Note: Descriptions are shown in the official language in which they were submitted.
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LIQUID DETERGENT COMPOSITIONS FOR
LAUNDERING COLORED FABRICS
Field of Invention
The present invention relates to liquid laundry detergent compositions which
can be used
for washing colored fabrics and which contain additives that provide color-
enhancing benefits.
Background of the Invention
Commercially available are various liquid laundry detergents directed at
select benefits
for clothing and textile washing. Some detergents are directed at deep
cleaning (for highly soiled
or industrial fabrics), others at gentle cleaning (for delicate fabrics or
lightly soiled garments),
others at bleaching white or light colored clothing. Also available are liquid
laundry detergents
marketed for the cleaning and/or protection of colored fabrics and clothing.
Colored fabrics are a sensitive class of fabrics warranting special care
during the normal
wash cycle. For instance, colored fabrics have a tendency to release dye into
the wash solution
which can cause fading. This released dye can also be transferred to other
fabrics in the same
wash solution or even to other differently-colored parts of the same fabric.
To help reduce the
negative affects of laundering colored fabrics, color-care laundry detergents
often contain
components that are useful for inhibiting or reducing dye-transfer between
fabrics during the
wash. One example of components that are known to inhibit or reduce dye-
transfer between
fabrics during the wash is a copolymer of N-vinylimidazole and N-
vinylpyrrolidone, commonly
referred to as "PVPVI" or "PVP/PVL" Another example is polyvinylpyrrolidone,
"PVP."
However, even when utilizing a polymeric dye transfer inhibiting agent such as
PVPVI or
PVP, colored fabrics may still be faded by the free chlorine present in most
residential water
sources. Chlorine is used in many parts of the world to purify water. To make
sure that the water
is safe, a small residual amount, typically about 1 part per million (ppm), of
chlorine is left in the
water. It has been found that even this small amount of chlorine can cause
fading of chlorine-
sensitive fabric dyes. In a typical wash, there is usually enough soil on the
fabrics to scavenge
residual chlorine and minimize damage to chlorine-sensitive dyes. However, in
the rinse cycle
the soil levels are greatly reduced, and chlorine-sensitive dyes can fade
after multiple laundering
cycles.
Therefore, it is also known to use chlorine scavengers, such as
monoethanolamine, to
reduce the level of free chlorine in the wash solution and correspondingly
reduce the fading
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associated with colored fabrics. Although the currently implemented levels of
chlorine
scavengers, such as monethanolamine, may carry over in part to the rinse cycle
with water
retained in the fabric fibers from the wash cycle, the level of scavenger
carryover is generally too
low to be efficacious. Therefore, even though the colored fabrics are
protected by the chlorine
scavenger during the wash cycle, the same fabrics may still be faded during
the rinse cycle by the
free chlorine present in the rinse solution.
Optical brighteners, or fluorescent whitening agents, are often used in
laundry detergents
to provide appearance benefits. Optical brighteners work by absorbing
ultraviolet light and re-
emitting most of the absorbed energy as blue fluorescent light between ca. 400
and 500 nm. In
daylight, optical brighteners can thus compensate for the aesthetically
undesirable yellowish cast
found in white or light colored fabrics and give such fabrics a dazzling
white. However, when
optical brighteners are used in laundering colored fabrics, there often
results an undesirable color
hue shift. Even more importantly, it is also known that certain optical
brighteners, when used in
conjunction with a polymeric dye transfer inhibiting agent, often complex with
the polymeric dye
transfer inhibiting agent, resulting in an undesirably cloudy product.
Notwithstanding prior art attempts to solve the color care problems (including
fading and
dye transfer) during fabric laundering, there is a continuing need to identify
detergent
compositions, detergent composition additives, and fabric laundering methods
which are
especially effective for laundering colored fabrics. There is further a need
to identify detergent
compositions wherein the color-care components do not negatively interact with
one another.
In short, there is a continuing need to develop liquid laundry detergents that
provide a
combined strategy for color care, including; (a) reduction in free dye
concentration during the
wash cycle, resulting in less color fading and less discoloration of fabrics
by dye redeposition; (b)
reduction of dye damage and subsequent fading and color changes associated
with oxidation by
chlorine in both the wash and the rinse cycles; and (c) improvement in the
compatibility of
polymeric dye transfer inhibiting agents with typical liquid laundry detergent
formulations.
Summary of the Invention
It has now surprisingly been discovered that the combination of an effective
amount of a
chlorine scavenger, a polymeric dye transfer inhibiting agent, and less than
0.02%
triazinylaminostilbene optical brightener is useful for protecting colored
textiles during the
laundering process. It has been discovered that such combination protects the
richness and
vibrancy of colors.
The present invention relates to liquid laundry detergents comprising
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a) an effective amount of a chlorine scavenger;
b) a polymer dye transfer inhibiting agent;
c) a surfactant; and
d) wherein the composition is substantially free of triazinylaminostilbene
optical
brightener.
The present invention also relates to methods of using such detergents for
laundering
colored fabrics and/or clothing and protecting the color of such fabrics
and/or clothing. Said
methods generally comprise the step of adding a safe and effective amount of
the composition to
the drum of a washer during the laundering process.
These and other features, aspects, and advantages of the present invention
will become
eviderit to those skilled in the art from a reading of the present disclosure.
Detailed Description of the Invention
While the specification concludes with the claims particularly pointing and
distinctly
claiming the invention, it is believed that the present invention will be
better understood from the
following description.
All percentages and ratios used herein are by weight of the total composition
and all
measurements made are at 25°C, unless otherwise designated.
The compositions of the present invention can include, consist essentially of,
or consist
of, the components of the present invention as well as other ingredients
described herein. As
used herein, "consisting essentially of means that the composition or
component may include
additional ingredients, but only if the additional ingredients do not
materially alter the basic and
novel characteristics of the claimed compositions or methods.
All percentages, parts and ratios are based upon the total weight of the
liquid laundry
detergent compositions of the present invention, unless otherwise specified.
All such weights as
they pertain to listed ingredients are based on the active level and,
therefore, do not include
carriers or by-products that may be included in commercially available
materials, unless
otherwise specified.
It has now been found that detergent compositions containing a combination of
a higher
level of chlorine scavenger with a detersive surfactant and a polymeric dye
transfer inhibitor, in
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the absence, or near absence, of triazinylaminostilbene optical brightener,
are useful for
providing improved colored fabric laundering results.
Without being limited by theory, it is believed that the higher level of
chlorine scavenger
in the formulation reduces the bleaching affect of free chlorine in both the
wash cycle and the
rinse cycle, as opposed to prior detergents which generally reduced the
bleaching affect during
only the wash cycle. In addition, it is believed that such higher levels of
chlorine scavengers, in
combination with a polymeric dye transfer inhibitor, provide advantages to
which the prior art is
unaware. Furthermore, the absence, or near absence, of triazinylaminostilbene
optical brightener
reduces the cloudiness of the formulation attributable to the interaction
between the optical
brightener and the polymeric dye transfer inhibitor. Cloudiness is especially
undesirable in liquid
detergent compositions.
Therefore, the liquid laundry detergent compositions of the present invention
contain an
effective amount of a chlorine scavenger, a polymeric dye transfer inhibiting
agent, and a
detersive surfactant. The compositions of the present invention contain less
than 0.02% of
triazinylaminostilbene optical brightener.
The compositions herein may also include a wide variety of other ingredients.
The
compositions of the present invention, are described in detail hereinafter.
I. Chlorine Scavenger
The compositions of the present invention comprise a chlorine scavenger. As
used
herein, the term "chlorine scavenger" refers to any compound or material that
is capable of de-
activating free chlorine (C12 and/or hypochlorite) in solution or at the
fabric/solution interface.
De-activation can take place either by direct reduction of chlorine species by
the chlorine
scavenger, such as to chloride, or by combination of the chlorine scavenger
with a chlorine
species to yield a less oxidizing species for dyes or chlorine bleach-
sensitive textile, fibers than
free chlorine. Such less oxidizing species include for example chlorine
adducts, e.g., chloramines
when the chlorine scavenger contains an amino nitrogen moiety.
Chlorine scavengers useful herein typically contain either an atom, site or
moiety that is
readily halogenated, e.g., a trivalent nitrogen, or another non-nitrogen
electron-rich site or moiety
which is readily susceptible to attack by chlorine or hypochlorite.
Chlorine scavengers useful herein include nonpolymeric types which tend to be
the most
rapidly reacting, and polymeric types, which can be preferred on account of
lower tendency to be
associated with odors. Also the chlorine scavenger can be nitrogen-containing
or nitrogen-free.
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Nonpolymeric nitrogen containing chlorine scavengers
For example, an especially preferred nonpolymeric nitrogen containing chlorine
scavenger is monoethanolamine. More generally a class of preferred
nonpolymeric nitrogen
containing chlorine scavengers to which monoethanolamine belongs are
nonpolymeric nitrogen
containing chlorine scavengers selected from hydroxyfunctional primary amines,
hydroxyfunctional secondary amines and mixtures thereof wherein such
hydroxyfunctional
amines comprise from two to eight carbon atoms. These highly preferred
chlorine scavenger
compounds have the unusual combination of properties of simultaneously having
chlorine
scavenging properties, polar solvent properties, buffering properties, and the
capacity to act as
neutralizing agents for the acid form of anionic detersive surfactants or for
fatty acids. Other
chlorine scavengers in this class include diethanolamine, isopropanolamine,
and mixtures of such
lower alkanolamines with monoethanolamine or with each other.
Preferably for rapid reaction, the chlorine scavenger is a nonpolymeric
chlorine
scavenger, or, when a polymeric chlorine scavenger is selected, it is selected
on the basis of being
relatively rapidly reacting with free chlorine as compared with other
polymers.
Other nonlimiting examples of nonpolymeric nitrogen containing chlorine
scavengers
useful herein include: ammonia or ammonium salts such as ammonium nitrate,
sulfate or
carbonate, nonpolymeric amines, imines, amidines, acrylamides, and mixtures
thereof. Suitable
amines for example include 2-methyl pentamethylene diamine (MPMD), triethylene
tetramine
(TETA) and dimethylamidopropylene (bis-DMAPA), diethylene triamine (DETA). Yet
other
nonpolymeric nitrogen containing chlorine scavengers include
aminomethanephosphonic acid or
its water soluble salts where the acid has the formula:
HO D
~!I
JP ~-CH' ~° NHz
lea
Still other nonpolymeric nitrogen containing chlorine scavengers include amino
acids (whether
natural or synthetic) or their water-soluble salts, aminocarboxylic acids or
their water-soluble
salts, sulfamic acid or its water-soluble salts, and mixtures of any of the
foregoing compounds.
When such nitrogen-containing chlorine scavenger can be used as a neutralizer
or counter-ion for
an anionic species of the composition, such as an anionic surfactant, this
provides another salt
form in which the chlorine scavenger can be introduced into the composition.
In such a situation,
for formula accounting purposes, the aminofunctional cation of the chlorine
scavenger will be
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WO 2004/031335 PCT/US2002/031050
accounted as a chlorine scavenger component and the surfactant anion as a
surfactant component
of the composition. Other less preferred nitrogen containing chlorine
scavengers include
hydrazine or its derivatives.
It is preferred that the volatility of nonpolymeric nitrogen containing
chlorine scavenger
compounds be relatively low, e.g., normal boiling points of about 50 deg. C or
higher , preferably
80 deg. C or higher. Substitution of an aminofunctional (e.g., trivalent
nitrogen containing
nonpolymeric) chlorine scavenger with -OH moieties helps reduce odor and
volatility as
compared to the corresponding unsubstituted amine.
Polymeric nitrogen containing chlorine scavengers
Nonlimiting examples of polymeric nitrogen containing chlorine scavengers
useful herein
include any suitable nitrogen containing polymeric derivatives, such as
polyamines, polyimines,
polyamidines, polyacrylamides, proteins, polypeptides of natural or synthetic
origin, such as
hydrolyzed vegetable proteins, derivatives of chitin or chitosan, and mixtures
thereof.
Polyamines are addition or condensation products from multivalent aliphatic
amines and
compounds with several groups capable of reacting, for example, epichlohydrin
or alkylene
dihalides. Therefore they contain several secondary, tertiary, or even
quaternary nitrogen atoms;
moreover they may further optionally comprise one or more hydroxyl groups in
the molecule.
They are hydrophilic, polar compounds that behave as polyelectrolytes and are
water soluble,
inasmuch as they do not contain large hydrophobic groups in the molecule. The
amines and
polyamines exhibit basic reaction in aqueous solution. Suitable compounds, for
example, are
described in U.S. Patent 2,969,302 to Nalco Chemical, issued January O1, 1961.
Polyimines, especially polyethyleneimines, may have desirable reactivity and
physical
attributes. Polyethyleneimines are obtained by acid-catalyzed polymerization
of ethyleneimine
and can be modified by urea and epichlorhydrin or dichloretheane. Polyimines
and
polyethyleneimines can contain primary, secondary, or tertiary amino groups as
well as
quarternary ammonium groups. Aqueous solutions of imines or polyimines show
basic reaction.
Polyamidines and polyamineamides contain amino and amido groups in the
molecule at
the same time. They are made, for example, by condensation of multibasic
acids, for example,
dibasic, saturated, aliphatic C3 to C$ acids and polyamines as well as with
compounds that
contain several groups capable of reacting, such as for example
epichlorhydrin. These
compounds also demonstrate basic reaction in aqueous solution. Suitable
compounds, for
example, are described in U.S. Patent 2,926,154 to Hercules Powder Company,
issued February
23, 1960.
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WO 2004/031335 PCT/US2002/031050
O -R2
/N
R~ R3
Amides are compounds with adjacent carbonyl and amine moieties, as exemplified
in the
above structure. When R, is C=C this is acrylamide, the basis for the
polyacrylamides.
Polyacrylamides having amino groups and molecular weights up to several
million are also
suitable for use herein. By building in carboxyl groups, which are formed, for
example, by
partial hydrolysis, anionic polyacrylamides are obtained in addition to amido
groups, while
polyacrylamides containing amino groups exhibit basic reaction in aqueous
solution.
Other Non-aminofunctional Chlorine Scavengers
Other non-aminofunctional chlorine scavengers useful herein include anions of
reducing
materials such as sulfite, bisulfate, thiosulfite, thiosulfate, iodide,
nitrite, etc and antioxidants
such as carbamate, ascorbate, etc. and mixtures thereof. Additionally,
conventional non-chlorine
scavenging anions like sulfite, bisulfate, carbonate, bicarbonate, nitrate,
acetate, benzoate, citrate,
formate, lactate, salicylate, etc. and mixtures thereof can be used with any
water-soluble counter-
ions. Yet other non-aminofunctional chlorine scavengers include 2,2-
oxydisuccinate, sodium
perborate, inorganic peroxo-compounds, nitric acid and 4-hydroxybenzoic acid;
alkyl benzoic
acids and alkyl benzene sulfonic acids having a short chain alkyl substituent
such that they are
not appreciably active as surfactants, e.g., methyl.
Salts of phosphorous acid and sodium hypophosphite are also useful herein as
chlorine
scavengers. In addition, chlorine scavengers such as the hydroxysulfinate
adducts of aliphatic,
aromatic, or heterocyclic mono- or dialdehyde or ammonia adduct thereof,
disclosed in U.S.
Patent 4,786,434, to Gunter, et al. Issued Nov. 22, 1988, may also be used
herein.
Levels of Chlorine Scavenger
The compositions preferably contain from about 0.1% to about 20%, more
preferably
from about 0.1 % to about 10%, more preferably from about 1 % to about 10%,
more preferably
from about 1.5% to about 5%, by weight of the composition, of the chlorine
scavenger. The level
selected is preferably that which adequately eliminates (or nearly eliminates)
ambient chlorine
levels in the water supply (approximately 0.8ppm average in United States'
water supplies) for
both the wash cycle and the rinse cycle of a typical United States washing
machine. The actual
amount of chlorine scavenger needed will vary based on the molecule selected,
the extent of the
wash water carryover to the rinse, product dosage, and level of residual
chlorine in the rinse
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water. For example, under typical U.S. washing conditions, greater than
approximately 1.5%, by
weight of the composition, of monoethanolamine in a liquid laundry detergent
would be needed
to scavenge the chlorine in the rinse water, assuming approximately 5% of the
wash water is
carried over to the rinse cycle and approximately 0.8ppm of residual chlorine
in the rinse water.
Mixtures of more than one chlorine scavenger may be used. Suitable chlorine
scavengers
for use herein are commercially available from a number of sources, e.g.,
BASF, Union Carbide,
Dow Chemical, Jefferson Chemical Company, Allied Chemical Company, and
Huntsman.
Odor Suppression with aminofunctional chlorine scavengers
In order to suppress any malodor associated with the use of certain
aminofunctional
chlorine scavengers, packages and perfumes such as those disclosed in PCT
Published
Application WO 00123274 A1, to Kaiser, et al., published Apr. 5, 2001, may be
used in
conjunction with compositions according to the present invention.
II. Polymeric Dye Transfer Inhibiting Agent
The compositions of the present invention may contain a polymeric dye transfer
inhibiting agent. Polymeric dye transfer inhibiting agents are known in the
art for reducing or
preventing dye-transfer during the laundering process. Polymeric dye transfer
inhibiting agents
useful herein include polyvinylpyrrolidone and copolymers thereof.
a) Pol v~in~pyrrolidone
Polyvinylpyrrolidone ("PVP") has an amphiphilic character with a highly polar
amide
group conferring hydrophilic and polar attracting properties, and also has
apolar methylene and
methane groups, in the backbone and/or the ring, conferring hydrophobic
properties. The rings
may also provide planar alignment with the aromatic rings, in the dye
molecules. PVP is readily
soluble in aqueous and organic solvent systems. PVP is commercially available
from BASF
Corporation, Parsippany, N.J. in either powder or aqueous solutions in several
viscosity grades.
b) Copolymers of N-vinylpxrrolidone and N-vinylimidazole
The detergent compositions of the present invention may also utilize a
copolymer of N-
vinylpyrrolidone and N-vinylimidazole (also abbreviated herein as "PVPVI"). It
has been found
that copolymers of N-vinylpyrrolidone and N-vinylimidazole can provide
excellent dye transfer
inhibiting performance when utilized in the compositions of this invention.
In a preferred embodiment, the copolymer of N-vinylpyrrolidone and N-
vinylimidazole
polymers has an average molecular weight range from 5,000 to 1,000,000, more
preferably from
5,000 to 200,000. A highly preferred copolymer for use in detergent
compositions according to
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the present invention has an average molecular weight range from 5,000 to
50,000, more
preferably from 8,000 to 30,000 and, most preferably from 10,000 to 20,000.
The average
molecular weight range is determined by light scattering as described in Barth
J. H. G. and Mays
J. W. Chemical Analysis Vol 113. "Modern Methods of Polymer Characterization."
The copolymers of N-vinylpyrrolidone and N-vinylimidazole useful in the
present
invention can have a molar ratio of N-vinylimidazole to N-vinylpyn olidone
from 1:1 to 0.2:1,
more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. It
should be understood
that the copolymer of N-vinylpyrrolidone and N-vinylimidazole can be either
linear or branched.
Copolymers of poly(N-vinyl-2-pyrrolidone) and poly(N-vinyl-imidazole) are
commercially
available from a number of sources including BASF and International Specialty
Products. U.S.
Patent 6,391,995 Issued May 21, 2002 to Muragan, assigned to Reilly
Industries, lnc. teaches
process for preparing dye-transfer inhibiting polymers. Such process is
preferred for preparation
of the PVP and PVPVI agents herein.
Preferably, the polymeric dye transfer inhibiting agent is a copolymer of
poly(N-vinyl-2-
pyrollidone) and poly(N-vinyl-imidazole) (commonly referred to as PVPVI).
The compositions preferably contain from about 0.001% to about 10%, more
preferably
from about 0.01% to about 5%, even more preferably from about 0.05% to about
1%, by weight
of the composition, of the polymeric dye transfer inhibiting agent.
Mixtures of more than one polymeric dye transfer inhibiting agent may be used.
BI. Detersive Surfactant
The detergent compositions herein comprise from about 1% to 80%, by weight of
the
composition, of a detersive surfactant. Preferably such compositions comprise
from about 5% to
50%, by weight of the composition, of the surfactant. Detersive surfactants
utilized can be of the
anionic, nonionic, zwitterionic, amphoteric or cationic type or can comprise
compatible mixtures
of these types. Detergent surfactants useful herein are described in U.S.
Patent 3,664,961, Norris,
issued May 23, 1972, U.S. Patent 3,919,678, Laughlin et al., issued December
30, 1975, U.S.
Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent
4,239,659, Murphy,
issued December 16, 1980.
Anionic surfactants which suitable for use herein include the water-soluble
salts, preferably
the alkali metal, ammonium and alkylammonium salts, of organic sulfuric
reaction products
having in their molecular structure an alkyl group containing from about 10 to
about 20 carbon
atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term
"alkyl" is the alkyl
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portion of acyl groups.) Examples of this group of synthetic surfactants are
a) the sodium,
potassium and ethanolamine alkyl sulfates, especially those obtained by
sulfating the higher
alcohols (C8 C18 carbon atoms) such as those produced by reducing the
glycerides of tallow or
coconut oil; b) the sodium, potassium and ethanolamine alkyl polyethoxylate
sulfates,
particularly those in which the alkyl group contains from 10 to 22, preferably
from 12 to 18
carbon atoms, and wherein the polyethoxylate chain contains from 1 to 15,
preferably 1 to 6
ethoxylate moieties; and c) the sodium and potassium alkylbenzene sulfonates
in which the alkyl
group contains from about 9 to about 1 S carbon atoms, in straight chain or
branched chain
configuration, e.g., those of the type described in U.S. Patents 2,220,099 and
2,477,383.
Especially valuable are linear straight chain alkylbenzene sulfonates in which
the average number
of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C11-
13 LAS.
Preferred nonionic surfactants are those of the formula R1(OC2H4)nOH, wherein
R1 is a
C10 C16 alkyl group or a C8-C12 alkyl phenyl group, and n is from 3 to about
80. Particularly
preferred are condensation products of C12-C15 alcohols with from about 5 to
about 20 moles of
ethylene oxide per mole of alcohol, e.g., C12-C13 alcohol condensed with about
6.5 moles of
ethylene oxide per mole of alcohol. Additional suitable nonionic surfactants
include polyhydroxy
fatty acid amides of the formula
R-C-N-Z
wherein R is a C9_17 alkyl or alkenyl, R1 is a methyl group and Z is glycityl
derived from a
reduced sugar or alkoxylated derivative thereof. Examples are N-methyl N-1-
deoxyglucityl
cocoamide and N-methyl N-1-deoxyglucityl oleamide. Processes for making
polyhydroxy fatty
acid amides are known and can be found in Wilson, U.S. Patent 2,965,576 and
Schwartz, U.S.
Patent 2,703,798 .
In addition to the anionic and nonionic surfactants describe, the compositions
of the
present invention may also contain cationic, amphoteric, or zwitterionic
surfactants, typically
added to improve surfactancy. Preferred cationic surfactants include amine
oxides, for example,
C8-C16 alkyl dimethylamine N-oxides, or amino functional surfactants.
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Mixtures of surfactants, such as LAS (linear alkyl benzene sulfonate) in
combination
with a co-surfactant such as ethoxylated alkyl sulfate (such as AES) and/or
nonionic surfactant
are preferably used herein.
Detersive surfactants such as those disclosed in U.S. Patent No. 5,466,802 to
Panandiker,
Issued November 14, 1995, assigned to Procter & Gamble, may also be used
herein.
IV. Substantially Free of Optical Brightener
The compositions of the present invention contain very low levels of optical
brighteners
that react with the polymeric dye transfer inhibiting agent to cause
unacceptable product
cloudiness. Preferably, the level of optical brightener in the composition is
less than about
0.02%, by weight of the composition.
However, it is possible that certain optical brighteners, which do not react
with the
polymeric dye transfer inhibiting agent may be included in the compositions of
the present
invention at levels somewhat higher than 0.02%. To determine whether a given
brightener may
be included in the compositions of the present invention, and at what level, a
product cloudiness
determination may be made. Product cloudiness does not necessarily affect the
performance of a
given composition, but it is often aesthetically unacceptable to the consumer.
To determine the
product cloudiness attributable to the inclusion of optical brightener, a
simple comparison test
may be utilized. First, a sample of a brightener-free detergent composition is
dosed with a
specified amount of optical brightener and mixed well. The mixture is stored
for 48 hours at
70°F. Then, the optical absorbance of both the control brightener-free
detergent and the optical
brightener-containing detergent are measured at a wavelength well removed from
brightener
fluorescence emission and intrinsic product absorbance (for example, 750 nm
for a typical
nominally blue liquid laundry formulation). Such readings provide a measure of
transmitted light
loss due to both intrinsic absorbance and loss due to scattering in cloudy
product. The readings
are compared. If the increase in absorbance readings from the control to the
brightener-
containing composition are equal to or less than about 0.15 absorbance units,
then the product is
considered to have an acceptable level of cloudiness. These measurements may
be used to
determine the maximum level of a given brightener that may be included in the
formula.
Preferably, the compositions of the present invention containing brightener
have an increase of
less than 0.05 absorbance units, and more preferably, no detectable change in
optical absorbance
if a brightener is included, in comparison to a brightener-free control
composition.
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For example, 1,3,5-Triazinyl derivatives of 4,4'-diaminostilbene-2,2'-
disulfonic acid is
the class of optical brightener generally referred to as
triazinylaminostilbene brighteners.
Brighteners in the class of triazinylaminostilbenes have been found to complex
with the
. polymeric dye transfer inhibiting agent and cause undesirable cloudiness in
the formula. By
using the above comparison test, it was determined that the compositions of
the present invention
should contain less than 0.02%, by weight of the composition, of the
trizinylaminostilbene
brightener sold under the trademark "Tinopal-UNPA-GX" (discussed below) in
order to avoid
unacceptable product cloudiness.
Triazinyl aminostilbene optical brighteners generally conform to the following
structural
formula:
H
R2 R
N ~N
N N R2
M+ H
wherein R1 may be selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is
selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morpholino, chloro and
amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a
cation
such as sodium, the brightener is 4,4,~-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-triazine-2-
yl)amino]-2,2~-stilbenedisulfonic acid disodium salt. This particular
brightener species is
commercially marketed under the trademark Tinopal-UNPA-GX by Ciba-Geigy
Corporation.
When in the above formula, Rl is anilino, R2 is morpholino and M is a cation
such as
sodium, the brightener is 4,4,~-bis[(4-anilino-6-morphilino-s-triazine-2-
yl)amino]-2,2~-
stilbenedisulfonic acid, sodium salt. This particular brightener species is
commercially marketed
under the trademarkTinopal AMS-GX by Ciga-Geigy Corporation.
Brighteners in other classes can also cause unacceptable product cloudiness.
Ciba Tinopal
CBS can cause product cloudiness at levels of 0.05% or greater, by weight of
the composition,
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WO 2004/031335 PCT/US2002/031050
when included in compositions of the present invention. Tinopal CBS is a
distyrylbiphenyl and
is in the carbocycle class of optical brighteners.
Preferably, the compositions of the present invention contain only very low
levels of
optical brighteners in the triazinylaminostilbene or carbocycle classes, where
the acceptable level
of brightener is determined by the amount of cloudiness developed in a given
detergent
formulation. Other brighteners may be present in the formulation, provided
that they do not
cause unacceptable product cloudiness as determined by the comparison test set
out above. More
preferably, the compositions of the present invention are substantially free
of all hydrophilic
optical brightener. Even more preferably, the compositions of the present
invention are
substantially free of all optical brighteners. Optical brighteners, including
triazinylaminostilbenes, are more fully discussed in Ullman's Encyclopedia of
Industrial
Chemistry, Fifth Edition, Vol. A18, Pages 153 to 176.
As used herein, "substantially free" of brightener means that the compositions
of the
present invention contains less than or equal to about 0.02%, by weight of the
composition, of the
brightener. Preferably, the compositions of the present invention contain less
than about 0.001%,
more preferably contain less than about 0.0001%, by weight of the composition,
more preferably
contain no detectable percentage, of brightener.
OPTIONAL INGREDIENTS
The compositions of the present invention may contain one or more additional
liquid
laundry detergent components. Classifications herein are made for the sake of
convenience and
are not intended to limit the ingredient to that particular application or
applications listed.
Builders
The laundry detergent compositions of the present invention preferably
comprise one ore
more detergent builders or builder systems. When present, the compositions
will typically
comprise from about 1% builder, preferably from about 5%, more preferably from
about 10% to
about 80%, preferably to about 50%, more preferably to about 30% by weight of
the composition,
of detergent builder.
Inorganic or phosphorus-containing detergent builders include, but are not
limited to, the
alkali metal, ammonium and alkanolammonium salts of polyphosphates
(exemplified by the
tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates),
phosphonates, phytic
acid, silicates, carbonates (including bicarbonates and sesquicarbonates),
sulfates, and
13
CA 02496527 2005-02-24
aluminosilicates. Phosphate builders may not be appropriate for use in some
U.S. formulations
due to environmental constraints. 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 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
SiO2:Na20 ratio in the range of 1.6:1 to 3.2:1 and layered silicates, such as
the layered sodium
silicates described in U.S. 4,664,839 to Rieck, issued May 12, 1987. NaSKS-6
is the trademark
for a crystalline layered silicate marketed by Hoechst (commonly abbreviated
herein as "SKS-
6"). Unlike zeolite builders, the NaSKS-6 silicate builder does not contain
aluminum. Various
TM TM TM
other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as
the alpha,
beta and gamma forms.
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.
Organic~detergent builders suitable for the purposes of the present invention
include, but
are not restricted to, a wide variety of polycarboxylate 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 form, alkali
metals, such as sodium potassium, and lithium, or alkanolammonium salts are
preferred.
Included among the polycarboxylate builders are the following categories of
useful
materials: ether polycarboxylates (including oxydisuccinate); "TMSfTDS"
builders of U.S.
4,663,071 to Bush, et al., issued May 5, 1987. Other suitable ether
polycarboxylates include
cyclic compounds, particularly alicyclic compounds.
Other useful detergency builders include the ether hydroxypolycarboxylates,
copolymers
of malefic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxy
benzene-2,4,6-
trisulfonic acid, and carboxymethyloxysuccinic acid, the various alkali metal,
ammonium and
substituted ammonium salts of polyaeetic acids such as ethylenediamine
tetraacetie acid and
nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid,
succinic acid,
oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,
carboxymethyloxysuccinic
acid, and soluble salts thereof.
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Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium salt), are
polycarboxylate builders of particular importance for heavy duty liquid
detergent formulations
due to their availability from renewable resources and their biodegradability.
Also suitable in the detergent compositions of the present invention are the
3,3-
dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S.
4,566,984, Bush,
issued January 28, 1986. Useful succinic acid builders include the CS-CZO
alkyl and alkenyl
succinic acids and salts thereof. A particularly preferred compound of this
type is
dodecenylsuccinic acid. Specific examples of succinate builders include:
laurylsuccinate,
myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-
pentadecenylsuccinate,
and the like. Laurylsuccinates are the preferred builders of this group.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,
Crutchfield, et al,
issued March 13, 1979 and in U.S. 3,308,067, Diehl, issued March 7, 1967.
Fatty acids, e.g., C,z-C,8 monocarboxylic acids, can also be incorporated into
the
compositions alone, or in combination with the aforesaid builders, especially
citrate and/or 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.
Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other
known
phosphonates, can also be used.
Dispersants
Any suitable clay/soil dispersant or anti-redeposition agent can be used in
the laundry
compositions of the present invention. Polylalkyleneimine dispersants, which
are known in the
art, may also be used in the compositions of the present invention.
Acrylic/maleic-based copolymers may also be used as a preferred component of
the
dispersing/anti-redeposition agent. Such materials include the water-soluble
salts of copolymers
of acrylic acid and malefic acid. The average molecular weight of such
copolymers in the acid
form preferably ranges from about 2,000, more preferably from about 5,000,
more preferably
from about 7,000 to 100,000, more preferably to 75,000, most preferably to
65,000. The ratio of
acrylate to maleate segments in such copolymers will generally range from
about 30:1 to about
1:1, more preferably from about 10:1 to 2:1. Water-soluble salts of such
acrylic acid/maleic acid
copolymers can include, for example, the alkali metal, ammonium and
substituted ammonium
salts. Such polymers may also comprise hydroxypropylacrylate. Still other
dispersing agents
include the maleic/acrylic/vinyl alcohol terpolymers.
CA 02496527 2005-02-24
WO 2004/031335 PCT/US2002/031050
Another polymeric material which can be included is polyethylene glycol (PEG).
PEG
can exhibit dispersing agent performance as well as act as a clay soil removal-
antiredeposition
agent. Typical molecular weight ranges for these purposes range from about 500
to about
100,000, preferably from about 1,000 to about 50,000, more preferably from
about 1,500 to about
10,000.
Polyaspartate and polyglutamate dispersing agents may also be used, especially
in
conjunction with zeolite builders. Dispersing agents such as polyaspartate
preferably have a
molecular weight (avg.) of about 10,000.
Soil Release Agents
The compositions according to the present invention may optionally comprise
one or
more soil release agents. If utilized, soil release agents will generally
comprise from about
0.01 %, preferably about 0.1 %, more preferably from about 0.2% to about 10%,
preferably to
about 5%, more preferably to about 3% by weight, of the composition. Polymeric
soil release
agents are characterized by having both hydrophilic segments, to hydrophilize
the surface of
hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to
deposit upon
hydrophobic fibers and remain adhered thereto through completion of the
laundry cycle and, thus,
serve as an anchor for the hydrophilic segments. This can enable stains
occurring subsequent to
treatment with the soil release agent to be more easily cleaned in later
washing procedures.
The following references describe non-limiting examples of soil release
polymers
suitable for use in the present invention. U.S. Patent 5,728,671 to Rohrbaugh,
et al., issued Mar.
17, 1998; U.S. Patent 5,691,298 to Gosselink, et al., issued Nov. 25, 1997;
U.S. 5,599,782 to
Pan, et al., issued Feb. 4, 1997; U.S. Patent 5,415,807 to Gosselink, et al.,
issued May 16, 1995;
U.S. Patent 5,182,043 to Morrall, et al., issued Jan. 26, 1993; U.S. 4,956,447
to Gosselink, et al.,
issued Sep. 11, 1990; U.S. Patent 4,976,879 to Maldonado, et al., issued Dec.
11, 1990; U.S.
4,968,451 to Scheibel, et al., issued Nov. 6, 1990; U.S. Patent 4,925,577 to
Borcher, Sr., et al.,
issued May 15, 1990; U.S. Patent 4,861,512 to Gosselink, issued Aug. 29, 1989;
U.S. Patent
4,877,896 to Maldonado, et al., issued Oct. 31, 1989; U.S. Patent 4,721,580 to
Gosselink, issued
Jan. 26, 1988.
The detergent compositions of the present invention may comprise other soil
release
agents known in the art. The compositions may also comprise mixtures of two or
more soil
release agents.
Other Optional Components
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The detergent composition of the present invention can also include any number
of additional
optional ingredients. These include conventional detergent composition
components such as suds
boosters or suds suppressers, anti-tarnish and anticorrosion agents, soil
suspending agents, soil
release agents, germicides, pH adjusting agents, non-builder alkalinity
sources, chelating agents,
smectite clays, enzymes, enzyme-stabilizing agents and perfumes. (S~e, U.S.
Patent 3,936,537,
issued February 3, 1976 to Baskerville, Jr. et al., See also, U.S. Patent
4,285,841, Barrat et al., issued
Aug. 25, 1981, and See also. U.S. Patent No. 4,844,824 Mermelstein et al.,
issued Jul. 4, 1989).
Additional dye transfer inhibiting agents and additional optical brighteners
may also be
included. For example, polyvinylpyridine N-oxide (PVNO) is a suitable dye
transfer inhibiting
polymer for use in the present detergent composition. Furthermore, additional
relatively
hydrophobic brighteners optionally may be employed. However, the detergent
compositions herein
are preferably substantially free of all optical brighteners.
Chelating agents are described in U.S. Patent 4,663,071, Bush et al., from
Column 17, line
54 through Column 18, line 68, and are also described in U.S. Patent
4,909,953, Sadlowski, et al.
issued Mar. 20, 1990. Suds modifiers are also optional ingredients and are
described in U.S.
Patents 3,933,672, issued January 20, 1976 to Bartoletta et al., and
4,136,045, issued January 23,
1979 to Gault et al.. Suitable smectite clays for use herein are described in
U.S. Patent
4,762,645, Tucker et al, issued August 9, 1988, Column 6, line 3 through
Column 7, line 24.
While not essential to the detergent composition of the invention, it is
preferable to include
an enzyme component. Suitable enzyme components are available from a wide
variety of
commercial sources. For example, suitable enzymes are available from NOVO
Industries under
product names T-GranulateTM and SavinaseTM, and Gist-Brocades under product
names Maxaeal~
and Maxatase~. Included within the group of enzymes are proteases, amylases,
lipases,
cellulases and mixtures thereof. A preferred cellulase enzyme is Carezyme~.
The enzyme
concentration preferably should be from about 0% to about 5%, more preferably
from about 0.1%
to about 2.5%, and most preferably from about 0.2% to about 1 %. Typically,
proteases are used
at an Activity Unit (Arson Unit) level of from about 0.001 to about 0.05, most
preferably from
about 0.002 to about 0.02, while amylases are used at an amylase unit level of
from about 5 to
about 5000, most preferably from about SO to about 500 per gram of detergent
composition.
Thickeners such as trihydroxystearin may also be used herein.
Detergent Comuosition Formulation
The detergent compositions according to the present invention are in liquid
form. Liquid
detergent compositions can be prepared by admixing the essential and optional
ingredients
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WO 2004/031335 PCT/US2002/031050
thereof in any desired order to provide compositions containing components in
the requisite
concentrations. Liquid compositions according to the present invention can
also be in "compact
form", in such case, the liquid detergent compositions according to the
present invention will
contain a lower amount of water, compared to conventional liquid detergents.
The chlorine
scavenger can be dissolved or can be suspended. If the chlorine scavenger is
solid, rapidly
dissolving forms for wash bath are preferred.
The detergent compositions may be isotropic or non-isotropic liquids, may be
Newtonian,
or non-newtonian. The detergent compositions may be structured liquids, both
internally and/or
externally structured. Preferably, the compositions of the present invention
are isotropic liquids.
Detergent Packaging
The detergent compositions according to the present invention may be presented
to the
consumer in standard packaging, or may be presented in any suitable packaging.
Recently,
multiple compartment bottles containing multiple formulations that are
dispensed and combined
have become used for detergent compositions. The compositions of the present
invention may be
formulated for inclusion in such packages. In addition, unit dose packages
have also become
commonly used for detergent compositions. Such packages are also suitable for
use with the
compositions of the present invention.
Methods of Use
The present invention also provides a method for improved laundering of
colored fabrics.
Such a method employs contacting these fabrics with an aqueous washing
solution formed from
an effective amount of the detergent compositions hereinbefore described.
Contacting of fabrics
with washing solution will generally occur under conditions of agitation.
Agitation is preferably provided in a washing machine for good cleaning.
Washing is
preferably followed by drying the wet fabric in a conventional clothes dryer.
An effective
amount of the liquid detergent composition in the aqueous wash solution in the
washing machine
is preferably from about 500 to about 7000 ppm, more preferably from about
1000 to about 3000
ppm, under typical U.S. washing conditions. In the newer high efficiency (HE)
washing
machines, higher product concentrations are delivered to fabric, and therefore
soil and dye-loads
in the wash solution are even higher. Product concentration and raw material
levels are thereby
adjusted to accommodate these changes in wash conditions due to washing
machine changes.
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Examples
The following examples A through X further describe and demonstrate
embodiments
within the scope of the present invention. The examples are given solely for
the purpose of
illustration and are not to be construed as limitations of the present
invention, as many variations
thereof are possible without departing from the spirit and scope of the
invention.
All of these compositions provide an acceptable level of product cloudiness
and provide
effective cleaning of colored fabrics while reducing dye transfer and fading.
All percentages are
listed by weight of the composition formed.
EXAMPLES A-D
Liquid laundry detergents according to the present invention having improved
performance with colored fabrics are prepared by conventional means:
Component A B C D
Linear Alkyl Benzene3.0 1.5 12 10.0
Sulfonate
A1 1 Ethox Sulfate9.5 8.5 7.0
Fatty alcohol ethoxylate1.5 1.5 8 6.0
9E0
Sodium Citrate S.0
Citric Acid 1.5 3.0 1.0
Fa Acid 0.5 0.5 4.0
En es 1.0 1.0 2.0
Borax 1.5 0.75 3.0
Soil Release Pol 1.0 2.0 2.0
ers
Ethanol 1.5 1.0
Pro anediol 3.0 3.0 8.0
Pro lene Gl col 8.0
Sorbitol 4.5
Monoethanolamine 2.0 2.0 3.0 2.0
PVPVI 0.1 0.1 0.1 0.5
Water / Minors Balance
up to
100%
EXAMPLES E-G
Liquid laundry detergents according to the present invention having improved
performance with colored fabrics are prepared by conventional means:
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WO 2004/031335 PCT/US2002/031050
Com onent E F G
A1 1 Sulfate 10.0
Linear Alkyl Benzene 5.0 10.0
Sulfonate
A1 1 Ethox Sulfate 7.0 15.0
Fat alcohol ethox 6.0 2.0 10.0
late 9E0
Amine Oxide 1.0
Sodium Citrate 5.0
Citric Acid 3.0 3.0
Fa Acid 3.0 8.0
En es 2.0 1.3 1.1
Borax 3.0 1.5 1.5
Soil Release Pol 2.0 2.0 2.7
ers
Ethanol 2.5 2.0
Pro anediol 5.0 5.0
Pro lene G1 col 8.0
G1 cerine 3.0
Sorbitol 4.5
Monoethanolamine 2.0 1.5 4.0
PVPVI 0.5 0.2 0.2
Water / Minors Balance
a to
100%
EXAMPLES H-K
Liquid laundry detergents according to the present invention having improved
performance with colored fabrics are prepared by conventional means:
Component H I J K
Linear Alkyl 3.0 3.0 12 12
Benzene
Sulfonate
A1 1 Ethox Sulfate9.5 9.5
Fatty alcohol 1.5 1.5 8 8
ethox late 9E0
Citric Acid 1.5 1.5 1.0 1.0
Fat Acid 0.5 0.5 4.0 4.0
En es 1.0 1.0
Borax 1.5 1.5
Soil Release 1.0 1.0
Pol ers
Ethanol 1.5 1.5
Pro anediol 3.0 3.0 8.0 8.0
Monoethanolamine2.0 2.0 3.0 3.0
PVPVI 0.1 0.1 0.1
PVP 0.2
PVNO 0.1
Water / Minors Balance
a to
100%
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EXAMPLES L-O
Liquid laundry detergents according to the present invention having improved
performance with colored fabrics are prepared by conventional means:
Com onent L M N O
A1 1 Sulfate 10.0 10.0
Linear Alkyl Benzene 10.0 10.0
Sulfonate
A1 1 Ethox Sulfate7.0 7.0
Fatty alcohol 6.0 6.0 10.0 10.0
ethoxylate
9E0
Sodium Citrate 5.0 5.0
Citric Acid 3.0 3.0
Fa Acid 8.0 8.0
En es 1.0 1.0 1.1 1.1
Borax 3.0 3.0 1.5 1.5
Soil Release Pol 1.0 1.0 2.7 2.7
ers
Ethanol 2.0 2.0
Pro anediol 5.0 5.0
Pro lene Glycol 8.0 8.0
Sorbitol 4.5 4.5
Monoethanolamine 2.0 2.0 4.0 4.0
PVPVI 0.5 0.05
pVP 1.0 0.1
Water / Minors Balance
a to
100%
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EXAMPLES P-S
Liquid laundry detergents according to the present invention having improved
performance with colored fabrics are prepared by conventional means:
Component P Q R S
Linear Alkyl Benzene3.0 3.0 12 12
Sulfonate
A1 1 Ethox Sulfate9.5 9.5
Fatty alcohol 1.5 1.5 8 8
ethoxylate
9E0
Sodium Citrate
Citric Acid 1.5 1.5 1.0 1.0
Fatty Acid 0.5 0.5 4.0 4.0
En es 1.0 1.0
Borax 1.5 1.5
Soil Release Pol 1.0 1.0
ers
Ethanol 1.5 1.5
Pro anediol 3.0 3.0 8.0 8.0
Monoethanolamine 2.0 5.0
Dieth lene triamine 3.5
Pol eth leneimine 5.0
PVPVI 0.1 0.2 0.1 0.2
Water / Minors Balance
a to
100%
Examples T-W
Liquid laundry detergents according to the present invention having improved
performance with colored fabrics are prepared by conventional means:
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Com onent T U V W
A1 1 Sulfate 10.0 10.0
Linear Alkyl 10.0 10.0
Benzene Sulfonate
Alkyl Ethoxy 7.0 7.0
Sulfate
Fatty alcohol6.0 6.0 10.0 10.0
ethox late
9E0
Sodium Citrate5.0 5.0
Citric Acid 3.0 3.0
Fa Acid 8.0 8.0
En es 1.0 1.0 1.1 1.1
Borax 3.0 3.0 1.5 1.5
Soil Release 1.0 1.0 2.7 2.7
Polymers
Ethanol 2.0 2.0
Pro anediol 5.0 5.0
Pro lene Gl 8.0 8.0
col
Sorbitol 4.5 4.5
Monoethanolamine5.0
Dieth lene 6.5 5.0
triamine
Polyeth leneimine 6.0
PVPVI 0.5 0.5 0.05 0.05_
Water / MinorsBalance
up
to
100%
Example X
Liquid laundry detergents according to the present invention having improved
performance with colored fabrics are prepared by conventional means:
Com onent X
Linear Alkyl Benzene 3.0
Sulfonate
Al 1 Ethox Sulfate 9.5
Fa alcohol ethox late1.5
9E0
Citric Acid 1.5
Fa Acid 0.5
En es 1.0
Borax 1.5
Soil Release Pol ers 1.0
Ethanol 1.5
Pro anediol 3.0
Monoethanolamine 2.0
PVPVI 0.1
Tino al-UNPA-GX 0.005
Water / Minors Balance
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While particular embodiments of the present invention have been illustrated
and
described, it would be obvious to those skilled in the art that various other
changes and
modifications can be made without departing from the spirit and scope of the
invention. It is
therefore intended to cover in the appended claims all such changes and
modifications that are
within the scope of this invention.
24
