 4,397,757, EP-A-284292, EP-A-331,229 and EP-A-03520 including 2-
(N,N,N-trimethyl ammonium) ethyl-4-sulphophenyl carbonate-(SPCC); N-
octyI,N,N-dimethyl-N 10-carbophenoxy decyl ammonium chloride-{ODC); 3-
20 {N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate; and
N,N,N-trimethyl ammonium toluyloxy benzene sulfonate. Also useful are cationic
nitrites as disclosed in EP-A-303,520 and in European Patent Specification
458,396 and 464,880. Other nitrite types have electron-withdrawing
substituents
as described in U.S. 5,591,378; examples including 3,5-dimethoxybenzonitrile
2s and 3,5-dinitrobenzonitrile.
Other bleach activator disclosures include GB 836,988; 864,798; 907,356;
1,003,310 and 1,519,351; German Patent 3,337,921; EP A-0185522; EP-A-
0174132; EP-A-0120591; U.S. Pat. Nos. 1,246,339; 3,332,882; 4,128,494;
4,412,934 and 4,675,393, and the phenol sulfonate ester of alkanoyl aminoacids
CA 02318559 2000-07-07
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disclosed in U.S. 5,523,434. Suitable bleach activators include any acetylated
diamine types, whether hydrophilic or hydrophobic in character.
Of the above classes of bleach precursors, preferred classes include the
esters, including acyl phenol sulfonates, acyl alkyl phenol sulfonates or aryl
s oxybenzenesulfonates (OBS leaving-group); the acyl-amides; and the
quaternary
ammonium substituted peroxyacid precursors including the cationic nitrites.
Preferred bleach activators include N,N,N'N'-tetraacetyl ethylene diamine
(TAED) or any of its close relatives including the triacetyl or other
unsymmetrical
derivatives. TAED and the acetylated carbohydrates such as glucose
~o pentaacetate and tetraacetyl xylose are preferred hydrophilic bleach
activators.
Depending on the application, acetyl triethyl citrate, a liquid, also has some
utility,
as does phenyl benzoate.
Preferred hydrophobic bleach activators include decyl oxybenzoic acid,
sodium lauroyl oxybenzene sulfonate, sodium nonanoyioxybenzene sulfonate
is (NOES or SNOBS), substituted amide types and activators related to certain
imidoperacid bleaches, for example as described in U.S. Patent 5,061,807,
issued October 29, 1991 and assigned to Hoechst Aktiengesellschaft of
Frankfurt, Germany. Japanese Laid-Open Patent Application (Kokai) No. 4-
28799 for example describes a bleaching agent and a bleaching detergent
2o composition comprising an organic peracid precursor described by a general
formula and illustrated by compounds which may be summarized more
particularly as conforming to the formula:
1 O
R
N-(CH2~-C-L
R O
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37 -
wherein L is sodium p-phenolsulfonate, R~ is CH3 or C~2H25 and R2 is H.
Analogs of these compounds having any of the leaving-groups identified herein
and/or having R1 being linear or branched C6-C16 are also useful.
Another group of peracids and bleach activators herein are those derivable
from acyclic imidoperoxycarboxylic acids and salts thereof of the formula:
O
E -
( N-X-~-00 ) M q+
g -C y z
(i)
cyclic imidoperoxycarboxylic acids and salts thereof of the formula:
O
I
q+
( A~ N-X- -00 )y M z
(n)
and (iii) mixtures of said compounds, (i) and {ii); wherein M is selected from
hydrogen and bleach-compatible rations having charge q; and y and z are
integers such that said compound is electrically neutral; E, A and X comprise
hydrocarbyl groups; and said terminal hydrocarbyl groups are contained within
E
is and A. The structure of the corresponding bleach activators is obtained by
deleting the peroxy moiety and the metal and replacing it with a leaving-group
L,
which can be any of the leaving-group moieties defined elsewhere herein. In
preferred embodiments, there are encompassed detergent compositions
wherein, in any of said compounds, X is linear C3-Cg alkyl; A is selected
from:
1 3
1
R
RFC=CSR Ri ~C-(CH - C~ R4
/ \ / ~Jn
wherein n is from 0 to about 4, and
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38
R~
R3
wherein R1 and E are said terminal hydrocarbyl groups, R2, R3 and
R4 are independently selected from H, C1-C3 saturated alkyl, and C1-C3
unsaturated alkyl; and wherein said terminal hydrocarbyl groups are alkyl
groups
s comprising at least six carbon atoms, more typically linear or branched
alkyl
having from about 8 to about 16 carbon atoms.
Other suitable bleach activators include sodium-4-benzoyloxy benzene
sulfonate (SBOBS); sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate;
sodium-4-methyl-3-benzoyloxy benzoate (SPCC); trimethyl ammonium
1o toluyloxy-benzene sulfonate; or sodium 3,5,5-trimethyl hexanoyloxybenzene
sulfonate (STHOBS).
Bleach activators may be used in an amount of up to 20%, preferably from
0.1-10% by weight, of the composition, though higher levels, 40% or more, are
acceptable, for example in highly concentrated bleach additive product forms
or
1s forms intended for appliance automated dosing.
Highly preferred bleach activators useful herein are amide-substituted and
have either of the formulae:
O O
O O
R'~-C-N-R2-C-L, R'i--N-C-R2-C-L
Rs Rs
or mixtures thereof, wherein R1 is alkyl, aryl, or alkaryl containing from
about 1 to
2o about 14 carbon atoms including both hydrophilic types (short R1) and
hydrophobic types (R1 is especially from about 8 to about 12), R2 is alkylene,
arylene or alkarylene containing from about 1 to about 14 carbon atoms, R5 is
H,
or an alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon
atoms, and
L is a leaving group.
CA 02318559 2000-07-07
WO 99136494 PCTNS98100571
39
A leaving group as defined herein is any group that is displaced from the
bleach activator as a consequence of attack by perhydroxide or equivalent
reagent capable of liberating a more potent bleach from the reaction.
Perhydrolysis is a term used to describe such reaction. Thus bleach activators
s perhydrolyze to liberate peracid. Leaving groups of bleach activators for
relatively
low-pH washing are suitably electron-withdrawing. Preferred leaving groups
have
slow rates of reassociation with the~moiety from which they have been
displaced.
Leaving groups of bleach activators are preferably selected such that their
removal and peracid formation are at rates consistent with the desired
1o application, e.g., a wash cycle. In practice, a balance is struck such that
leaving-
groups are not appreciably liberated, and the corresponding activators do not
appreciably hydrolyze or perhydrolyze, while stored in a bleaching
composition.
The pK of the conjugate acid of the leaving group is a measure of suitability,
and
is typically from about 4 to about 16, or higher, preferably from about 6 to
about
1s 12, more preferably from about 8 to about 11.
Preferred bleach activators include those of the formulae, for example the
amide-substituted formulae, hereinabove, wherein R1, R2 and R5 are as defined
for the corresponding peroxyacid and L is selected from the group consisting
of:
Y Rs RsY
Y ,. and
-~-R1 O
-N N -N-C-C H-R4
Rs ~ ~ ~ ,
I R3 Y
Y
R3 Y
-O-CH=C-CH=CH2 -O-CH=C-CH=CH2
, ,
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WO 99136494 PCT/US98100571
O CH -O Y p
-C 4
-O-C-R~ -N~ ,NR4 -N ~NR
C , ~C/ ,
O O
R3
O Y
-O-C=CHR4 , and -N-S-CH-R4
R3 O
and mixtures thereof, wherein R~ is a linear or branched alkyl, aryl, or
alkaryl
group containing from about 1 to about 14 carbon atoms, R3 is an alkyl chain
s containing from 1 to about 8 carbon atoms, R4 is H or R3, and Y is H or a
solubilizing group. These and other known leaving groups are, more generally,
general suitable alternatives for introduction into any bleach activator
herein.
Preferred solubilizing groups include -S03-M~, -C02-M+, -S04-M+, -N+(R)
4X- and O~-N(R3)2, more preferably -S03-M+ and -C02-M+ wherein R3 is
~o an alkyl chain containing from about 1 to about 4 carbon atoms, M is a
bleach-
stable ration and X is a bleach-stable anion, each of which is selected
consistent with maintaining solubility of the activator. Under some
circumstances, for example solid-form European heavy-duty granular detergents,
any of the above bleach activators are preferably solids having crystalline
~s character and melting-point above about 50 deg. C; in these cases, branched
alkyl groups are preferably not included in the oxygen bleach or bleach
activator.
Meking-point reduction can be favored by incorporating branched, rather than
linear alkyl moieties into the oxygen bleach or precursor.
When solubilizing groups are added to the leaving group, the activator can
2o have good water-solubility or dispersibility while still being capable of
delivering a
relatively hydrophobic peracid. Preferably, M is alkali metal, ammonium or
substituted ammonium, more preferably Na or K, and X is halide, hydroxide,
methylsulfate or acetate. Solubilizing groups can, more generally, be used in
any
bleach activator herein. Bleach activators of lower solubility, for example
those
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41
with leaving group not having a solubilizing group, may need to be finely
divided
or dispersed in bleaching solutions for acceptable results.
Preferred bleach activators also include those of the above general formula
wherein L is selected from the group consisting of:
Y R3 RsY
Y , and
s
wherein R3 is as defned above and Y is -S03-M+ or -C02-M+ wherein M is as
defined above.
Preferred examples of bleach activators of the above formulae include:
(6-octanamidocaproyl)oxybenzenesulfonate,
to (6-nonanamidocaproyl)oxybenzenesulfonate,
(6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof.
Other useful activators, disclosed in U.S. 4,96fi,723, are benzoxazin-type,
such as a C6H4 ring to which is fused in the 1,2-positions a moiety
-C(O)OC(R1 )=N-.
is Depending on the activator and precise application, good bleaching results
can be obtained from bleaching systems having with in-use pH of from about 6
to
about 13, preferably from about 9.0 to about 10.5. Typically, for example,
activators with electron-withdrawing moieties are used for near neutral or sub-
neutral pH ranges. Alkalis and buffering agents can be used to secure such pH.
2o Acyl lactam activators are very useful herein, especially the aryl
caprolactams (see for example WO 94-28102 A) and acyl valerolactams (see
U.S. 5,503,639) of the formulae:
p OC
R~/CwN~C
and
wherein R6 is H, alkyl, aryl, alkoxyaryl, an alkaryl group containing from 1
to
2s about 12 carbon atoms, or substituted phenyl containing from about 6 to
about
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42
18 carbons. See also U.S. 4,545,784 which discloses acyl caprolactams,
including benzoyl caprolactam adsorbed into sodium perborate. In certain
preferred embodiments of the detergent composition, NOBS, lactam activators,
imide activators or amide-functional activators, especially the more
hydrophobic
s derivatives, are desirably combined with hydrophilic activators such as
TAED,
typically at weight ratios of hydrophobic activator:TAED in the range of 1:5
to 5:1,
preferably about 1:1. Other suitable lactam activators are alpha-modified, see
WO 96-22350 A1, July 25, 1996. Lactam activators, especially the more
hydrophobic types, are desirably used in combination with TAED, typically at
to weight ratios of amido-derived or caprolactam activators:TAED in the range
of
1:5 to 5:1, preferably about 1:1. See also the bleach activators having cyclic
amidine leaving~roup disclosed in U.S. 5,552,556.
Nonlimiting examples of additional activators useful herein are to be found
in U.S. 4,915,854, U.S. 4,412,934 and 4,634,551. The hydrophobic activator
1s nonanoyloxybenzene sulfonate (NOES) and the hydrophilic tetraacetyl
ethylene
diamine (TAED) activator are typical, and mixtures thereof can also be used.
The superior bleachinglcleaning action of the detergent compositions is
also preferably achieved with safety to natural rubber machine parts, for
example
of certain European washing appliances (see WO 94-28104) and other natural
2o rubber articles, including fabrics containing natural rubber and natural
rubber
elastic materials. Complexities of bleaching mechanisms are legion and are not
completely understood.
Additional activators useful herein include those of U.S. 5,545,349.
Examples include esters of an organic acid and ethylene glycol, diethylene
glycol
2s or glycerin, or the acid imide of an organic acid and ethylenediamine;
wherein the
organic acid is selected from methoxyacetic acid, 2-methoxypropionic acid, p-
methoxybenzoic acid, ethoxyacetic acid, 2-ethoxypropionic acid, p-
ethoxybenzoic
acid, propoxyacetic acid, 2-propoxypropionic acid, p-propoxybenzoic acid,
butoxyacetic acid, 2-butoxypropionic acid, p-butoxybenzoic acid, 2-
3o methoxyethoxyacetic acid,2-methoxy-1-methylethoxyacetic acid, 2-methoxy-2-
CA 02318559 2000-07-07
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43
methylethoxyacetic acid,2-ethoxyethoxyacetic acid, 2-(2-ethoxyethoxy)propionic
acid, p-(2-ethoxyethoxy)benzoic acid, 2-ethoxy-I-methylethoxyacetic acid, 2-
ethoxy-2-methylethoxyacetic acid, 2-propoxyethoxyacetic acid, 2-propoxy-1-
methylethoxyaceticacid, 2-propoxy-2-methylethoxyacetic acid, 2-
s butoxyethoxyacetic acid ,2-butoxy-1-methylethoxyacetic acid, 2-butoxy-2-
methylethoxyacetic acid, 2-(2-methoxyethoxy}ethoxyacetic acid, 2-(2-methoxy-1-
methylethoxy)ethoxyacetic acid, 2-(2-methoxy-2-methylethoxy)ethoxyacetic acid
and 2-(2-ethoxyethoxy)ethoxyacetic acid.
(5) Bleach Catalysts
io If desired, the bleaching compounds can be catalyzed by means of a
manganese compound. Such compounds are well known in the art and include,
for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621,
U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European
Pat. App. Pub. Nos. 549,271A1, 549,272A1, 544,440A2, and 544,490A1;
~s Preferred examples of these catalysts indude MnIV2(u-O)3(1,4,7-trimethyl-
1,4,7-
trtazacyclononane)2(PF6)2, Mnll l2(u-O)1 (u-OAc)2(1,4,7-trimethyl-1,4,7-
triazacydononane)2-(CI04)2, MnIV4(u-O)6(1,4,7-triazacyclononane)4(C104)4,
MnIIIMnIV4(u-O)1 (u-OAc)2_(1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)3,
MnIV(1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures
2o thereof. Other metal-based bleach catalysts include those disclosed in U.S.
Pat.
4,430,243 and U.S. Pat. 5,114,611. The use of manganese with various
complex ligands to enhance bleaching is also reported in the following United
States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117;
5,274,147; 5,153,161; and 5,227,084.
2s As a practical matter, and not by way of limitation, the compositions and
processes herein can be adjusted to provide on the order of at least one part
per
ten million of the active bleach catalyst species in the aqueous washing
liquor,
and will preferably provide from about 0.1 ppm to about 700 ppm, more
preferably from about 1 ppm to about 500 ppm, of the catalyst species in the
30 laundry liquor.
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(6) Bleach Reducing Agent
Any bleach reducing agent known in the art can be incorporated at levels
typically from about 0.01 % to about 10%, by weight, into the detergent
compositions herein. Non limiting examples of bleach reducing agents include
s sulfurous acid or its salt (i.e., sulfite), hydrosu~ite (Na2S204
dihydrates),
rongalite (mixture of hydrosulfi#e + formalin), and thioureadioxide.
5. Bri~ htener
Any optical brighteners or other brightening or whitening agents known in
the art can be incorporated at levels typically from about 0.05% to about
1.2%,
to by weight, into the detergent compositions herein. Commercial optical
brighteners which may be useful in the detergent composition can be classified
into subgroups, which include, but are not necessarily limited to, derivatives
of
stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines,
dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and
is 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).
8. Chelating Agents
The detergent compositions herein may also optionally contain one or
2o more iron andlor manganese chelating agents. Such chelating agents can be
selected from the group consisting of amino carboxylates, amino phosphonates,
polyfunctionaAy-substituted aromatic chelating agents and mixtures therein,
all as
hereinafter defined.
Amino carboxyiates useful as optional chelating agents include
2s ethyienediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,
nitrilotriacetates, ethylenediamine tetraproprionates,
triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and
ethanoldiglyanes, alkali metal, ammonium, and substituted ammonium salts
therein and mixtures therein.
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Amino phosphonates are also suitable for use as chelating agents in the
compositions when at least low levels of total phosphorus are permitted in
detergent compositions, and include ethylenediaminetetrakis
(methylenephosphonates) as DEQUEST.
s 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
1o disuccinate ("EDDS"), especially the [S,SJ isomer as described in U.S.
Patent
4,704,233, November 3, 1987, to Hartman and Perkins.
The compos~ions 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.
1s If utilized, these chelating agents will generally comprise from about 0.1%
to about 15% by weight of the detergent compositions herein.
7. Clav Soil Removal / Anti-redenosition Agents
The detergent compositions can also optionally contain water-soluble
ethoxylated amines having clay soil removal and antiredeposition properties.
2o Granular detergent compositions which contain these compounds typically
contain from about 0.01 % to about 10.0% by weight of the water-soluble
ethoxylates amines.
The most preferred soil release and anti-redeposition agent is ethoxylated
tetraethylenepentamine. Exemplary ethoxylated amines are further described in
2s U.S. Patent 4,597,898 to VanderMeer, issued July 1, 1986. Another group of
preferred clay soil removal-antiredeposition agents are the cationic compounds
disclosed in European Patent Application 111,965, Oh and Gosselink, published
June 27, 1984. Other clay soil removal/antiredeposition agents which can be
used include the ethoxylated amine polymers disclosed in European Patent
3o Application 111,984, Gosselink, published June 27, 1984; the zwitterionic
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46
polymers disclosed in European Patent Application 112,592, Gosselink,
published July 4, 1984; and the amine oxides disclosed in U.S. Patent
4,548,744,
Connor, issued October 22, 1985. Other clay soil removal and/or anti
redeposition agents known in the art can also be utilized in the compositions
s herein. Another type of preferred antiredeposition agent includes the
carboxy
methyl cellulose (CMC) materials. These materials are well known in the art.
8. Dve Transfer Inhibiting Agients
The detergent compositions may also include one or more materials
effective for inhibiting the transfer of dyes from one fabric to another
during the
io cleaning process. Generally, such dye transfer inhibiting agents include
polyvinyl
pyrroiidone polymers, polyamine N-oxide polymers, copolymers of N-
vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases,
and mixtures thereof. If used, these agents typically comprise from about 0.01
to about 10% by weight of the composition, preferably from about 0.01 % to
about
is 5%, and more preferably from about 0.05% to about 2%.
The most preferred polyamine N-oxide useful as dye transfer inhibiting
polymers 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.
2o Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred
to as a class as "PVPVI") are also suitable for use herein. Preferably the
PVPVI
has an average molecular weight range from 5,000 to 1,000,000, more preferably
from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The
average molecular weight range is determined by light scattering as described
in
2s Barth, et al., Chemical Analyrsis, Vol 113. "Modern Methods of Polymer
Characterization".) The PVPVI copolymers typically have a molar ratio of N-
vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:7 , 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.
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The detergent composition also may employ as a dye transfer inhibitor a
polyvinyipyrrolidone ("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
s in the detergent field; see, for example, EP A-262,897 and EP-A-256,696.
Compositions containing PVP dye transfer inhibitors 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
1o to about 50:1, and more preferably from about 3:1 to about 10:1.
9. Enzymes
Enzymes can be included in the detergent compositions for a variety of
purposes, including removal of protein-based, carbohydrate-based, or
triglyceride-based stains from substrates, for the prevention of refugee dye
1s transfer in fabric laundering, and for fabric restoration. Suitable enzymes
include
proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of
any suitable origin, such as vegetable, animal, bacterial, fungal and yeast
origin.
Preferred selections are influenced by factors such as pH-activity and/or
stability
optima, thermostability, and stability to active detergents, builders and the
like. In
2o this respect bacterial or fungal enzymes are preferred, such as bacterial
amylases and proteases, and fungal cellulases.
"Detersive enzyme", as used herein, means any enzyme having a
cleaning, stain removing or othervvise beneficial effect in a laundry, hard
surface
cleaning or personal care detergent composition. Preferred detersive enzymes
2s are hydrolases such as proteases, amylases and lipases. Preferred enzymes
for
laundry purposes include, but are not limited to, proteases, cellulases,
lipases
and peroxidases. Highly preferred for automatic dishwashing are amylases
andlor proteases, including both current commercially available types and
improved types which, though more and more bleach compatible though
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successive improvements, have a remaining degree of bleach deactivation
susceptibility.
Enzymes are normally incorporated into detergent or detergent additive
compositions at levels sufficient to provide a "cleaning-effective amount".
The
s term "cleaning effective amount" refers to any amount capable of producing a
cleaning, stain removal, soil removal, whitening, deodorizing, or freshness
improving effect on substrates such as fabrics, dishware and the like. In
practical
terms for current commercial preparations, typical amounts are up to about 5
mg
by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the
io detergent composition. Stated otherwise, the compositions herein will
typically
comprise from 0.001 % to 5%, preferably 0.01 %-1 % by weight of a commercial
enzyme preparation. Protease enzymes are usually present in such commercial
preparations at levels sufficient to provide from 0.005 to 0.1 Anson units
(AU) of
activity per gram of composition. For certain detergents, such as in automatic
~s dishwashing, it may be desirable to increase the active enzyme content of
the
commercial preparation in order to minimize the total amount of non-
catalytically
active materials and thereby improve spottingffilming or other end-results.
Higher active levels may also be desirable in highly concentrated detergent
formulations.
20 10. 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 detergent
2s 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.
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11. Polymeric Soil Release Agent
Known polymeric soil release agents, hereinafter "SRA", 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%
s to 3.0% by weight, of the compositions.
Preferred SRA's include oligomeric terephthalate esters.
Suitable SRA's also include a sulfonated product of a substantially linear
ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and
oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties
to covalently attached to the backbone, for example as described in U.S.
4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other SRA's
include the nonionic end-capped 1,2-propylene/polyoxyethylene terephthalate
polyesters of U.S. 4,711,730, December 8, 1987 to Gosselink et al., for
example
those produced by transesterification/oligomerization of poly(ethyleneglycol)
is methyl ether, DMT, PG and poty(ethyieneglycol) ("PEG"). Other examples of
SRA's inGude: the partly- and fully- anionio-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,
2o October 27, 1987 to Gosselink, for example produced from DMT, methyl (Me)-
capped PEG and EG and/or PG, or a combination of DMT, EG andlor PG, Me-
capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially
sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31,
1989
to Maldonado, Gosselink et al., the latter being typical of SRA's useful in
both
2s laundry and fabric conditioning products, an example being an ester
composition
made from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but
preferably further comprising added PEG, e.g., PEG 3400.
SRA's also include: simple copolymeric blocks of ethylene terephthalate or
propylene terephthalate with polyethylene oxide or polypropylene oxide
3o terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929
to
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Basadur, July 8, 1975; ceilulosic derivatives such as the hydroxyether
cellulosic
polymers available as METHOCEL from Dow; the C1-C4 alkyl celluloses and C4
hydroxyalkyl celluloses, see U.S. 4,000,093, December 28, 1976 to Nicol, et
al.;
and the methyl cellulose ethers having an average degree of substitution
s (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution
viscosity of from about 80 to about 120 centipoise measured at 20°C as
a 2%
aqueous solution. Such materials are available as METOLOSE SM100 and
METOLOSE SM200, which are the trade names of methyl cellulose ethers
manufactured by Shin-etsu Kagaku Kogyo KK.
io Suitable SRA's characterized by polyvinyl ester) hydrophobe segments
include graft copolymers of polyvinyl ester), e.g., C1-Cg vinyl esters,
preferably
polyvinyl acetate), grafted onto polyalkylene oxide backbones. See European
Patent Application 0 219 048, published April 22, 1987 by Kud, et al.
Commercially available examples include SOKALAN SRA's such as SOKALAN
is HP-22, available from BASF, Germany. Other SRA's are polyesters with repeat
units containing 10-15% by weight of ethylene terephthalate together with 80-
90% 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.
2o Another preferred SRA is an oligomer having empirical formula
(CAP)2(EGIPG)5(T)5(SIP)1 which comprises terephthaloyl {'~; sulfoisophthaloyl
(SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units and which is
preferably terminated with end-caps (CAP), preferably modified isethionates,
as
in an oligomer comprising one sulfoisophthaloyl unit, 5 terephthaloyl units,
2s oxyethyleneoxy and oxy-1,2-propyleneoxy units in a defined ratio,
preferably
about 0.5:1 to about 10:1, and two end-cap units derived from sodium 2-{2-
hydroxyethoxy)-ethanesulfonate.
Yet another group of preferred SRA's are oligomeric esters comprising:
(i) a backbone comprising (a) at least one unit selected from the group
so consisting of dihydroxysulfonates, polyhydroxy sulfonates, a unit which is
at least
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51
trifunctional whereby ester linkages are formed resulting in a branched
oligomer
backbone, and combinations thereof; (b) at least one unit which is a
terephthaloyl moiety; and (c) at least one unsulfonated unit which is a 1,2-
oxyalkyleneoxy moiety; and (2) one or more capping units selected from
nonionic
s capping units, anionic capping units such as alkoxyiated, preferably
ethoxylated,
isethionates, alkoxylated propanesulfonates, alkoxylated propanedisulfonates,
alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof.
Additional classes of SRA's include: (I) nonionic terephthalates using
diisocyanate coupling agents to link polymeric ester structures, see U.S.
4,201,824, Holland et al. and U.S. 4,240,918 to Lagasse et al.; and (II) SRA's
with carboxylate terminal groups made by adding trimellitic anhydride to known
SRA's to convert terminal hydroxyl groups to trirnellitate esters. Other
classes
include: (III) anionic terephthalate-based SRA's of the urethane-finked
variety,
see U.S. 4,201,824, Violland et al.; (IV) polyvinyl caprolactam) and related
co-
ts 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 onto sulfonated polyesters. Still
other
classes include: (VI) grafts of vinyl monomers such as acrylic acid and vinyl
2o acetate onto proteins such as caseins, see EP 457,205 A to BASF (1991); and
(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 and 4,525,524.
2s The detergent composition can optionally contain a polyamine soil release
agent related to modified polyamines. See U.S. 5,565,145 issued October 15,
1996 to Watson et al.
The preferred poiyamine soil release agents that comprise the backbone
of the compounds are generally polyalkyleneamines (PAA's), polyalkyleneimines
30 (PAI's), preferably polyethyleneamine (PEA's), polyethyleneimines (PEI's),
or
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PEA's or PEI's connected - by moieties having longer R units than the parent
PAA's, PAI's, PEA's or PEI's. A common polyalkyleneamine (PAA) is
tetrabutylenepentamine. The common PEA's obtained are, triethylenetetramine
(TETA) and teraethylenepentamine (TEPA). Above the pentamines, i.e., the
s hexamines, heptamines, octamines and possibly nonamines, the cogenerically
derived mixture does not appear to separate by distillation and can include
other
materials such as cyclic amines and particularly piperazines. There can also
be
present cyclic amines with side chains in which nitrogen atoms appear. See
U.S.
Patent 2,792,372 to Dickinson, issued May 14, 1957, which describes the
to preparation of PEA's.
The polyamine soil release agents if included in the detergent
composition, is included from about 0.01 % to about 5%; preferably about 0.3%
to
about 4%; more preferably about 0.5% to about 2.5%, by weight of the detergent
composition.
is 12. Polymeric Dis~ersing~ Agent
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 glycois,
2o although others known in the art can also be used.
Particularly suitable polymeric polycarboxylates can be derived from
acrylic acid. Such acrylic acid-based polymers which are useful herein are the
water soluble salts of polymerized acrylic acid. The average molecular weight
of
such polymers in the acid form preferably ranges from about 2,000 to 10,000,
2s 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 poiyacrylates of this type
in
detergent compositions has been disclosed, for example, in Diehl, U.S. Patent
30 3,308,067, issued march 7, 1967.
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Acryliclmaleic-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
s 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 acrytate 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.
Another polymeric material which can be included is polyethylene glycol
(PEG). PEG can exhibit dispersing agent performance as welt 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,
1s especially in conjunction with zeolite builders. Dispersing agents such as
polyaspartate preferably have a molecular weight (avg.) of about 10,000.
13. Suds Suppressors
Compounds for reducing or suppressing the formation of suds can be
incorporated into the detergent compositions. Suds suppression can be of
2o 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
2s Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages
430-447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of
particular interest encompasses monocarboxylic fatty acid and soluble salts
therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St.
John. The monocarboxylic fatty acids and salts thereof used as suds suppressor
3o typically have hydrocarbyl chains of 10 to about 24 carbon atoms,
preferably 12
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to 18 carbon atoms. Suitable salts include the alkali metal salts such as
sodium,
potassium, and lithium salts, and ammonium and alkanolammonium salts.
The detergent compositions herein may also contain non-surfactant suds
suppressors. These include, for example: high molecular weight hydrocarbons
s such as paraffin, fatty acid esters (e.g., fatty acid trigiycerides), fatty
acid esters
of monovalent alcohols, aliphatic ClB-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
to containing 1 to 24 carbon atoms, propylene oxide, and monostearyl
phosphates
such as monostearyl alcohol phosphate ester and monostearyi di-alkali metal
(e.g., K, Na, and Li) phosphates and phosphate esters.
Another preferred category of non-surfactant suds suppressors comprises
silicone suds suppressors. This category includes the use of
polyorganosiloxane
is oils, such as polydimethylsiloxane, dispersions or emulsions of
polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with
silica particles wherein the polyorganosiloxane is chemisorbed or fused onto
the
silica.
Mixtures of silicone and silanated silica are described, for instance, in
2o 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.
The silicone suds suppressor herein preferably comprises polyethylene
2s glycol and a copolymer of polyethylene glycoUpolypropylene glycol, all
having an
average molecular weight of less than about 1,000, preferably between about
100 and 800. The polyethylene glycol and polyethylenelpolypropylene
copolymers herein have a solubility in water at room temperature of more than
about 2 weight %, preferabiy more than about 5 weight %.
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Other suds suppressors useful herein comprise the secondary alcohols
(e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils,
such as
the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The
secondary alcohols include the Cg-C16 alkyl alcohols having a C1-C16 chain.
s For any detergent compositions to be used in automatic laundry washing
machines, suds should not form to the extent that they overflow the washing
machine. Suds suppressors, when utilized, are preferably present in a "suds
suppressing amount. By "suds suppressing amount" is meant that the formulator
of the composition can select an amount of this suds controlling agent that
will
io sufficiently control the suds to result in a low-sudsing laundry detergent
for use in
automatic laundry washing machines.
The compositions herein will generally comprise from 0°~ to about
5% of
suds suppressor.
14. Additional Other Detersive Ingredients
is A wide variety of other ingredients useful in detergent compositions can be
included in the compositions herein, including other active ingredients,
carriers,
hydrotropes, processing aids, dyes or pigments, fillers for solid
compositions, etc.
If high sudsing is desired, suds boosters such as the C1p-C1g alkanolamides
can be incorporated into the compositions, typically at 1 %-10% levels. The
C10-
2o C14 monoethanol and diethanol amides illustrate a typical class of such
suds
boosters. Use of such suds boosters with high sudsing adjunct surfactants such
as the amine oxides, betaines and suhaines noted above is also advantageous.
If desired, soluble magnesium salts such as MgCl2, MgS04, and the like, can be
added at levels of, typically, 0.1 %-2%, to provide additional suds and to
enhance
2s grease removal performance.
The detergent compositions herein will preferably be formulated such that,
during use in aqueous cleaning operations, the wash water will have a pH of
between about 6.5 and about 11, preferably between about 7.5 and 10.5.
Laundry product formulations preferably have a pH between about 9 and about
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56
11. Techniques for controlling pH at recommended usage levels include the use
of buffers, alkalis, acids, etc., and are well known to those skilled in the
art.
E. Form of the composition
The bulk density of granular detergent compositions in accordance with
s the present invention preferably have a bulk density of at least about 250
gllitre,
more preferably from about 400 g/litre to 1200 gllitre.
In one embodiment of the present invention, the detergent composition is
made into a solid form, such as a tablet or other solid form.
The alkaline carbonate source is preferably either dry-added, delivered via
~o agglomerates, and/or added as a spray dried granule. It is especially
preferred
that at least 1 %, preferably at least 5%, of the alkaline carbonate source is
admixed. The addition of the particulate acid source, preferably citric acid,
(up to
10%) may be preferably introduced into the product as a dry-add, or via a
separate particle.
is The potassium ion source is preferably added as a spray dried granule,
agglomerate, or as a dry-add.
F. Laundry Methods
Machine laundry methods herein typically comprise treating soiled laundry
with an aqueous wash solution in a washing machine having dissolved or
2o dispensed therein an effective amount of a machine laundry detergent
composition in accord with the invention. By an effective amount of the
detergent composition it is meant from 20g to 3008 of product dissolved or
dispersed in a wash solution of volume from 5 to 65 litres, as are typical
product
dosages and wash solution volumes commonly employed in conventional
2s machine laundry methods.
In one example, a dispensing device is employed in the washing method.
The dispensing device is charged with the detergent product, and is used to
introduce the product directly into the drum of the washing machine before the
commencement of the wash cycle. Its volume capacity should be such as to be
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able to contain sufficient detergent product as would normally be used in the
washing method.
Once the washing machine has been loaded with laundry the dispensing
device containing the detergent product is placed inside the drum. At the
s commencement of the wash cycle of the washing machine water is introduced
into the drum and the drum periodically rotates. The design of the dispensing
device should be such that it permits containment of the dry detergent product
but then allows release of this product during the wash cycle in response to
its
agitation as the drum rotates and also as a result of its contact with the
wash
io water.
Attematively, the dispensing device may be a flexible container, such as a
bag or pouch. The bag may be of fibrous construction coated with a water
impermeable protective material so as to retain the contents, such as is
disclosed
in European published Patent Application No. 0018678. Alternatively it may be
is formed of a water-insoluble synthetic polymeric material provided with an
edge
seal or closure designed to rupture in aqueous media as disclosed in European
published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968.
A convenient form of water frangible closure comprises a water soluble
adhesive
disposed along and sealing one edge of a pouch formed of a water impermeable
20 polymeric film such as polyethylene or polypropylene.
G. Examples
In the following Examples, the abbreviations for the various ingredients
used for the compositions have the following meanings.
NaLAS : Sodium linear C12 alkyl benzene sulfonate
2s KLAS : Potassium linear C12 alkyl benzene sulfonate
~S : Potassium C14-15 linear alkyl sulfate
~~S : Potassium Mid-chain branched primary alkyl sulfate
KMBAES : Potassium Mid-chain branched primary alkyl
ethoxylate (Ave. EO = 1 ) sulfate
3o SRP 1 : Sulfobenzoyl end capped esters with oxyethylene oxy
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and terephtaioyl backbone
Borax : Na tetraborate decahydrate
Polyacrylic Acid (mw = 4500)
PEG : Polyethylene glycol (mw=4600)
s NaMES : Alkyl methyl ester sulfonate, sodium salt
NaSAS : Secondary alkyl sulfate, sodium salt
NaPS : Sodium paraffin sulfonate
STPP : Sodium Tri-polyphosphate
QAS : R2.N+(CHg)2(C2H40H) with R2 = C12 - C14
io TFAA : C16-C18 alkyl N-methyl glucamide
STPP y Anhydrous sodium tripolyphosphate
NaZeolite A : Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si02)12. 27H20 having a primary
particle
size in the range from 0.1 to 10 micrometers
~s size in the range from 0.1 to 10 micrometers
NaSKS-6 : Crystalline layered silicate of formula 8
-Na2Si205
NaCarbonate : Anhydrous sodium carbonate (mean size of
the
particle size distribution is between 200pm
and
900~m)
2o KCarbonate : Anhydrous potassium carbonate (mean size
of the
particle size distribution is between 200p.m
and
900~m)
NaBicarbonate : Anhydrous sodium bicarbonate (mean size of
the
particle size distribution is between 400pm
and
2s 1200p,m}
KBicarbonate : Anhydrous potassium bicarbonate (mean size
of the
particle size distribution is between 400pm
and
1200pm)
NaSilicate : Amorphous Sodium Silicate (Si02:Na2C~; 2.0
ratio)
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KSilicate : Amorphous Potassium Silicate (Si02:K20;
2.0 ratio)
MAIAA : Copolymer of 1:4 maleiclacrylic acid, average
molecular weight about 70,000.
CMC : Sodium carboxymethyl cellulose
s Protease : Proteolytic enzyme of activity 4KNPUIg sold
by
NOVO Industries AIS under the tradename
Savinase
Amylase : Amylolytic enzyme of activity 60KNU/g sold
by
NOVO Industries A/S under the tradename
Termamyl
t o 60T
Lipase : Lipolytic enzyme of activity 100kLUlg sold
by NOVO
Industries AIS under the tradename Lipolase
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g
sold by
NOVO Industries AIS under the tradename
i s Carezyme.
NaPercarbonate : Sodium Percarbonate
Kpercarbonate : Potassium Percarbonate
NOES : Nonanoyloxybenzene sulfonate in the form
of the
sodium salt.
2o DOBA : Decyl oxybenzoic acid
LOBS . Sodium lauroyl oxybenzene sulfonate
NACA-OBS . Phenol sulfonate esther of N-nonanoyl-6-aminocaproic
acid
TAED : Tetraacetylethylenediamine
2s HEDP : 1,1-hydroxyethane diphosphonic acid
Silicone antifoam : Polydimethylsiloxane foam controller with
siloxane-
oxyalkylene copolymer as dispersing agent
with a
ratio of said foam controller to said dispersing
agent of
10:1 to 100:1.
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In the following Examples all levels are quoted as % by weight of the
composition. The following examples are illustrative of the present invention,
but
are not meant to limit or otherwise define its scope. Ali parts, percentages
and
s ratios used herein are expressed as percent weight unless otherwise
specified.
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Example 1
The following laundry detergent compositions A to D are prepared in accordance
with the invention:
A B C D E F
KLAS 22 15 0 11 0 0
~S 0 7 0 0 0 0
KMBS (avg. total 0 0 0 0 11 0
carbon=16.5)
KMBAES 0 0 0 0 0 11
Any Combination 0 0 22 11 11 11
of:
NaC45 AS
NaC45E1S
NaLAS
C 16 NaSAS
C14-17 NaPS
C14-18 NaMES
C23E6.5 1.5 1.5 1.5 1.5 1.5 1.5
NaZeolite A 27.8 27.8 27.8 27.8 27.8 27.8
2.3 2.3 2.3 2.3 2.3 2.3
NaCarbonate 0 5 0 20 20 20
KCarbonate 20 30 20 0 0 0
NaSilicate 0.6 0.6 0.6 0.6 0.6 0.6
Perborate 1.0 1.0 1.0 1.0 1.0 1.0
Protease 0.3 0.3 0.3 0.3 0.3 0.3
Cellulase 0.3 0.3 0.3 0.3 0.3 0.3
SRP 0.4 0.4 0.4 0.4 0.4 0.4
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Brightener 0.2 0.2 0.2 0.2 0.2 0.2
PEG 1.6 1.6 1.6 1.6 1.6 1.6
Sulfate 5.5 5.5 5.5 5.5 5.5 5.5
Silicone Antifoam0.42 0.42 0.42 0.42 0.42 0.42
Citric Acid 3 5 0 0 0 0
Oxalic Acid 0 0 3 0 0 0
Succinic Acrd 0 0 0 10 10 10
K+ in total 13 18 10 1.2 1.2 1.1
composition
Moisture & Minors---Balance---
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Example 2
The following laundry detergent compositions G to J are prepared in accordance
with the invention:
G H I J
KLAS 20 8 20 0
~S 0 8 0 0
NaI.AS 0 2.5 0 20
NaC45 AS 5 3 5 5
C23E6.5 1.5 1.5 1.5 1.5
NaZeolite A 27.8 27.8 27.8 27.8
2.3 2.3 2.3 2.3
NaCarbonate 10 10 10 10
NaSilicate 0.6 0.6 0.6 0.6
Perborate 1.0 1.0 1.0 1.0
Protease 0.3 0.3 0.3 0.3
Cellulase 0.3 0.3 0.3 0.3
SRP 0.4 0.4 0.4 0.4
Brightener 0.2 0.2 0.2 0.2
PEG 1.6 1.6 1.6 1.6
NaSulfaite 5.5 5.5 5.5 5.5
Silicone Antifoam0.42 0.42 0.42 0.42
NaBicarbonate 10 0 0 0
Kcarbonate 0 10 0 10
Kbicarbonate 0 0 10 10
Citric Acid 3 3 3 3
K+ in total 2.2 6.9 6.8 9.7
composition
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Moisture 8~ Minors ~-Balance---
Example 3
The following laundry detergent compositions K to O are prepared in accordance
with the invention:
K L M N O
KLAS 14.8 16.4 12.3 8.2 4.1
Any Combination 0 0 4.1 8.2 12.3
of:
NaC45 AS
NaC45E1S
NaLAS
C16NaSAS
C14-17 NaPS
C14-18 Na MES
TFAA 1.6 0 0 0 0
C24E3 4.9 4.9 4.9 4.9 4.9
NaZeolite A 15 15 15 15 15
NaSKS-6 11 11 11 11 11
Citrate 3 3 3 3 3
4.8 4.8 4.8 4.8 4.8
HEDP 0.5 0.5 0.5 0.5 0.5
NaCarbonate 0 5 0 10 10
KCarbonate 10 5 20 10 1
NaPercarbonate 20.7 20.7 20.7 20.7 20.7
TAED 4.8 4.8 4.8 4.8 4.8
Protease 0.9 0.9 0.9 0.9 0.9
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Lipase 0.15 0.15 0.15 0.15 0.
9
5
Cellulase 0.26 0.26 0.26 0.26 0.26
Amylase 0.36 0.36 0.36 0.36 0.36
SRP 0.2 0.2 0.2 0.2 0.2
Brightener 0.2 0.2 0.2 0.2 0.2
NaSulfate 2.3 2.3 2.3 2.3 2..3
Silicone Antifoam0.4 0.4 0.4 0.4 0.4
Citric Acid 3 0 0 0 0
Oxalic Acid 0 3 0 0 0
Trataric Acid 0 0 3 0 0
Succinic Acid 0 0 0 3 0
Malic Acid 0 0 0 0 3
K+ in total 7.1 4.fi 12 6.4 1.0
composition
Moisture & Minors---Balance---
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Example 4
The following laundry detergent compositions P to Q are prepared in accordance
with the invention:
Q
NaC45AS 0 8
NaLAS p g
KLAS 14.8 0
TFAA 1.6 0
C24E3 . 4.9 4.9
NaZeolite A 15 15
NaSKS-6 11 11
Citrate 3 3
4.8 4.8
HEDP 0.5 0.5
NaCarbonate - 8.5 8.5
NaPercarbonate 20.7 0
Kpercarbonate 0 20.7
Citric Acid 3 3
TAED - 4.8 4.8
Protease 0.9 0.9
Lipase 0.15 0.15
CeNulase 0.26 0.26
Amylase 0.36 0.36
SRP 0.2 0.2
Brightener 0.2 0.2
NaSuliate 2.3 2.3
Silicone Antifoam0.4 0.4
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K+ in total 1.6 9.3
composition
Moisture & Minors---Balance---
Example 5
The following laundry detergent compositions R to V are prepared in accordance
with the invention:
R S T U V
KLAS 32 32 24 16 16
Any Combination 0 0 8 16 16
of:
NaC45 AS
NaC45E1S
NaLAS
C16 Na SAS
C14-17 NaPS
C14-18 Na MES
C23E6.5 3.6 3.6 3.6 3.6 3.6
~S - 0.5 - 0.5
NaZeolite A 9.0 9.0 9.0 9.0 9.0
Poiycarboxylate 7.0 7.0 7.0 7.0 7.0
NaCarbonate 0 5 0 10 10
Kcarbonate 10 5 20 10 0
NaSilicate 11.3 11.3 11.3 11.3 0
Ksilicate 0 0 0 0 11.3
Perborate 3.9 3.9 3.9 3.9 3.9
NOBS 4.1 4.1 0 0 0
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LOBS 0 0 4.1 0 0
DOBA 0 0 0 4.1 0
NACA-OBS 0 0 0 0 4.1
Protease 0.9 0.9 0.9 0.9 0.9
SRP 0.5 0.5 0.5 0.5 0.5
Brightener 0.3 0.3 0.3 0.3 0.3
PEG 0.2 0.2 0.2 0.2 0.2
NaSulfate 5.1 5.1 5.1 5.1 5.1
Silicone Antifoam0.2 0.2 0.2 0.2 0.2
Citric Acid 1 5 8 3 0.5
K+ in total 9.0 6.3 14 7.2 6.0
composition
Moisture ~ Minors-Balance---
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Example 6
The following laundry detergent compositions W to Z are prepared in accordance
with the invention:
W X Y Z
KLAS 22 16.5 11 5.5
Any Combination 0 5.5 11 16.5
of:
C45 Na AS
C45 Na E1 S
LAS
C 16 Na SAS
C14-17 NaPS
C14-18 Na MES
C23E6.5 1.2 1.2 1.2 1.2
STPP 35.0 35.0 35.0 35.0
NaCarbonate 6 5 0 10
Kcarbonate 10 5 20 10
NaZeolite A 16.0 16.0 16.0 18.0
NaSilicate 2.0 2.0 2.0 2.0
CMC 0.3 0:3 0.3 0.3
Protease 1.4 1.4 1.4 1.4
Lipolase 0.12 0.12 0.12 0.12
SRP 0.3 0.3 0.3 0.3
Brightener 0.2 0.2 0.2 0.2
Citric Acid 3 3 3 3
K+ in total 7.5 4.3 11 5.7
composition
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Moisture 8~ Minors I ---Balance---
Example 7
The following laundry detergent compositions AA to AB are prepared in
accordance with the invention:
AA AB
KAS 0 8
KLAS 22 8
C23E6.5 1.2 1.2
STPP 35.0 35.0
KCarbonate 19.0 19.0
NaZeolite A 16.0 16.0
NaSilicate 2.0 2.0
CMC 0.3 0.3
Protease 1.4 1.4
Lipolase 0.12 0.12
SRP 0.3 0.3
Brightener 0.2 0.2
K+ in total 12 11
composi5on
Moisture & Minors---Balance--
Citric Acid 1 5
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Example 8
The following laundry detergent compositions AC to AF are prepared in
accordance with the invention:
AC AD AE AF
KAS 0 8 11 0
KLAS 22 8 0 5.5
C45 NaAS 0 0 17 8
C45KE1 S 8
C23E6.5 1.5 1.5 1.5 1.5
NaZeolite A 27.8 27.8 27.8 27.8
PAA 2.3 2.3 2.3 2.3
KCarbonate 27.3 27.3 27.3 27.3
NaSilicate 0.6 0.6 0.6 0.6
Perborate 1.0 1.0 1.0 1:0
Protease 0.3 0.3 0.3 0.3
Cellulase 0.3 0.3 0.3 0.3
SRP 0.4 0.4 0.4 0.4
Brightener 0.2 0.2 0.2 0.2
PEG 1.6 1.6 1.6 1.6
NaSulfate 5.5 5.5 5.5 5.5
Silicone Antifoam0.42 0.42 0.42 0.42
Citric Acid 1 2 3 5
K+ in total 16 16 16 15
compositions
Moisture & Minors---Balance---
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Example 9
The following laundry detergent compositions AG to AH are prepared in
accordance with the invention:
AG AH
KAS 0 8
KLAS 22 8
C23E6.5 1.5 1.5
NaZeolite A 27.8 27.8
PAA 2.3 2.3
KCarbonate 10 10
KSilicate 0.6 0.6
Perborate 1.0 1.0
Protease 0.3 0.3
Cellulase 0.3 0.3
SRP 0.4 0.4
Brightener 0.2 0.2
PEG 1.6 1.6
KSulfate 5.5 5.5
Silicone Antifoam0.42 0.42
Citric Acid 3 5
K+ in total 9.9 9.3
composition
Moisture & Minors---Balance---
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Example 10
The following laundry detergent compositions AI to AL are prepared in
accordance with the invention:
AI AJ AK AL
KLAS 22 16.5 11 5.5
Any Combination 0 5.5 11 16.5
of:
NaC45 AS
NaC45E1S
NaLAS
C1fi Na SAS
C14-17 NaPS
C14-18 Na MES
C23E6.5 1.5 1.5 1.5 1.5
NaZeolite A 27.8 27.8 27.8 27.8
PAA 2.3 2.3 2.3 2.3
NaCarbonate 0 5 0 10
KCarbonate 10 5 20 10
NaSilicate 0.6 0.6 0.6 0.6
NaPerborate 1.0 1.0 0 0
Kpercarbonate 0 0 1.0 1.0
Protease 0.3 0.3 0.3 0.3
Cellulase 0.3 0.3 0.3 0.3
SRP 0.4 0.4 0.4 0.4
Brightener 0.2 0.2 0.2 0.2
PEG 1.6 1.6 1.6 1.6
NaSutfate 5.5 5.5 5.5 5.5
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Silicone Antifoam0.42 0.42 0.42 0.42
Citric Acid 2 5 10 1
K+ in total 7.5 4.3 12 6.1
composition)
Moisture 8~ Minors---Balance---
Examele 11
The following laundry detergent compositions AM to AP are prepared in
accordance with the invention:
AM AN AO AP
KLAS 14.8 16.4 12.3 8.2
Any Combination 0 0 4.1 8.2
of:
C45 NaAS
C45NaE1S
NaL~S
C16 NaSAS
C14-17 NaPS
C14-18 NaMES
TFAA 1.6 0 0 0
C24E3 4.9 4.9 4.9 4.9
NaZeolite A 15 15 15 15
NaSKS-6 11 11 0 0
KSKS-6 0 0 11 11
Citrate 3 3 3 3
MAIAA 4.8 4.8 4.8 4.8
HEDP 0.5 0.5 0.5 0.5
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NaCarbonate 0 5 0 10
KCarbonate 10 5 20 10
NaPercarbonate 20.7 20.7 10 0
TAED 4.8 4.8 4.8 4.8
Protease 0.9 0.9 0.9 0.9
Lipase 0.15 0.15 0.15 0.15
Cellulase 0.26 0.26 0.26 0.26
Amylase 0.36 0.36 0.36 0.36
SRP 0.2 0.2 0.2 0.2
Brightener 0.2 0.2 0.2 0.2
NaSulfate 2.3 2.3 2.3 2.3
Silicone Antifoam0.4 0.4 0.4 0.4
Kpercarbonate 0 0 10.7 20.7
Citric Acid 1 3 5 7
K+ in total 6.7 4.3 20 19
composition
Moisture & Minors--Balance--
Example 12
The following iaundry detergent compositions AQ to AR are prepared in
acoor~dan~ with the invention:
AQ AR
KAS 0 8
KLAS 14.8 8
TFAA 1.6 0
C24E3 4.9 4.9
NaZeolite A 15 15
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NaSKS-6 11 11
Citrate 3 3
MA/AA 4.8 4.8
HEDP 0.5 0.5
NaCarbonate 8.5 8.5
KCarbonate 5 5
NaPercarbonate 20.7 20.7
TAED 4.8 4.8
Protease 0.9 0.9
Lipase 0.15 0.15
Carezyn~e 0.26 0.26
Amylase 0.36 0.38
SRP 0.2 0.2
Brightener 0.2 0.2
NaSulfate 2.3 2.3
Silicone Antifoam0.4 0.4
Citric Acid 1 3
K+ in total 4.1 4.3
composition)
Moisture & Minors--Balance--
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Example 13
The following laundry detergent compositions AS to AT are prepared in
acconiance with the invention:
AS AT
KLAS 10 10
KAS 0 0
Any Combination 10 10
of:
NaC45 AS
NaC45E1S
NaLAS
C16 NaSAS
C14-17 NaPS
C14-18 NaMES
C24E5 5 5
NaPercarbonate 12 12
TAED 3 3
NACA-OBS 2 2
NaZeolite A 27.8 27.8
PAA 2.3 2.3
NaCarbonate 15 15
NaSilicate 0.6 0.6
Perborate 1.0 1.0
Protease 0.3 0.3
Cellulase 0.3 0.3
SRP 0.4 0.4
Brightener 0.2 0.2
.
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PEG 1.6 1.6
Sulfate 5.5 5.5
Silicone Antifoam0.42 0.42
Fumaric Acid 3 0
Acrylic Acid 0 3
K+ in total 1.1 1.1
composition)
Moisture & Minors---Balance---
