CA 02310373 2000-OS-17
WO 99127052 PCT/US98I24817
Use of a crystal growth inhibitor to reduce fabric abrasion
Technical field of the invention
The present invention relates to the use of a crystal growth inhibitor for
reducing the abrasion of fabrics arising upon laundering treatment.
Background of the invention
The appearance of fabrics, e.g., clothing, bedding, household fabrics such
as table linens is one of the areas of concern for consumers. Indeed, upon
typical consumer's uses of the fabrics such as wearing, washing, rinsing
andlor tumble-drying of fabrics, a loss in the fabric appearance can take
place. It has now been found that this loss is at least partly due to abrasion
of the fabrics fibers upon laundering treatments. Such a problem of fabric
abrasion is even more acute after multiwash cycles.
The solving of this problem has been achieved in the art by at least two
ways either (i) remedying the fabric abrasion which has already occurred or
by (ii) preventing the problem of fabric abrasion.
One solution for solving this problem by means of (i) is given in US 3 894
318 whereby the fabric abrasion problem, which in turn results in a pilling
effect on the fabric, is reduced by further abrading the fabric.
On the other hand, one solution for solving this problem by means of (ii) is
by treating the fabric with polymeric substances which will deposit onto the
fabric and and thus protect the fibers from abrasion. Typical disclosure can
CA 02310373 2000-OS-17
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be found in US 4985040 which provides firstly the deposition of a
polyamide-epichlorhydrin resin and then that of a polyurethane.
Notwithstanding the advances in the art represented by the above
disclosure, there is still a need for solutions that will provide efficient
fabric
abrasion reduction.
It has now been found that the use of a crystal growth inhibitor (CGI), in
particular a iimescale CGI, fulfills such a need.
By "efficient fabric abrasion reduction", it is meant that fabrics treated
with
the CGI exhibit an improved appearance due to a reduced fabric abrasion
compared to untreated laundered fabrics.
Crystal growth inhibitors, in particular of the organic diphosphonic type have
long been known in the art of detergent to reduce limescale build up to
washing machine parts {e.g. heating resistance). A typical disclosure can be
found in WO 97!05226 wherein the CGI ameliorates the white deposits
problem caused by carbonate salts. Their use as a fabric abrasion reduction
agent is not disclosed.
By "crystal growth inhibitor", it is meant a compound that reduces the rate of
formation of inorganic microcrystals, thereby reducing the size and/or the
amount of such micro-crystals at the fabric surface.
It is therefore an advantage of the invention to provide the use of a crystal
growth inhibitor for reducing fabric abrasion, in particular fabric abrasion
which occur upon domestic laundering process.
Summary of the invention
The present invention relates to the use of a crystal growth inhibitor for
reducing fabric abrasion, in particular fabric abrasion which arises upon the
domestic laundering process of fabrics.
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In a preferred embodiment there is provided a method for reducing
fabric abrasion, which comprises the steps of contacting the fabrics with a
crystal growth inhibitor wherein said crystal inhibitor is selected from
glycolic
acid, phytic acid, oxydisuccinate, mellitic acid, succinic acid, oxydisuccinic
acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,
carboxymethyloxysuccinic acid, ether hydroxypolycarboxylates, organic
diphosphonic acid, and mixtures thereof.
Detailed description of the invention
rrXstal growth inhibitor
A crystal growth inhibitor is the essential component of the invention.
The suitable CGI for use herein can be defined by the following test
procedure, so called crystal growth inhibition test measurement.
Cryrstal growth inhibition test measurement
The ability for a compound to inhibit crystal growth can be assessed by
evaluating the impact in vitro on the growth rate of inorganic micro-crystals.
For this purpose, a system developed by G. H. Nancollas in 1964, described
in Nancollas, G. H and Koutsoukos, P. G. "Calcium Phosphate Nucleation
and Growth in solution." PrQg~. Clyrstal Growth Charact. 3, 77-102 (1980) can
be used. This system consists of measuring the growth rate of calcium
phosphate crystals seeded with hydroxyapatite ([Ca5(PO,)30Hj or HAP) in
the presence of .CaClz and NaH2P0,. Calcium phosphate growth liberates
protons that can be titrated with a strong base. The amount of base needed
to keep the pH constant over the crystal growth enables persons skilled in
the art to measure the crystal growth rate directly as well as to determine
the
effects of potential crystal growth rate inhibitors. A typiical plot of such
an
experiment is given below:
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WO 99127052 PGT/US98/Z4817
4
Volume
base adc
TIME
t-lag
The observed t-lag value defines the efficiency of a compound to inhibit the
growth of calcium phosphate crystals; wherein the higher the t-lag, the better
the CGI.
The following procedure can be used to build the plot given above
experimentally:
Place 350 mL of distilled water (distilled twice), 35 mL of KCI 2.1M, 50 mL of
CaCl2 0.0175M and 50 mL of KHzP04 0.01 M in a reaction vessel. Insert a
glass pH electrode and a standard calomel reference electrode connected to
an auto-titrator. Bubble nitrogen gas and stabilize the temperature of the
reaction mixture to 37 °C. When temperature and pH are stabilized, add
the
CGI candidate at the concentration to be tested (e.g. 1.10$M). Titrate to pH
7.4 with KOH 0.05M. Then seed the reaction mixture with 5 mL of
hydroxyapatite slurry [Ca6(P04)OH].
The hydroxyapatite slurry is prepared as follows:
100 gr of Bio-Gel HTP hydroxyapatite powder is dispersed in 1 L of
distilled water. The pH of the resulting slurry is lowered to 2.5 by
dropwise addition of HCI 6N. This is then heated to boiling and
refluxed while stirring for seven days in a 2L round-bottom flask
connected to a condenser. After cooling, to room temperature, pH is
adjusted to 12.0 by dropwise addition of 50% NaOH and the slurry is
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WO 99/27U52 PCTNS98/24817
5
refluxed for another seven days as before. The slurry is allowed to
settle for two days and the supernatant is suctioned off. The flask is
refilled with 1.5L of distilled water, stirred vigorously, an allowed to
settle again for two days. A total of seven rinses as described above
are performed. The pH is adjusted to 7.o by dropwise addition of HCI
2N while stirring vigorously. The resulting slurry is stored at 37°C
for
eleven months.
The plot shown above is obtained by recording the amount of base added
over time to maintain the pH of the reaction medium. T-lag for a particular
crystal growth inhibitor is determined graphically as described in the figure
above.
The crystal growth inhibitors to be used for the purpose of this invention
have a t-lag of at least 10 minutes at a concentration of 1.10'°M,
preferably
at least 20 minutes, most preferably at least 50 minutes.
Still another suitable method for determining the crystal growth inhibition
property of the selected component which is comparable to the T-lag
method is by a visual grading. The method is as follows:
A multicycle laundry test is performed over several (e.g. 10) cycles of
repeated washing and tumble drying. The conditions used are
representative for the desired geographical region (e.g. domestic washing
machine used, detergent used, rinse added product use, water hardness,
clothing articles washed etc.). At least two test legs are run in parallel,
including the composition of the invention and a separate reference leg.
After the required number of washing cycles have been performed the test
garments (articles of clothing) are taken for comparison by expert graders
under controlled fighting conditions. The visual grading is a betterlworse
comparison of the visible crystalline residue on the surface of the test
garments, comparing the test leg to the reference leg. Dark coloured,
knitted cotton articles are most suitable for this comparison.
In addition, the crystal growth inhibitors, differentiate themselves from the
chelating agents by their low binding affinity for copper defined by its Log
K,
i.e. the MLIM.L Log K at 25C, 0.1 ionic strength, of the CGI is of less than
15, preferably less than 12.
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Preferably, the CGI for use in the present invention are selected from
carboxylic compounds, organic monophosphonic acids, organic
diphosphonic acids, and mixtures thereof.
Carboxylic compounds
Typical of carboxylic compound for use herein are the carboxylic compounds
selected from gNoolic acid, monomeric polycarboxylic aads, homo or copoMneric
polycarboxylic aads or their salts in which the polycarboxylic add comprises
at I~st iwo
carboxylic radicals separa~d from each other tar rrot more than fiNO carbon
atoms. AI~-ror.~ghh
riot a carboxylic aad, phytic aad is also suihable for use as the cxystal
gr~nAh inh~itor.
When utilised in salt form, alkali metals, such as sodium, potassium and
lithium, or alkanolammonium salts are preferred.
Organic detergent CGIs suitable for the purposes of the present invention
include, but are not restricted to, a wide variety of polycarboxyiate
compounds. As used herein, "polycarboxylate" refers to compounds having
a plurality of carboxylate groups, preferably at least 3 carboxylates.
Polycarboxylate CGI can generally be added to the composition in acid
form, but can also be added in the form of a neutralised salt. When utilized
in salt form, alkali metals, such as sodium, potassium, and lithium, or
alkanolammonium salts are preferred.
Included among the polycarboxylate CGIs are a variety of categories of
useful materials. One important category of polycarboxylate CGIs
encompasses the ether polycarboxylates, including oxydisuccinate, as
disclosed in U.S. Patent 3,128,287 and U.S. Patent 3,635,830. See also
"TMSlTDS" CGIs of U.S. Patent 4,663,071. Suitable ether polycarboxylates
also include cyclic compounds, particularly alicyclic compounds, such as
those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874
and 4,102,903.
Other useful CGI include the ether hydroxypolycarboxylates, poiyacrylate
polymers, copolymers of malefic anhydride with ethylene or vinyl methyl
ether, or acrylic acid, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid,
and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and
CA 02310373 2004-04-15
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substituted ammonium salts of polyacetic acids such as ethylenediamine
tetraacetic 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.
The molecular weight for these polymers and copolymers is preferably
below 100,000, most preferably between 500 and 50,000.
Commercially available polymers, suitable for use herein, which prevent the
precipitation of the salts of the buffering component upon dilution of the
composition in water are the polyacrylate polymers sold under the
trademark Good-Rite~ from BF Goodrich, Acrysol~ from Rohm 8~ Haas,
Sokalan~ from BASF, Norasol~ from Norso Haas. Preferred commercially
available polymers are the polyacrylate polymers, especially the NorasotC~
polyacrylate polymers and more preferred are the poiyacrylate polymer
Norasol~ 410N (MW 10,000) and the polyacrylate polymer modified with
aminophosphonic groups Norasol~ 440N (MW 4000) and its corresponding
acid form Norasol~ QR 784 (MW 4000) from Norso-Haas.
Citrates, e.g., citric acid and soluble salts thereof (particularly sodium
salt),
are polycarboxylate CGI suitable for use herein.
Also suitable in the compositions containing the present invention are the
3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds
disclosed in U.S. Patent 4,566,984. Useful succinic acid CGI include the
C5-C2p alkyl and afkenyl succinic acids and salts thereof. A particularly
preferred compound of this type is dodecenylsuccinic acid. Specific
examples of succinate CGIs include: laurylsuccinate, myristylsuccinate,
paimityisuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsucci-
nate, and the like. Laurylsuccinates are the preferred CGIs of this group,
and are described in EP 0,200,263.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226 and
in U.S. Patent 3,308,067. See also U.S. Pat. 3,723,322.
Organic monophosphonic acid
CA 02310373 2004-04-15
Organo monophosphonic acid or one of its salts or complexes is also
suitable for use herein as a CGI.
By organo monophosphonic acid it is meant herein an organo
monophosphonic acid which does not contain nitrogen as part of its
chemical structure. This definition therefore excludes the organo
aminophosphonates, which however may be included in compositions of the
invention as heavy metal ion sequestrants.
The organo monophosphonic acid component may be present in its acid
form or in the form of one of its salts or complexes with a suitable counter
cation. Preferably any salts/complexes are water soluble, with the alkali
metal and alkaline earth metal salts/complexes being especially preferred.
A prefered organo monophosphonic acid is 2-phosphonobutane-1,2,4-
tricarboxylic acid commercially available from Bayer under the trademark of
Bayhibit.
Organodiphosphonic acid
Organo diphosphonic acid or one of its salts or complexes is also suitable
for use herein as a CGI.
By organo diphosphonic acid it is meant herein an organo diphosphonic acid
which does not contain nitrogen as part of its chemical structure. This
definition therefore excludes the organo aminophosphonates, which
however may be included in compositions of the invention as heavy metal
ion sequestrants.
The organo diphosphonic acid component may be present in its acid form or
in the form of one of its salts or complexes with a suitable counter cation.
Preferably any salts/complexes are water soluble, with the alkali metal and
alkaline earth metal salts/complexes being especially preferred.
The organo diphosphonic acid is preferably a C1-C4 diphosphonic acid and
more preferably a C2 diphosphonic acid selected from ethylene
diphosphonic acid, a-hydroxy-2 phenyl ethyl diphosphonic acid, methylene
diphosphonic acid , vinylidene 1,1 diphosphonic acid , 1,2 dihydroxyethane
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1,7 diphosphonic acid and hydroxy-ethane 1,1 diphosphonic acid and any
salts thereof and mixtures thereof.
A most preferred organo diphosphonic acid is hydroxy-ethane 1,1
diphosphonic acid (HEDP).
Among the above described classes of CGI, preferred classes for use herein
are the class of organic monophosphonic acids and/or organic diphosphonic
acids.
The CGI can be employed in stand alone product including pre-or post-wash
additives. It can also be employed It can also be used in fully-formulated
compositions including laundry compositions as well as rinse added fabric
softener compositions and dryer added compositions (e.g. sheets) which
provide softening andlor antistatic benefits, and rinse added compositions.
Typical levels of incorporation of the CGI within the compositions is of less
than 10%, preferably less than 1 %, more preferably from 0.005% to 0.5%,
most preferably from 0.05% to 0.25%, and even most preferably from 0.1
to 0.2% by weight of the composition.
Selection of the components typical for use in such fully formulated
compositions is made depending on their end use. For example, when
formulated as a softening composition, it will comprises a fabric softening
compound.
Fabric softening comno
Typical levels of incorporation of the softening compound in the softening
composition are of from 1 % to 80% by weight, preferably from 5% to 75%,
more preferably from 15% to 70%, and even more preferably from 19% to
fi5%, by weight of the composition.
The fabric softener compound is preferably selected from a cationic,
nonionic, amphoteric or anionic fabric softening component. Typical of the
cationic softening components are the quaternary ammonium compounds or
amine precursors thereof as defined hereinafter.
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WO 99/27052 PCT/US98n4817
y-Quatemarrr Ammonium Fabric So~~~jpg Active Comoo,-and
(1) Preferred quaternary ammonium fabric softening active compound
have the formula
(R)4_~ N (CH2~-Q-Rl X-
m
(1)
or the formula:
(~,-~-~Z -Q-R~ X
m
Q - R~ (2)
wherein Q is a carbonyl unit having the formula:
2 2
-O-O- , O -O-O-O- , -N-O- , -O-N-
-C-O- ,
each R unit is independently hydrogen, C1-Cg alkyl, C1-Cg hydroxyalkyl,
and mixtures thereof, preferably methyl or hydroxy alkyl; each R1 unit is
independently linear or branched C11-C22 alkyl, linear or branched C11-
C22 alkenyl, and mixtures thereof, R2 is hydrogen, C1-C4 alkyl, C1-C4
hydroxyalkyl, and mixtures thereof; X is an anion which is compatible with
fabric softener actives and adjunct ingredients; the index m is from 1 to 4,
preferably 2; the index n is from 1 to 4, preferably 2.
An example of a preferred fabric softener active is a mixture of quaternized
amines having the formula:
+ O
R2-N (CHz~-O-C-Rl X -
2
wherein R is preferably methyl; R1 is a linear or branched alkyl or alkenyl
chain comprising at least 11 atoms, preferably at least 15 atoms. In the
above fabric softener example, the unit -02CR1 represents a fatty acyl unit
which is typically derived from a triglyceride source. The triglyceride source
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is preferably derived from tallow, partially hydrogenated tallow, lard,
partially
hydrogenated lard, vegetable oils andlor partially hydrogenated vegetable
oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, com oil,
soybean oil, tall oil, rice bran oil, etc. and mixtures of these oils.
The preferred fabric softening actives of the present invention are the
Diester andlor Diamide Quaternary Ammonium (DEQA) compounds, the
diesters and diamides having the formula:
+ _
(R)4-m N (CH2)ri Q-Rl
m
wherein R, R1, X, and n are the same as defined herein above for formulas
(1 ) and (2), and Q has the formula:
O H O
II I I)
-O-C-. or -N-C-
These preferred fabric softening actives are formed from the reaction of an
amine with a fatty acyl unit to form an amine intermediate having the
formula:
R N (CH2)n-Q-Rl
2
wherein R is preferably methyl, Q and R' are as defined herein before;
followed by quaternization to the final softener active.
Non-limiting examples of preferred amines which are used to form the
DEQA fabric softening actives according to the present invention include
methyl bis{2-hydroxyethyl)amine having the formula:
CH3
HO~N~OH
methyl bis(2-hydroxypropyl)amine having the formula:
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12
CH3
N
HO OH
methyl (3-aminopropyl) (2-hydroxyethyl)amine having the formula:
CH3
HON ~NH2
methyl bis(2-aminoethyl)amine having the formula:
CH3
H2N ~N ~NH2
triethanol amine having the formula:
~OH
HO~''N OOH
,
di{2-aminoethyl) ethanolamine having the formula:
~OH
H2N ~N ~NHZ
The counterion, X(-) above, can be any softener-compatible anion,
preferably the anion of a strong acid, for example, chloride, bromide,
methylsulfate, ethylsulfate, sulfate, nitrate and the like, more preferably
chloride or methyl sulfate. The anion can also, but less preferably, carry a
double charge in which case X{-) represents half a group.
Tallow and canola oil are convenient and inexpensive sources of fatty acyl
units which are suitable for use in the present invention as R1 units. The
following are non-limiting examples of quaternary ammonium compounds
suitable for use in the compositions of the present invention. The term
"tallowyl" as used herein below indicates the R1 unit is derived from a tallow
triglyceride source and is a mixture of fatty acyl units. Likewise, the use of
the term canolyl refers to a mixture of fatty acyl units derived from canola
oil.
CA 02310373 2004-04-15
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Table II
Fabric Softener Actives
N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride;
N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride;
N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride
N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium
chloride;
N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium
chloride;
N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl
ammonium chloride;
N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-ethyl)-N, N-d imethyl
ammonium chloride;
N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;
N,N,N-tricanolyl-oxy-ethyl)-N-methyl ammonium chloride;
N-(2-tallowyloxy-2-oxoethyl}-N-(tallowyl)-N,N-dimethyl ammonium chloride;
N-(2-canolyloxy-2-oxoethyl)-N-(canolyl)-N,N-dimethyl ammonium chloride;
1,2-ditallowyloxy-3-N,N,N-trimethylammoniopropane chloride; and
1,2-dicanolyloxy-3-N,N,N-trimethylammoniopropane chloride;
and mixtures of the above actives.
Other examples of quaternary ammonium softening compounds are
methylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate and
methylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammonium
methylsulfate; these materials are available from Witco Chemical Company
under the trade marks Varisoft~ 222 and Varisoft~ 110, respectively.
Particularly preferred is N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium
chloride, where the tallow chains are at least partially unsaturated.
The level of unsaturation contained within the tallow, canola, or other fatty
acyl unit chain can be measured by the Iodine Value (IV) of the
corresponding fatty acid, which in the present case should preferably be in
CA 02310373 2000-OS-17
WO 99127052 PCT/US98n4817
14
the range of from 5 to 100 with two categories of compounds being
distinguished, having a IV below or above 25.
Indeed, for compounds having the formula:
+ _
~)4_m N (CH2~-Q-Rl X
m
derived from tallow fatty acids, when the Iodine Value is from 5 to 25,
preferably 15 to 20, it has been found that a cisltrans isomer weight ratio
greater than about 30170, preferably greater than about 50150 and more
preferably greater than about 70130 provides optimal concentrability.
For compounds of this type made from tallow fatty acids having a Iodine
Value of above 25, the ratio of cis to trans isomers has been found to be
less critical unless very high concentratioris are needed.
Other suitable examples of fabric softener actives are derived from fatty acyl
groups wherein the terms "tallowyl" and canolyl" in the above examples are
replaced by the terms "cocoyi, palmyl, lauryl, oleyl, ricinoleyl, stearyl,
palmityl," which correspond to the triglyceride source from which the fatty
acyl units are derived. These alternative fatty acyl sources can comprise
either fully saturated, or preferably at least partly unsaturated chains.
As described herein before, R units are preferably methyl, however, suitable
fabric softener actives are described by replacing the term "methyl" in the
above examples in Table II with the units "ethyl, ethoxy, propyl, propoxy,
isopropyl, butyl, isobutyl and t-butyl.
The counter ion, X, in the examples of Table II can be suitably replaced by
bromide, methylsulfate, formate, sulfate, nitrate, and mixtures thereof. In
fact, the anion, X, is merely present as a counterion of the positively
charged
quaternary ammonium compounds. The scope of this invention is not
considered limited to any particular anion.
For the preceding ester fabric softening agents, the pH of the compositions
herein is an important parameter of the present invention. Indeed, it
CA 02310373 2000-OS-17
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15
influences the stability of the quaternary ammonium or amine precursors
compounds, especially in prolonged storage conditions.
The pH, as defined in the present context, is measured in the neat
compositions at 20 °C. While these compositions are operable at pH of
less
than about 6.0, for optimum hydrolytic stability of these compositions, the
neat pH, measured in the above-mentioned conditions, must preferably be
in the range of from about 2.0 to about 5, preferably in the range of 2.5 to
4.5, preferably about 2.5 to about 3.5. The pH of these compositions herein
can be regulated by the addition of a Bronsted acid.
Examples of suitable acids include the inorganic mineral acids, carboxylic
acids, in particular the low molecular weight (C1-C5) carboxylic acids, and
alkylsulfonic acids. Suitable inorganic acids include HCI, H2S04, HN03 and
H3P04. Suitable organic acids include formic, acetic, citric, methylsulfonic
and ethylsulfonic acid. Preferred acids are citric, hydrochloric, phosphoric,
formic, methylsulfonic acid, and benzoic acids.
The use of the ethoxylated amino-functional-polymers in this context is
particularly beneficial. Indeed, as stated herein before, the softening
compositions are preferably used in the pH ranges above mentioned, that is
acidic conditions. In such acidic conditions, ethoxylated amino-functional
polymers which have not been treated so as to eliminate the aldehydes
andlor ketones present within the raw material will produce these
undesirable by-product thus producing a malodour and discoloration. With
the amino-functional polymer of the invention, this is not so, the polymer are
stable upon acidic conditions and so is their resulting odor and color.
As used herein, when the diester is specified, it will include the monoester
that is normally present in manufacture. For softening, under no/low
detergent carry-over laundry conditions the percentage of monoester should
be as low as possible, preferably no more than about 2.5%. However,
under high detergent carry-over conditions, some monoester is preferred.
The overall ratios of diester to monoester are from about 100:1 to about 2:1,
preferably ftom about 50:1 to about 5:1, more preferably from about 13:1 to
about 8:1. Under high detergent carry-over conditions, the dilmonoester
ratio is preferably about 11:1. The level of monoester present can be
controlled in the manufacturing of the softener compound.
Mixtures of actives of formula (1 ) and (2) may also be prepared.
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2)-Still other suitable quaternary ammonium fabric softening compounds for
use herein are cationic nitrogenous salts having finro or more long chain
acyclic aliphatic Cg-C22 hydrocarbon groups or one said group and an
arylalkyl group which can be used either alone or as part of a mixture are
selected from the group consisting of:
(i) acyclic quaternary ammonium salts having the formula:
Ra +
R8-N-RS A
~s
wherein R4 is an acyclic aliphatic Cg-C22 hydrocarbon group, R5 is a C1-C4
saturated alkyl or hydroxyalkyl group, R8 is selected from the group
consisting of R4 and R5 groups, and A- is an anion defined as above;
(ii) diamino alkoxylated quaternary ammonium salts having the formula:
O Rs O
Ri-C-NH-R2-N-R2-NH-C-R~ ~1
I
(CH2CH20~H
wherein n is equal to 1 to about 5, and R1, R2, R5 and A- are as defined
above;
(iii) mixtures thereof.
Exampies of the above class cationic nitrogenous salts are the well-known
diaikyldi methylammonium salts such as ditallowdimethylammonium
chloride, ditallowdimethylammonium methylsulfate,
di(hydrogenatedtallow)dimethylammonium chloride,
distearyldimethylammonium chloride, dibehenyldimethylammonium chloride.
Di(hydrogenatedtallow)di methylammonium chloride and
ditallowdimethylammonium chloride are preferred. Examples of
commercially available dialkyldimethyl ammonium salts usable in the
CA 02310373 2004-04-15
17
present invention are di(hydrogenatedtallow)dimethylammonium chloride
(trade mark Adogen~ 442), ditallowdimethylammonium chloride (trade
mark Adogen~ 470, Praepagen~ 3445), distearyl dimethyiammonium
chloride (trade mark Arosurf~ TA-100), all available from Witco Chemical
Company. Dibehenyldimethylammonium chloride is sold under the trade
mark Kemamine Q-2802C by Humko Chemical Division of Witco Chemical
Corporation.
Dimethylstearylbenzyl ammonium chloride is sold under the trade marks.
Varisoft~ SDC by Witco Chemical Company and Ammonyx~ 490 by Onyx
Chemical Company.
-Amine Fabric Softening Active Coml o~ and
Suitable amine fabric softening compounds for use herein, which may be in
amine form or cationic form are selected from:
(i)- Reaction products of higher fatty acids with a polyamine selected from
the group consisting of hydroxyalkylalkylenediamines and
dialkylenetriamines and mixtures thereof. These reaction products are
mixtures of several compounds in view of the mufti-functional structure of the
polyamines.
The preferred Component (i) is a nitrogenous compound selected from the
group consisting of the reaction product mixtures or some selected
components of the mixtures.
One preferred component (i) is a compound selected from the group
consisting of substituted imidazoline compounds having the formula:
N
N
I
Rg-NH-C-R~
I I
O
wherein R7 is an acyclic aliphatic C15-C21 hydrocarbon group and R8 is a
divalent C1-Cg alkylene group.
Component (i) materials are commercially available as: Mazamide4 6, sold
by Mazer Chemicals, or Ceranine~ HC, sold by Sandoz Colors &
Chemicals; stearic hydroxyethyl imidazoline sold under the trade marks of
CA 02310373 2004-04-15
18
Alkazine~ ST by Alkaril Chemicals, Inc., or Schercozoline~ S by Scher
Chemicals, Inc.; N,N"-ditallowalkoyldiethylenetriamine; 1-tallowamidoethyl-2-
tallowimidazoline (wherein in the preceding structure R1 is an aliphatic C15-
C17 hydrocarbon group and R8 is a divalent ethylene group).
Certain of the Components (i) can also be first dispersed in a Bronsted acid
dispersing aid having a pKa value of not greater than about 4; provided that
the pH of the final composition is not greater than about 6. Some preferred
dispersing aids are hydrochloric acid, phosphoric acid, or methylsulfonic
acid.
Both N,N"-ditallowalkoyldiethylenetriamine and 1-tallow(amidoethyl)-2-
tallowimidazoline are reaction products of tallow fatty acids and
diethylenetriamine, and are precursors of the cationic fabric softening agent
methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate (see
"Cationic Surface Active Agents as Fabric Softeners," R. R. Egan, Journal of
the American Oil Chemicals' Society, January 1978, pages 118-121). N,N"-
ditallow alkoyldiethylenetriamine and 1-tallowamidoethyl-2-tallowimidazoline
can be obtained from Witco Chemical Company as experimental chemicals.
Methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate is sold by
Witco Chemical Company under the trademark Varisoft~ 475.
(ii)-softener having the formula:
N
R' i
v
o N c> ~
Rs
R' C G
wherein each R2 is a C1_g alkylene group, preferably an ethylene group;
and G is an oxygen atom or an -NR- group; and each R, R1, R2 and R5
have the definitions given above and A- has the definitions given above for
X-.
CA 02310373 2004-04-15
19
An example of Compound (ii) is 1-oleylamidoethyl-2-oleylimidazolinium
chloride wherein R1 is an acyclic aliphatic C15-C17 hydrocarbon group, R2
is an ethylene group, G is a NH group, R5 is a methyl group and A- is a
chloride anion.
(iii)- softener having the formula:
H H
\N-RZ-N
N -N 2A0
Ri Ri
wherein R, R1, R2, and A- are defined as above.
An example of Compound (iii) is the compound having the formula:
~ H H~
1V-CHZCH2-N f Cl C
R~ R~
wherein R1 is derived from oleic acid
Additional fabric softening agents useful herein are described in U.S. Pat.
No. 4,661,269, issued April 28, 1987, in the names of Toan Trinh, Errol H.
Wahl, Donald M. Swartley, and Ronald L. Hemingway; U.S. Pat. No.
4,439,335, Burns, issued March 27, 1984; and in U.S. Pat. Nos.: 3,861,870,
Edwards and Diehi; 4,308,151, Cambre; 3,886,075, Bernardino; 4,233,164,
Davis; 4,401,578, Verbruggen; 3,974,076, Wiersema and Rieke; 4,237,016,
Rudkin, Clint, and Young; and European Patent Application publication No.
472,178, by Yamamura et al.
Of course, the term "softening active" can also encompass mixed softening
active agents.
Preferred among the classes of softener compounds disclosed herein before
are the diester or diamido quaternary ammonium fabric softening active
compound (DEQA).
CA 02310373 2000-OS-17
WO 99127052 PCT/US98n4817
20
The invention composition may contain, in addition or alternatively to the
herein before described components, one or more of the following
ingredients.
(0)-Liquid carrier
An optional, but prefen-ed, ingredient is a liquid carrier. The liquid carrier
employed in the instant compositions is preferably at least primarily water
due to its low cost, relative availability, safety, and environmental
compatibility. The level of water in the liquid carrier is preferably at least
about 50%, most preferably at least about 60%, by weight of the carrier.
Mixtures of water and low molecular weight, e.g., <about 200, organic
solvent, e.g., lower alcohols such as ethanol, propanol, isopropanol or
butanol are useful as the carrier liquid. Low molecular weight alcohols
include monohydric, dihydric (glycol, etc.) trihydric (glycerol, etc.), and
higher
polyhydric (polyols) alcohols.
,(~~~_Additional Solvents
The compositions of the present invention may comprise one or more
solvents which provide increased ease of formulation. These ease of
formulation solvents are all disclosed in WO 97103169. This is particularly
the case when formulating liquid, clear fabric softening compositions. When
employed, the ease of formulation solvent system preferably comprises less
than about 40%, preferably from about 10% to about 35%, more preferably
from about 12% to about 25%, and even more preferably from about 14% to
about 20%, by weight of the composition. The ease of formulation solvent is
selected to minimize solvent odor impact in the composition and to provide a
low viscosity to the final composition. For example, isopropyl alcohol is not
very effective and has a strong odor. n-Propyl alcohol is more effective, but
also has a distinct odor. Several butyl alcohols also have odors but can be
used for effective claritylstability, especially when used as part of a ease
of
formulation solvent system to minimize their odor. The aicohols are also
selected for optimum low temperature stability, that is they are able to form
compositions that are liquid with acceptable low viscosities and translucent,
preferably clear, down to about 40°F (about 4.4°C) and are able
to recover
after storage down to about 20°F (about minus 6.7°C).
CA 02310373 2000-OS-17
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21
The suitability of any ease of formulation solvent for the formulation of the
liquid, concentrated, preferably clear, fabric softener compositions herein
with the requisite stability is surprisingly selective. Suitable solvents can
be
selected based upon their octanollwater partition coefficient (P) as defined
in
WO 97103169.
The ease of formulation solvents herein are selected from those having a
CIogP of from about 0.15 to about 0.64, preferably from about 0.25 to about
0.62, and more preferably from about 0.40 to about 0.60, said ease of
formulation solvent preferably being at least somewhat asymmetric, and
preferably having a melting, or solidification, point that allows it to be
liquid
at, or near room temperature. Solvents that have a low molecular weight
and are biodegradable are also desirable for some purposes. The more
asymmetric solvents appear to be very desirable, whereas the highly
symmetrical solvents such as 1,7-heptanediol, or 1,4-bis(hydroxymethyl)
cyclohexane, which have a center of symmetry, appear to be unable to
provide the essential clear compositions when used alone, even though their
CIogP values fall in the preferred range.
The most preferred ease of formulation solvents can be identified by the
appearance of the softener vesicles, as observed via cryogenic electron
microscopy of the compositions that have been diluted to the concentration
used in the rinse. These dilute compositions appear to have dispersions of
fabric softener that exhibit a more uni-lamellar appearance than
conventional fabric softener compositions. The closer to uni-lamellar the
appearance, the better the compositions seem to perform. These
compositions provide surprisingly good fabric softening as compared to
similar compositions prepared in the conventional way with the same fabric
softener active.
Operable ease of formulation solvents are disclosed and listed below which
have ClogP values which fall within the requisite range. These include
mono-ols, C6 diols, C7 diols, octanediol isomers, butanediol derivatives,
trimethylpentanediol isomers, ethylmethylpentanediol isomers, propyl
pentanediol isomers, dimethylhexanediol isomers, ethylhexanediol isomers,
methytheptanediol isomers, octanediol isomers, nonanediol isomers, alkyl
glyceryl ethers, di(hydroxy alkyl) ethers, and aryl glyceryl ethers, aromatic
,' CA 02310373 2004-04-15
22
glyceryl ethers, alicyclic diols and derivatives, C3C7 diol alkoxylated
derivatives, aromatic diols, and unsaturated diols. Particularly preferred
ease of formulation solvents include hexanediols such as 1,2-Hexanediol
and 2-Ethyl-1,3-hexanediol and pentanediols such as 2,2,4-Trimethyl-1,3-
pentanediol.
(C)-Dispe~sibilitli Aids
Relatively concentrated compositions containing both saturated and
unsaturated diester quaternary ammonium compounds can be prepared that
are stable without the addition of concentration aids. However, the
compositions of the present invention may require organic and/or inorganic
concentration aids to go to even higher concentrations and/or to meet higher
stability standards depending on the other ingredients. These concentration
aids which typically can be viscosity modifiers may be needed, or preferred,
for ensuring stability under extreme conditions when particular softener
active levels are used. The surfactant concentration aids are typically
selected from the group consisting of (1) single long chain alkyl cationic
surfactants; (2) nonionic surfactants; (3) amine oxides; (4) fatty acids; and
(5) mixtures thereof. These aids are described in WO 94/20597, specifically
on page 14, line 12 to page 20, line 12.
When said dispersibility aids are present , the total level is from 2% to 25%,
preferably from 3% to 17%, more preferably from 4% to 15%, and even
more preferably from 5% to 13% by weight of the composition. These
materials can either be added as part of the active softener raw material,
(I),
e.g., the mono-long chain alkyl cationic surfactant and/or the fatty acid
which
are reactants used to form the biodegradable fabric softener active as
discussed hereinbefore, or added as a separate component. The total level
of dispersibility aid includes any amount that may be present as part of
component (I).
Inorganic viscosity/dispersibility control agents which can also act like or
augment the effect of the surfactant concentration aids, include water-
soluble, ionizable salts which can also optionally be incorporated into the
compositions of the present invention. A wide variety of ionizable salts can
be used. Examples of suitable salts are the halides of the Group IA and IIA
metals of the Periodic Table of the Elements, e.g., calcium chloride,
CA 02310373 2004-04-15
23
magnesium chloride, sodium chloride, potassium bromide, and lithium
chloride. The ionizable salts are particularly useful during the process of
mixing the ingredients to make the compositions herein, and later to obtain
the desired viscosity. The amount of ionizable salts used depends on the
amount of active ingredients used in the compositions and can be adjusted
according to the desires of the formulator. Typical levels of salts used to
control the composition viscosity are from about 20 to about 20,000 parts
per million (ppm), preferably from about 20 to about 11,000 ppm, by weight
of the composition.
Alkylene polyammonium salts can be incorporated into the composition to
give viscosity control in addition to or in place of the water-soluble,
ionizable
salts above. In addition, these agents can act as scavengers, forming ion
pairs with anionic detergent carried over from the main wash, in the rinse,
and on the fabrics, and may improve softness performance. These agents
may stabilize the viscosity over a broader range of temperature, especially
at low temperatures, compared to the inorganic electrolytes.
Specific examples of alkylene polyammonium salts include I-lysine
monohydrochloride and 1,5-diammonium 2-methyl pentane dihydrochloride.
(DITDye fixing agent
The composition of the invention may optionally comprise a dye fixing agent.
Dye fixing agents, or "fixatives", are well-known, commercially available
materials which are designed to improve the appearance of dyed fabrics by
minimizing the loss of dye from fabrics due to washing. Not included within
this definition are components which are fabric softeners or those described
hereinbefore as amino-functional polymers.
Many dye fixing agents are cationic, and are based on various quaternized
or otherwise cationically charged organic nitrogen compounds. Cationic
fixatives are available under various trade namMS from several suppliers.
Representative examples include: CROSCOLOR PMF (July 1981, Code No.
7894) and CROSCOLOR NOFF (January 1988, Code No. 8544) from
TM
Crosfield; INDOSOL E-50 (February 27, 1984, RMf. No. 6008.35.84;
polyethyleneamine-based) from Sandoz; SANDOFIX TPS, which is also
available from Sandoz and is a preferred polycationic fixative Mor use herein
and SANDOFIX SWE (cationic resinous compound), REWIN SRF, REWIN
CA 02310373 2004-04-15
24
SRF-O and REWIN DWR from CHT-Beitlich GMBH, Tinofix~ ECO, Tinofix~
FRD and Solfin~ available from Ciba-Geigy.
Other cationic dye fixing agents are described in "Aftertreatments for
improving the fastness of dyes on textile fibres" by Christopher C. Cook
(REV. PROG. COLORATION Vol. 12, 1982). Dye fixing agents suitable for
use in the present invention are ammonium compounds such as fatty acid -
diamine condensates e.g. the hydrochloride, acetate, metosulphate and
benzyl hydrochloride of oleyldiethyl aminoethylamide, oleylmethyl-
diethyienediaminemethosulphate, monostearyl-ethylene
diaminotrimethylammonium methosulphate and oxidized products of tertiary
amines; derivatives of polymeric alkyldiamines, polyamine-cyanuric chloride
condensates and aminated glycerol dichlorohydrins.
A typical amount of the dye fixing agent to be employed in the composition
of the invention is preferably up 90% by weight, preferably up to 50% by
weight, more preferably from 0.001 % to 10% by weight, most preferably
from 0.5% to 5% active by weight of the composition.
,(E)- Stabilizers
Stabilizers can be present in the compositions of the present invention. The
term "stabilizer," as used herein, includes antioxidants and reductive agents.
These agents are present at a level of from 0% to about 2%, preferably from
about 0.01 % to about 0.2%, more preferably, from about 0.035% to about
0.1 % for antioxidants, and more preferably from about 0.01 % to about 0.2%
for reductive agents. These assure good odor stability under long term
storage conditions for the compositions and compounds stored in molten
form. The use of antioxidants and reductive agent stabilizers is especially
critical for low scent products (low perfume).
Examples of antioxidants that can be added to the compositions of this
invention include a mixture of ascorbic acid, ascorbic palmitate, propyl
gallate, available from Eastman Chemical Products, Inc., under the trade
marks Tenox~ PG and Tenox S-1; a mixture of BHT (butylated
hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and citric
CA 02310373 2000-OS-17
wo ~n~osz rcT~s9sn4sm
25
acid, available from Eastman Chemical Products, Inc., under the trade name
Tenox-6; butylated hydroxytoluene, available from UOP Process Division
under the trade name Sustane~ BHT; tertiary butylhydroquinone, Eastman
Chemical Products, Inc., as Tenox TBHQ; natural tocopherols, Eastman
Chemical Products, Inc., as Tenox GT-11GT-2; and butylated
hydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chain
esters (Cg-C22) of gallic acid, e.g., dodecyl gallate; Irganox~ 1010; lrganox
~ 1035; Irganox~ B 1171; Irganox~ 1425; Irganox~ 3114; irganox~ 3125;
and mixtures thereof; preferably irganox~ 3125, Irganox~ 1425, Irganox~
3114, and mixtures thereof; more preferably Irganox~ 3125 alone. The
chemical names and CAS numbers for some of the above stabilizers are
listed in Table ll below.
TABLE IIII
Antioxidant CAS No. Chemical Name used in Code of Federal
Irganox~ 1010 6683-19-8 Tetrakis (methylene(3,5-di-tert-butyl-4
hydroxyhydrocinnamate)) methane
Irganox~ 1035 41484-35-9 Thiodiethylene bis(3,5-di-tert-butyl-4.-
hydroxyhydrocinnamate
Irganox~ 1098 23128-74-7 N,N'-Hexamethylene bis(3,5-di-tert-butyl-
4-
hydroxyhydrocinnamamide
Irganox~ B 1171 31570-04-4
23128-74-7 1:1 Blend of Irganox~ 1098 and Irgafos~
168 .
lrganox~ 1425 65140-91-2 Calcium bis(rnonoethyl{3,5-di-tert-butyl-4-
hydroxybenzyl)phosphonate)
lrganox~ 3114 65140-91-2 Calcium bis(rnonoethyl(3,5-di-tert-butyl-4-
hydroxybenzyl)phosphonate)
Irganox~ 3125 34137-09-2 3,5-Di-tert-butyl-4-hydroxy-hydrocinnamic
acid
triester with 1,3,5-tris(2-hydroxyethyl)-S-
triazine-2,4,6-(1 H, 3H, 5H)-trione
Irgafos~ 168 31570-04-4 Tris(2,4-di-tert-butyl-phenyi)phosphite
CA 02310373 2004-04-15
26
Examples of reductive agents include sodium borohydride,
hypophosphorous acid, Irgafos~ 168, and mixtures thereof.
~F)-Soil Release Agent
Any polymeric soil release agent known to those skilled in the art can
optionally be employed in the compositions of this invention. 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 washing and rinsing cycles 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.
If utilized, soil release agents will generally comprise from about 0.01 % to
about 10.0%, by weight, of the detergent compositions herein, typically from
about 0.1 % to about 5%, preferably from about 0.2% to about 3.0%.
The following describe soil release polymers suitable
for use in the present invention. U.S. 3,959,230 Hays,
issued May 25, 1976; U.S. 3,893,929 Basadur, issued July 8, 1975; U.S.
4,000,093, Nicol, et al., issued December 28, 1976; U.S. Patent 4,702,857
Gosselink, issued October 27, 1987; U.S. 4,968,451, Scheibel et aL, issued
November 6; U.S. 4,702,857, Gosselink, issued October 27, 1987; U.S.
4,711,730, Gosselink et al., issued December 8, 1987; U.S. 4,721,580,
Gosselink, issued January 26, 1988; U.S. 4,877,896, Maldonado et aL,
issued October 31, 1989; U.S. 4,956,447, Gosselink et al., issued
September 11, 1990; U.S. 5,415,807 Gosselink et al., issued May 16, 1995;
European Patent Application 0 219 048, published April 22, 1987 by Kud, et
al..
Further suitable soil release agents are described in U.S. 4,201,824,
Violland et al.; U.S. 4,240,918 Lagasse ef al.; U.S. 4,525,524 Tung et al.;
U.S. 4,579,681, Ruppert et al.; U.S. 4,240,918; U.S. 4,787,989; U.S.
4,525,524; EP 279,134 A, 1988, to Rhone-Poulenc Chemie; EP 457,205 A
to BASF (1991 ); and DE 2,335,044 to Unilever N. V., 1974 .
CA 02310373 2004-04-15
27
TM
Commercially available soil release agents include the METOLOSE SM100,
METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo K.K.,
TM
SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF
TM TM
(Germany), ZELCON 5126 (from Dupont) and MILEASE T (from IGI).
~(G)-Bactericides
Examples of bactericides used in the compositions of this invention include
glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-diol sold by
Inolex Chemicals, located in Philadelphia, Pennsylvania, under the trade
mark Bronopol~, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-one
and 2-methyl-4-isothiazoline-3-one sold by Rohm and Haas Company under
the trade mark Kathon 1 to 1,000 ppm by weight of the agent.
(Hl-Perfume
The present invention can contain a perfume. Suitable perfumes are
disclosed in U.S. Pat. 5,500,138 .
As used herein, perfume includes fragrant substance or mixture of
substances including natural (i.e., obtained by extraction of flowers, herbs,
leaves, roots, barks, wood, blossoms or plants), artificial (i.e., a mixture
of
different nature oils or oil constituents) and synthetic (i.e., synthetically
produced) odoriferous substances. Such materials are often accompanied
by auxiliary materials, such as fixatives, extenders, stabilizers and
solvents.
These auxiliaries are also included within the meaning of "perFume", as used
herein. Typically, perfumes are complex mixtures of a plurality of organic
compounds.
The range of the natural raw substances can embrace not only readily-
volatile, but also moderately-volatile and slightly-volatile components and
that of the synthetics can include representatives from practically all
classes
of fragrant substances, as will be evident from the following illustrative
compilation: natural products, such as tree moss absolute, basil oil, citrus
fruit oils (such as bergamot oil, mandarin oil, etc.), mastix absolute, myrtle
oil, paimarosa oil, patchouli oil, petitgrain oil Paraguay, wormwood oil,
alcohols, such as FamesolT''", Geraniol"~", Linalool"'", NeroIT"", phenylethyl
alcohol, RhodinolT"", cinnamic alcohol, aldehydes, such as citral,
Helional'~''", alpha-
CA 02310373 2000-OS-17
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28
hexyl-cinnamaldehyde, hydroxycitronellal, LiliaITM (p-tert-butyl-alpha -
methyldihydrocinnamaldehyde), methylnonylacetaldehyde, ketones, such as
allylionone, alpha-ionone, beta -ionone, isoraldein (isomethyl- alpha -
ionone), methylionone, esters, such as allyl phenoxyacetate, benzyl
salicylate, cinnamyl propionate, citronellyl acetate, citronellyl ethoxolate,
decyl acetate, dimethylbenzylcarbinyl acetate, dimethylbenzylcarbinyl
butyrate, ethyl acetoacetate, ethyl acetylacetate, hexenyl isobutyrate,
linalyl
acetate, methyl dihydrojasmonate, styrallyl acetate, vetiveryl acetate, etc.,
lactones, such as gamma-undecalactone, various components often used in
perfumery, such as musk ketone, indole, p-menthane-8-thiol-3-one, and
methyl-eugenol. Likewise, any conventional fragrant acetal or ketal known
in the art can be added to the present composition as an optional
component of the conventionally formulated perfume (c). Such conventional
fragrant acetals and ketals include the well-known methyl and ethyl acetals
and ketals, as well as acetals or ketals based on benzaldehyde, those
comprising phenylethyl moieties, or more recently developed specialties
such as those described in a United States Patent entitled "Acetals and
Ketals of Oxo-Tetralins and Oxo-Indanes, see U.S. Pat. No. 5 ,084,440,
issued January 28, 1992, assigned to Givaudan Corp. Of course, other
recent synthetic specialties can be included in the perfume compositions for
fully-formulated fabric softening compositions. These include the enol
ethers of alkyl-substituted oxo-tetralins and oxo-indanes as described in
U.S. Pat. 5,332,725, July 26, 1994, assigned to Givaudan; or Schiff Bases
as described in U.S. Pat. 5,264,615, December 9, 1991, assigned to
Givaudan.
The perfumes useful in the present invention compositions are substantially
free of halogenated materials and nitromusks.
Perfume can be present at a level of from 0% to 10%, preferably from 0.1
to 5%, and more preferably from 0.2% to 3%, by weight of the finished
composition. Fabric softener compositions of the present invention provide
improved fabric perfume deposition.
(Il-Enzvme
The compositions and processes herein can optionally employ one or more
enzymes such as lipases, proteases, cellulase, amylases and peroxidases.
CA 02310373 2004-04-15
29
A preferred enzyme for use herein is a cellulase enzyme. Indeed, this type
of enzyme will further provide a color care benefit to the treated fabric.
Cellulases usable herein include both bacterial and fungal types, preferably
having a pH optimum between 5 and 9.5. U.S. 4,435,307 discloses suitable
fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a
cellulase 212-producing fungus belonging to the genus Aeromonas, and
cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella
Auricula Solander. Suitable cellulases are also disclosed in GB-A-
2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME~ and
CELLUZYME~ (Novo) are especially useful. Other suitable cellulases are
also disclosed in WO 91/17243 to Novo, WO 96/34092, WO 96/34945 and
EP-A-0,739,982. In practical terms for current commercial preparations,
typical amounts are up to 5 mg by weight, more typically 0.01 mg to 3 mg, of
active enzyme per gram of the detergent composition. Stated otherwise, the
compositions herein will typically comprise from 0.001 % to 5%, preferably
0.01 %-1 % by weight of a commercial enzyme preparation. In the particular
cases where activity of the enzyme preparation can be defined otherwise
such as with cellulases, corresponding activity units are preferred (e.g.
CEVU or cellulase Equivalent Viscosity Units). For instance, the
compositions of the present invention can contain cellulase enzymes at a
level equivalent to an activity from 0.5 to 1000 CEVU/gram of composition.
Cellulase enzyme preparations used for the purpose of formulating the
compositions of this invention typically have an activity comprised between
1,000 and 10,000 CEVU/gram in liquid form, around 1,000 CEVU/gram in
solid form.
(J)-Other Optional Ingredients
The present invention composition can include optional components
conventionally used in fully formulated laundry detergent compositions such
as described in WO 97/05226, for example builders, bleaches, brighteners,
colorants; surfactants; anti-shrinkage agents; fabric crisping agents;
spotting
agents; germicides; fungicides; anti-oxidants such as butylated hydroxy
toluene, anti-corrosion agents, antifoam agents, polyamino functional
polymer, dispersible polyolefin such as Velustrol~ as disclosed in
CA 02310373 2004-04-15
WO 97/28239, and the like. The present invention can also
contain optional chelating agents.
A typical amount of such optional components will be from 0% to 15% by
weight.
The present invention can also include other compatible ingredients,
including those as disclosed in W096/02625, W096/21714, and
W096/21715.
Reduction of the fabric abrasion
The benefit provided by the use of the present invention is that the fabric
abrasion which arises on fabrics, upon a laundering process, is reduced,
e.g. it is meant that laundered fabrics which are in contact with a CG1 or
composition thereof exhibit a reduced fabric abrasion versus fabrics which
are in contact with no CGI or no CGI containing- composition but still
laundered.
Not to be bound by theory, it is believed that the mechanism for producing
the benefit of the invention is due to the abrasive effect of inorganic micro-
crystals growing at the fabric surface upon laundering in the absence of
CGI. The source of inorganic compounds is believed to be the feed water of
the laundering process as well as the soil present on the laundered
garments.
The fabric abrasion reduction benefit is visually assessed using the following
fabric reduction test method:
Fabric reduction test method
The compositions according to the present invention may be measured for
fabric reduction by laundering a cotton terry over repeated cycles (e.g. 20
cycles) respectively with and without CGI.
CA 02310373 2004-04-15
31
The method is comparative and thus only one fabric's abrasion respective to
another may be tested at any one time. The fabric abrasion is evaluated
using the following scale:
0 No fabric abrasion
1 Very weak fabric abrasion
2 Weak fabric abrasion
3 Moderate fabric abrasion
4 Strong fabric abrasion
Very strong fabric abrasion
In another aspect of the invention, there is provided a method for reducing
the fabric abrasion, in particular upon domestic laundering processes, which
comprises the steps of contacting the fabrics with a CGI or a composition
thereof as defined hereinbefore. Most preferably, the application of the CGI
to the fabric surface is made upon the rinsing step of a laundry process.
More preferably, the CGl is incorporated in fabric softening compositions.
In the exemplified compositions, the abbreviated component identifications
have the following meanings:
DEQA : Di-(tailowyl-oxy-ethyl) dimethyl ammonium chloride
DOEQA : Di-(oleyloxyethyl) dimethyl ammonium methylsulfate
DTDMAC : Ditallow dimethylammonium chloride
DHEQA : Di-(soft-tallowyl-oxy-ethyl) hydroxyethyl methyl
ammonium
methylsulfate
Fatty acid : tallow fatty acid IV=18
Electrolyte Calcium chloride
:
DTDMAMS : Ditallow dimethyl ammonium methylsulfate
SDASA : 1:2 Ratio of stearyldimethyl amineariple-pressed
stearic acid
Glycosperse Polyethoxylated sorbitan monostearate available
S-20 : from Lonza
Clay : Calcium Bentonite Clay, Bentonite L, sold by
Southern Clay
Products
TAE25 : Tallow alcohol ethoxylated with 25 moles of ethylene oxide
per mole of alcohol
PEG : Polyethylene Glycol 4000
CA 02310373 2004-04-15
32
PEI 1200 E4 : Ethoxylated polyethylene imine {MW 1800, at 50% active) as
synthesised in Synthesis example 2
PEI 1800 E7 : Ethoxylated polyethylene imine (MW 1800, at 50% active) as
synthesised as per Synthesis example 1
PEI 1200 E1 : Ethoxylated polyethylene imine (MW 1200, at 50% active in
water) as synthesised in Synthesis example 2
Dye Fix 1 : Cationic dye fixing agent (50% active) available under the
trademark Tinofix Eco from Ciba-Geigy
Dye Fix 2 : Emulsified cationic dye fixative (30% active) available under
the trademark Rewin SRF-O from CHT-Beitlich
LAS : Sodium linear C12 alkyl benzene
sulphonate
TAS : Sodium tallow alcohol sulphate
C25AS : Sodium C12-C15 linear alkyl sulphate
CxyEzS : Sodium C1x-C1y branched alkyl sulphate
condensed with z moles of ethylene
oxide
C45E7 : A C14-15 predominantly linear primary
alcohol
condensed with an average of 7 moles
of
ethylene oxide
C25 E3 : A C12-15 branched primary alcohol
condensed
with an average of 3 moles of ethylene
oxide
Cationic ester: Mixture of C12/C14 choline ester
Soap : Sodium linear alkyl carboxylate derived
from an
80/20 mixture of tallow and a coconut
oils.
TFAA : C1g-C1g alkyl N-methyl glucamide
TPKFA : C12-C14 topped whole cut fatty acids
Zeolite A : Hydrated Sodium Aluminosilicate of formula
Na 12(A102Si02)12. 27H20
having a primary particle size in the range from
0.1 to 10 micrometers
Citric acid : Anhydrous citric acid
Carbonate : Anhydrous sodium carbonate with a particle size
between 200~,m and 900~m
Silicate : Amorphous Sodium Silicate (Si02:Na20; 2.0
ratio)
CA 02310373 2004-10-19
33
Sulphate : Anhydrous sodium sulphate
Citrate : Tri-sodium citrate dihydrate of activity 86.4% with
a particle size distribution between 425~m and
850p,m
MAIAA : Copolymer of 1:4 maleiclacrylic acid, average
molecular weight about 70,000.
CMC : Sodium carboxymethyl cellulose
TM
Savinase Proteolytic enzyme of activity 4KNPUIg
.
Carezyr~M , Cellulytic enzyme of activity
: 1000 CEVUIg
Termamyl Amylolytic enzyme of activity 60KNU/g
.
Lipolase Lipolytic enzyme of activity 1 OOkLU/g
.
all sold
by NOVO
Industries
AIS and
of activity
mentioned
above unless
otherwise
specked
PB4 : Sodium perborate tetrahydrate of nominal
formula NaB02.3H20.H202
PB1 : Anhydrous sodium perborate bleach of
nominal formula NaB02.H202
TAED : Tetraacetyl ethylene diamine
DTPMP : Diethylene triamine penta (methylene
phosphonate), marketed by Monsanto under
the
Trade mark bequest 2060
HEDP : 1,1-hydroxyethane diphosphonic acid
PBT : 2-phosphonobutane-1,2,4-tricarboxylic acid
Polycarboxylic : Polycarboxylic compound marketed by BASF
under the trademark Sokalan CP 10
Glycolic : Glycolic acid
Photoactivated : Sulphonated Zinc Phthalocyanin encapsulated in
bleach dextrin soluble polymer
Brightener : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-
triazin-2-yl)amino) stiibene-2:2'-disulphonate.
CA 02310373 2000-OS-17
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Silicone antifoam : Polydirnethyldiloxane foam controller with
Siloxane-oxyalkylene copolymer as
dispersing agent with a ratio of said foam
controller to said disprersing agent of 10:1 to 100:1.
~~mthesis Example 1 -PreGiaration of PEI 1800 E1
Step A)-The ethoxylation is conducted in a 2 gallon stirred stainless steel
autoclave equipped for temperature measurement and control, pressure
measurement, vacuum and inert gas purging, sampling, and for introduction
of ethylene oxide as a liquid. A ~20 Ib. net cylinder of ethylene oxide (ARC)
is set up to deliver ethylene oxide as a liquid by a pump to the autoclave
with the cylinder placed on a scale so that the weight change of the cylinder
could be monitored.
A 750 g portion of polyethyleneimine (PEI) (Nippon Shokubai, Epomin SP-
018 having a listed average molecular weight of 1800 equating to 0.417
moles of polymer and 17.4 moles of nitrogen functions) is added to the
autoclave. The autoclave is then sealed and purged of air (by applying
vacuum to minus 28" Hg followed by pressurization with nitrogen to 250
psia, then venting to atmospheric pressure). The autoclave contents are
heated to 130 °C while applying vacuum. After about one hour, the
autoclave is charged with nitrogen to about 250 psia while cooling the
autoclave to about 105 °C. Ethylene oxide is then added to the
autoclave
incrementally over time while closely monitoring the autoclave pressure,
temperature, and ethylene oxide flow rate. The ethylene oxide pump is
turned off and cooling is applied to limit any temperature increase resulting
from any reaction exotherm. The temperature is maintained between 100
and 110 °C while the total pressure is allowed to gradually increase
during
the course of the reaction. After a total of 750 grams of ethylene oxide has
been charged to the autoclave (roughly equivalent to one mole ethylene
oxide per PEI nitrogen function), the temperature is increased to 110
°C and
the autoclave is allowed to stir for an additional hour. At this point, vacuum
is applied to remove any residual unreacted ethylene oxide.
Step B)- The reaction mixture is then deodorized by passing about 100 cu.
ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through
the reaction mixture while agitating and heating the mixture to 130 °C.
CA 02310373 2000-OS-17
WO 99lZ7052 PCT/US98/?,4817
35
The final reaction product is cooled slightly and collected in glass
containers
purged with nitrogen.
In other preparations the neutralization and deodorization is accomplished in
the reactor before discharging the product.
If a PEI 1800 E7 is desired, the following step of catalyst addition will be
included between Step A and B.
Vacuum is continuously applied while the autoclave is cooled to about 50
°C
while introducing 376 g of a 25% sodium methoxide in methanol solution
(1.74 moles, to achieve a 10% catalyst loading based upon PEI nitrogen
functions). The methoxide solution is sucked into the autoclave under
vacuum and then the autoclave temperature controller setpoint is increased
to 130 °C. A device is used to monitor the power consumed by the
agitator.
The agitator power is monitored along with the temperature and pressure.
Agitator power and temperature values gradually increase as methanol is
removed from the autoclave and the viscosity of the mixture increases and
stabilizes in about 1 hour indicating that most of the methanol has been
removed. The mixture is further heated and agitated under vacuum for an
additional 30 minutes.
Vacuum is removed and the autoclave is cooled to 105 °C while it
is being
charged with nitrogen to 250 psia and then vented to ambient pressure. The
autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again
added to the autoclave incrementally as before while closely monitoring the
autoclave pressure, temperature, and ethylene oxide flow rate while
maintaining the temperature between 100 and 110 °C and limiting any
temperature increases due to reaction exotherm. After the addition of 4500
g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per
mole
of PEI nitrogen function) is achieved over several hours, the temperature is
increased to 110 °C and the mixture stirred for an additional hour.
The reaction mixture is then collected in nitrogen purged containers and
eventually transferred into a 22 L three neck round bottomed flask equipped
with heating and agitation. The strong alkali catalyst is neutralized by
adding 167 g methanesulfonic acid (1.74 moles).
Other preferred examples such as PEI 1800 E2, PEI 1800 E4, PEI 1800
E15 and PEI 1800 E20 can be prepared by the above method by adjusting
CA 02310373 2000-OS-17
WO 99/27052 PCT/US98lZ4817
36
the reaction time and the relative amount of ethylene oxide used in the
reaction.
$»pthesis Example 2 - Pren~ration of PEI 12001
Step A)-The ethoxylation is conducted in a 2 gallon stirred stainless steel
autoclave equipped for temperature measurement and control, pressure
measurement, vacuum and inert gas purging, sampling, and for introduction
of ethylene oxide as a liquid. A ~20 Ib. net cylinder of ethylene oxide (ARC)
is set up to deliver ethylene oxide as a liquid by a pump to the autoclave
with the cylinder placed on a scale so that the weight change of the cylinder
could be monitored.
A 750 g portion of polyethyleneimine (PEl) ( having a listed average
molecular weight of 1200 equating to about 0.625 moles of polymer and
17.4 moles of nitrogen functions) is added to the autoclave. The autoclave
is then sealed and purged of air (by applying vacuum to minus 28" Hg
followed by pressurization with nitrogen to 250 psia, then venting to
atmospheric pressure). The autoclave contents are heated to 130 °C
while
applying vacuum. After about one hour, the autoclave is charged with
nitrogen to about 250 psia while cooling the autoclave to about 105 °C.
Ethylene oxide is then added to the autoclave incrementally over time while
closely monitoring the autoclave pressure, temperature, and ethylene oxide
flow rate. The ethylene oxide pump is turned off and cooling is applied to
limit any temperature increase resulting from any reaction exotherm. The
temperature is maintained between 100 and 110 °C while the total
pressure
is allowed to gradually increase during the course of the reaction. After a
total of 750 grams of ethylene oxide has been charged to the autoclave
(roughly equivalent to one mole ethylene oxide per PEI nitrogen function),
the temperature is increased to 110 °C and the autoclave is allowed to
stir
for an additional hour. At this point, vacuum is applied to remove any
residual unreacted ethylene oxide.
Step B)- The reaction mixture is then deodorized by passing about 100 cu.
ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through
the reaction mixture while agitating and heating the mixture to 130 °C.
The final reaction product is cooled slightly and collected in glass
containers
purged with nitrogen.
CA 02310373 2000-OS-17
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37
In other preparations the neutralization and deodorization is accomplished in
the reactor before discharging the product.
If a PEI 1200 E7 is desired, the following step of catalyst addition will be
included between Step A and B.
Vacuum is continuously applied while the autoclave is cooled to about 50
°C
while introducing 376 g of a 25% sodium methoxide in methanol solution
(1.74 moles, to achieve a 10% catalyst loading based upon PEI nitrogen
functions). The methoxide solution is sucked into the autoclave under
vacuum and then the autoclave temperature controller setpoint is increased
to 130 °C. A device is used to monitor the power consumed by the
agitator.
The agitator power is monitored along with the temperature and pressure.
Agitator power and temperature values gradually increase as methanol is
removed from the autoclave and the viscosity of the mixture increases and
stabilizes in about 1 hour indicating that most of the methanol has been
removed. The mixture is further heated and agitated under vacuum for an
additional 30 minutes.
Vacuum is removed and the autoclave is cooled to 105 °C while it
is being
charged with nitrogen to 250 psia and then vented to ambient pressure. The
autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again
added to the autoclave incrementally as before while closely monitoring the
autoclave pressure, temperature, and ethylene oxide flow rate while
maintaining the temperature between 100 and 110 °C and limiting any
temperature increases due to reaction exotherm. After the addition of 4500
g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per
mole
of PEI nitrogen function) is achieved over several hours, the temperature is
increased to 110 °C and the mixture stin-ed for an additional hour.
The reaction mixture is then collected in nitrogen purged containers and
eventually transferred into a 22 L three neck round bottomed flask equipped
with heating and agitation. The strong alkali catalyst is neutralized by
adding 167 g rnethanesulfonic acid (1.74 moles).
Other preferred examples such as PEI 1200 E2, PEI 1200 E3, PEI 1200
E15 and PEI 1200 E20 can be prepared by the above method by adjusting
the reaction time and the relative amount of ethylene oxide used in the
reaction.
CA 02310373 2000-OS-17
WO 99127052 PCTIUS98/24817
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E~.mpl~.1
Using the test method defined above, fabrics were contacted with an
aqueous liquid composition comprising 2% by weight of HEDP and
thereafter fabric abrasion was measured.
It was observed that fabrics treated with the CGI exhibited less fabric
abrasion versus compositions that were not treated.
iE~c~mrsl~2
Similar results are obtained when the following compositions were used.
Component A B C D E F G H
DEQA 2.6 2.9 18.0 19.0 19.0 - - -
TAE25 1.0 - - - - -
Fatty acid 0.3 1.0 - - - -
Hydrochloride 0.02 0.02 0.02 0.02 0.02 -
acid
PEG 0.6 0.6 0.6 - - -
Perfume 1.0 1.0 1.0 1.0 1.0 0.1 0.1 0.1
Silicone antifoam0.01 0.01 0.01 0.01 0.01 - -
PEI 1200 E1 3 3 3 3 - 15 - 10
PEI 1200 E2 3 10 -
Dye fix 1 - 1 1 1 - 10 -
Dye fix 2 2 2 2 - - - -
HEDP 0.2 - - 0.2 - 0.4 - 0.8
GI colic 0.2 - 0.5 0.4 -
Pol carbo late - 0.5 0.4 -
Electrolyte ( - 600 600 1200 -
m)
D a (ppm) 10 10 50 50 50 -
Water and minors
to balance to
100
Component I~ J K L M
DEQA 2.6 19.0 -
Fa acid 0.3 - -
Hydrochloride acid 0.0 0.02
2
PEG - 0.6 - -
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WO 99/Z7052 PC"f/US98124817
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Perfume 1.0 1.0 0.1 0.1 0.2
Silicone antifoam 0.0 0.01 - - -
1
PEI 1200 E1 3 3 15 10
PEI 1200 E4 - 10 -
Dye fix 1 1 - - 2.5
Dye fix 2 2 -
pBT 0.2 0.2 0.4 0.8 0.5
Polycarbo late - 0.4 - -
Electrolyte (ppm) - 600 - -
Dye (ppm) 10 50 - -
Water and minors to balance
to 100
Component N O P Q R S
DTDMAC - 15 -
~
DEQA 2.6 19.0 - 2.6 19.0
TAE25 0.3 - - - 0.3 -
Fatty acid 0.3 - - 0.3
Hydrochloride0.02 0.02 - 0.02 0.02 0.02
acid
PEG 0.6 0.6 0.6
Perfume 1.0 1.0 0.1 1.0 1.0 1.0
Silicone 0.01 0.01 - 0.01 0.01 0.01
antifoam
PEI 1800 E1 3 3 10 3 3 3
HEDP 0.2 0.2 - - -
pgT 0.2 0.2
Glycolic - 0.2 - -
pol carboxylic- - - 0.2 -
Dye fix 1 1 1 10 1 1 1
Dye fix 2 2 2 - 2 2 2
Electrolyte - 600 600 - 600
(ppm)
Dye (ppm) 10 50 - 50 10 50
Water and
minors to
balance to
100
CA 02310373 2000-OS-17
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.E~~cam Ire 3_
Similar results are obtained when the following compositions for use as
dryer-added sheets were used.
T U V W X Y Z AA BB
DOEQA 40 40 25 -
DHEQA - - 20 20 - - - -
DTDMAMS - 20 20 12 60
SDASA 30 30 30 20 20 30 30 20 -
Glycosperse S-20 - - - 10 10 - - - -
Glycerol - 20 20 10 -
Monostearate
Clay 4 4 4 3 3 4 4 4 -
Perfume 0.7 0.7 1.1 0.7 0.7 1.6 1.6 2.6 1.4
PEI 1800 E4 - 5 - - -
PEI 1200 E1 - - 4 4 2.2 2.2 - -
PEI 1800 E3 2 2 - - 5 7.0
D efixl 2 2 5 4 4 2.2 2.2 5 3
HEDP 0.2 - 0.5 - - 0.7
BPT 0.2 - - 0.9 - 0.2
Glycolic - 0.2 - 0.2 - _
Polycarboxylic - 0.2 - - 0.4 -
Stearic acid to
balance
Examlhe 44
Similar results are obtained with the following detergent compositions.
CC DD EE
Zeolite A 24.0 23.0 23.0
Sulphate 9.0
MAIAA 4.0 4.0 4.0
LAS 8.0 8.0 8.0
TAS - 2.0 2.0
Silicate 3.0 3.0 3.0
CA 02310373 2000-OS-17
WO 99!27052 PCT/US98/Z4817
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CMC 1.0 0.4 0.4
Brightener 0.2 - -
Soap 1.0 -
DTPMP 0.4 0.4 0.4
C45E7 2.5 2.0 2.0
C25E3 2.5 2.0 2.0
Silicone antifoam 0.3 5.0 5.0
Perfume 0.3 0.3 0.3
Carbonate 13.0 16.0 16.0
Citrate 5.0 5.0
PB4 18.0 - -
PB1 4.0 14.0 14.0
TAED 3.0 6.0 6.0
Photoactivated bleach 0.02% - -
Savinase. 1.0 1.0 1.0
Lipolase 0.4 0.4 0.4
Termamyl 0.30 0.6 0.6
Care me 0.6 0.6
PEI 1800 E7 AO 1.0
PEI 1200 E7 AO 1.0 1.0
HEDP 0.2 - -
BPT - - 0.2
Glycolic - 0.2 0.2
Po1 carboxylic 0.2 0.2
Balance (Moisture and
Miscellaneous) to
100
Exam lp a 5
Similar results are obtained with the following liquid detergent compositions.
FF
C25AS 13
C25E3S 2
TFAA 6
C12-14 alkyl dimeth Ih dro eth I ammonium 1
chloride
Cationic ester 1.5
CA 02310373 2000-OS-17
WO 99127052 PCT/US98/24817
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TPKFA 15
Citric acid 1
Ethanol 2
1,2 Propanediol
NaOH up to H 7.5
DTPMP 1.2
Savinase 0.5
Termam I (300 KNUIg) 0.15
Boric acid 1.5
Softening clay of the bentonite pe 4
Suspending cla SD3 0.3
PEI 1200 E7 1
HEDP 0.2
Balance (Moisture and Miscellaneous) 100
