Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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CLEAR OR TRANSLUCENT AQUEOUS FABRIC SOFTENER COMPOSITIONS CONTAINING HIGH
ELECTROLYTE
CONTENT AND OPTIONAL PHASE STABILIZER
TECHNICAL FIELD
The present invention relates to specific clear or translucent fabric softener
compositions. Specifically, clear, or translucent liquid compositions are
prepared with
high electrolyte levels to provide a dilution viscosity benefit and/or to
allow the use of
less and/or additional principal solvents as described hereinafter.
Optionally, but
preferably, the compositions can also contain an optional phase stabilizer,
e.g., nonionic,
ethoxylated cationic, etc. surfactant to improve properties.
BACKGROUND OF THE INVENTION
Concentrated clear compositions containing ester and/or amide linked fabric
softening actives and specific principal solvents are disclosed in U. S. Pat.
No.
5,759,990, issued Jun. 2, 1998 in the names of E. H. Wahl, H. B. Tordil, T.
Trinh, E. R.
Carr, R. O. Keys, and L. M. Meyer, for Concentrated Fabric Softening
Composition
With Good Freeze/Thaw Recovery and Highly Unsaturated Fabric Softener Compound
Therefor, and in U. S. Pat. No. 5,747,443, issued May 5, 1998 in the names of
Wahl,
Trinh, Gosselinl:, Letton, and Sivik for Fabric Softening
Compound/Composition, said
patents being incorporated herein by reference. The fabric softener actives in
said
patents are preferably biodegradable ester-linked materials, containing, long
hydrophobic
groups with unsaturated chains. Similar clear liquid fabric softening
compositions are
described in WO 97/03169, incorporated herein by reference, which describes
the
formulation of liquid fabric softening compositions using said specific
principal solvents.
Lowering the principal solventlsoftener ratio below a critical point can
result in
an increase in viscosity and/or gelling of the fabric softener composition on
dilution into
water which adversely affects performance through an increase in fabric
staining
incidents, more residue left in machine-attached and machine-independent
dispensers,
less deposition of fabric softener active, and less uniform deposition of
fabric softener
active. This critical ratio differs for the different solvents, but in general
it is believed
that the solvent/softener ratio at which gelling occurs is higher for
relatively water
immiscible solvents vs. water miscible solvents. The gelling and/or increased
viscosity
upon dilution is particularly unacceptable when it occurs between the dilution
ratios of
from about 1:1 to about 1:5 (fabric softener composition to water) since many
consumers
practice the habit of pre-diluting fabric softener compositions to these
ratios. This habit
is typical and is recommended by many washing machine manufacturers for
consumers
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using the automatic dispensing device supplied with their washing machine.
Increased
viscosity or gelling of the fabric softener upon dilution, whether the
dilution is a pre-
dilution carried out by the consumer or the machine or whether dilution is
carried out
during the rinse cycle through dispensing into the rinse by the consumer, by
an
appliance, or by the machine, can adversely affect the dispersion of the
fabric softener
composition in the rinse, resulting in poor performance, including an increase
in fabric
staining incidents.
SUMMARY OF THE INVENTION
The clear, or translucent liquid fabric softener compositions herein comprise:
A. from about 2% to about 80%, preferably from about 13% to about 75%,
more preferably from about 17% to about 70%, and even more preferably from
about
19% to about 65%, by weight of the composition, of fabric softener active,
more
preferably biodegradable fabric softener actives as disclosed hereinafter. The
phase
transition temperature of the softener active or mixture of actives,
containing less than
5% organic solvent or water, is preferably less than 50°C, more
preferably less than
about 35°C, even more preferably less than about 20°C, and yet
even more preferably
less than about 10°C, or is amorphous and has no significant
endothermic phase
transition in the region -50°C to 100°C, as measured by
differential scanning calorimetry
as disclosed hereinafter.
B. at least an effective level of principal solvent preferably having a ClogP
of from
about -2.0 to about 2.6 , more preferably from about -1.7 to about 1.6, and
even more
preferably from about -1.0 to about 1.0, as defined hereinafter, typically at
a level that is
less than about 40%, preferably from about 1% to about 25%, more preferably
from
about 3% to about 10% by weight of the composition;
C. from about 0.5 % to about 10% by weight, preferably from about 0.75 % to
about
2.5 % by weight of the composition, and more preferably from about 1 % to
about 2
by weight of the composition of electrolyte as defined hereinafter;
D. optionally, but preferably, from 0% to about 1 S%, preferably from about
0.1% to about 7%, and more preferably from about 1% to about 6%, by weight of
the composition of phase stabilizer, preferably surfactant containing
alkoxylation,
and also preferably having an HLB of from about 8 to about 20, more preferably
from about 10 to about 18, and even more preferably from about 11 to about 15,
and more preferably as described hereinafter; and
E. the balance water.
The clear, or translucent liquid fabric softener compositions can optionally
also
contain:
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(a) optionally, but preferably, from 0% to about 15%, more preferably from
about 0.1 % to about 8%, and even more preferably from about 0.2% to about 5%,
of
perfume;
(b) principal solvent extenders;
(c) cationic charge boosters;
(d) other optional ingredients such as brighteners, chemical stabilizers,
enzymes, soil release agents, bactericides, chelating agents, silicones, color
care agents;
and
(e) mixtures thereof.
Preferably, the compositions herein are aqueous, translucent or clear,
preferably
clear, compositions containing from about 10% to about 95%, preferably from
about
20% to about 80%, more preferably from about 30% to about 70%, and even more
preferably from about 40% to about 60%, water. These products (compositions)
are
usually not translucent or clear without principal solvent B.
The principal solvent and/or electrolyte levels, as well as the identity of
the
principal solvent, are related to the level and identity of the softener. The
higher the
softener level, surprisingly, the greater the choice of level and identity of
principal
solvent, electrolyte, and phase stabilizer which will yield clear stable
compositions. The
electrolyte and phase stabilizer are typically used at the lowest level that
will provide the
desired result.
The pH of the compositions, especially those containing the preferred softener
actives comprising an ester linkage, should be from about 1 to about 5,
preferably from
about 2 to about 4, and more preferably from about 2.7 to about 3.5.
DETAILED DESCRIPTION OF THE INVENTION
A. FABRIC SOFTENER ACTIVES
Typical levels of incorporation of the softening compound (active) in the
softening composition are of from 2% to 80% by weight, preferably from 5% to
75%,
more preferably from 15% to ?0%, and even more preferably from 19% to 65%, by
weight of the composition, and preferably is biodegradable as disclosed
hereinafter.
As has been previously disclosed in U. S. Pat. No. 5,759,990, issued Jun. 2,
1998
in the names of E. H. Wahl, H. B. Tordil, T. Trinh, E. R. Carr, R. O. Keys,
and L. M.
Meyer, for Concentrated Fabric Softening Composition with Good Freeze/Thaw
Recovery and Highly Unsaturated Fabric Softener Compound Therefor, and in U.
S. Pat.
No. 5,747,443, issued May 5, 1998 in the names of Wahl, Trinh, Gosselink,
Letton, and
Sivik for Fabric Softening Compound/Composition, it has been found that
softener
actives with alkyl chains that are unsaturated or branched are particularly
well suited for
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use in clear or translucent aqueous fabric softener compositions. An indicator
of the
suitability of softener actives for use in the compositions of this invention
is the phase
transition temperature. Preferably, the phase transition temperature of the
softener
active or mixture of actives, containing less than 5% organic solvent or
water, is less than
~~'°C, more preferably less than about 35°C, even more
preferably less than about 20°C,
and yet even more preferably less than about 10°C, or is amorphous and
has no
significant endothermic phase transition in the region -50°C to
100°C.
The phase transition temperature can be measured with a Mettler TA 3000
differential scanning calorimeter with Mettler TC l0A Processor.
The softening compound can be selected from cationic, nonionic, and/or
amphoteric fabric softening compounds. Typical of the cationic softening
compounds
are the quaternary ammonium compounds or amine precursors thereof as defined
hereinafter.
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Preferred Diester Quaternary Ammonium Fabric Softenine Active _Compound (DEOA)
(1) The first type of DEQA preferably comprises, as the principal active,
(DEQA ( 1 )J compounds of the formula
]R4-m - N+ - ((CH2)n - Y - R 1 Jm ) X_
wherein each R substituent is either hydrogen, a short chain Cl-C6, preferably
Cl-C3
alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl,
hydroxyethyl,
and the like, poly (C2_3 alkoxy), preferably polyethoxy, group, benzyl, or
mixtures
thereof; each m is 2 or 3; each n is from 1 to about 4, preferably 2; each Y
is -O-(O)C-,
-C(O)-O-, -NR-C(O)-, or -C(O)-NR-; the sum of carbons in each R l , plus one
when Y is
-O-(O)C- or -NR-C(O) -, is C 12-C22~ Preferably C 14-C20, with each R 1 being
a
hydrocarbyl, or substituted hydrocarbyl group, and X- can be any softener-
compatible
anion, preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate,
and nitrate,
more preferably chloride or methyl sulfate (As used herein, the "percent of
softener
active" containing a given Rl group is based upon taking a percentage of the
total active
based upon the percentage that the given R1 group is, of the total Rl groups
present.);
(2) A second type of DEQA active [DEQA (2)] has the general formula:
[R3N+CH2CH(YR 1 )(CH2YR 1 )J X-
wherein each Y, R, R1, and X- have the same meanings as before. Such compounds
include those having the formula:
[CH3J3 N(+)(CH2CH(CH20(O)CR1)O(O)CR1] C1(-)
wherein each R is a methyl or ethyl group and preferably each R 1 is in the
range of C 15
to C 1 g. As used herein, when the diester is specified, it can include the
monoester that is
present. The amount of monoester that can be present is the same as in DEQA (
1 ).
These types of agents and general methods of making them are disclosed in U.S.
Pat. No. 4,137,180, Naik et al., issued Jan. 30, 1979, which is incorporated
herein by
reference. An example of a preferred DEQA (2) is the "propyl" ester quaternary
ammonium fabric softener active having the formula 1,2-di(acyloxy)-3-
trimethylammoniopropane chloride, where the acyl is the same as that of FA 1
disclosed
hereinafter.
Some preferred clear fabric softening compositions of the present invention
contain as an essential component from about 2% to about 75%, preferably from
about
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8% to about 70%, more preferably from about 13% to about 65%, and even more
preferably from about 18% to about 45% by weight of the composition, of
softener active
having the formula:
(R1C(O)OC2H4~mN+(R)4-m X_
wherein each R1 in a compound is a C6-C22 hydrocarbyl group, preferably having
an
IV from about 70 to about 140 based upon the IV of the equivalent fatty acid
with the
cis/trans ratio preferably being as described hereinafter, m is a number from
1 to 3 on the
weight average in any mixture of compounds, each R in a compound is a C1-3
alkyl or
hydroxy alkyl group, the total of m and the number of R groups that are
hydroxyethyl
groups equaling 3, and X is a softener compatible anion, preferably methyl
sulfate.
Preferably the cisarans isomer ratio of the fatty acid (of the C 18:1
component) is at least
about l:l, preferably about 2:1, more preferably about 3:1, and even more
preferably
about 4:1, or higher.
These preferred compounds, or mixtures of compounds, have (a) either a Hunter
"L" transmission of at least about 85, typically from about 85 to about 95,
preferably
from about 90 to about 95, more preferably above about 95, if possible, (b)
only low,
relatively non-detectable levels, at the conditions of use, of odorous
compounds selected
from the group consisting of: isopropyl acetate; 2,2'-ethylidenebis(oxy)bis-
propane;
1,3,5-trioxane; and/or short chain fatty acid (4-12, especially 6-10, carbon
atoms) esters,
especially methyl esters; or (c) preferably, both.
The Hunter L transmission is measured by (1) mixing the softener active with
solvent at a level of about 10% of active, to assure clarity, the preferred
solvent being
ethoxylated (one mole EO) 2,2,4-trimethyl-1,3-pentanedial and (2) measuring
the L color
value against distilled water with a Hunter ColorQUEST~ colorimeter made by
Hunter
Associates Laboratory, Reston, Virginia.
The level of odorant is defined by measuring the level of odorant in a
headspace
over a sample of the softener active (about 92% active). Chromatograms are
generated
using about 200 mL of head space sample over about 2.0 grams of sample. The
head
space sample is trapped on to a solid absorbent and thermally desorbed onto a
column
directly via cryofocussing at about -100°C. The identifications of
materials is based on
the peaks in the chromatograms. Some impurities identified are related to the
solvent
used in the quaternization process, (e.g., ethanol and isopropanol). The
ethoxy and
methoxy ethers are typically sweet in odor. There are C6 -Cg methyl esters
found in a
typical current commercial sample, but not in the typical softener actives of
this
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invention. These esters contribute to the perceived poorer odor of the current
commercial samples. The level of each odorant in ng/L found in the head space
over a
preferred active is as follows: Isopropyl acetate - < l; 1,3,5-trioxane - 5;
2,2'-
ethylidenebis(oxy)-bispropane - < 1; C6 methyl ester - < 1; Cg Methyl ester -
< 1; and C, o
Methyl ester - < 1. odorant
The acceptable level of each odorant is as follows: isopropyl acetate should
be
less than about S, preferably less than about 3, and more preferably less than
about 2,
nanograms per liter (rIg/L.); 2,2'-ethylidenebis(oxy)bis-propane should be
less than about
200, preferably less than about 100, more preferably less than about 10, and
even more
preferably less than about 5, nanograms per liter (11g/L.); 1,3,5-trioxane
should be less
than about 50, preferably less than about 20, more preferably less than about
10, and
even more preferably less than about 7, nanograms per liter (r)g/L.); and/or
each short
chain fatty acid (4-12, especially 6-10, carbon atoms) ester, especially
methyl esters
should be less than about 4, preferably less than about 3, and more preferably
less than
about 2, nanograms per liter (rlg/L.).
The elimination of color and odor materials can either be accomplished after
formation of the compound, or, preferably, by selection of the reactants and
the reaction
conditions. Preferably, the reactants are selected to have good odor and
color. For
example, it is possible to obtain fatty acids, or their esters, for sources of
the long fatty
acyl group, that have good color and odor and which have extremely low levels
of short
chain (C4_12, especially C6_10) fatty acyl groups. Also, the reactants can be
cleaned up
prior to use. For example, the fatty acid reactant can be double or triple
distilled to
remove color and odor causing bodies and remove short chain fatty acids.
Additionally,
the color of a triethanolamine reactant if used needs to be controlled to a
low color level
(e.g. a color reading of about 20 or less on the APHA scale). The degree of
clean up
required is dependent on the level of use and the presence of other
ingredients. For
example, adding a dye can cover up some colors. However, for clear and/or
light colored
products, the color must be almost non-detectable. This is especially true for
higher
levels of active, e.g., from about 2% to about 80%, preferably from about 13%
to about
75%, more preferably from about 17% to about 70%, and even more preferably
from
about 19% to about 65% of the softener active by weight of the composition.
Similarly,
the odor can be covered up by higher levels of perfume, but at the higher
levels of
softener active there is a relatively high cost associated with such an
approach, especially
in terms of having to compromise the odor quality. Odor quality can be further
improved
by use of ethanol as the quaternization reaction solvent.
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A preferred biodegradable fabric softener compounds comprises quaternary
ammonium salt, the quaternized ammonium salt being a quaternized product of
condensation between:
a)-a fraction of saturated or unsaturated, linear or branched fatty acids, or
of derivatives
of said acids, said fatty acids or derivatives each possessing a hydrocarbon
chain in
which the number of atoms is between 5 and 21, and
b)-triethanolamine,
characterized in that said condensation product has an acid value, measured by
titration
of the condensation product with a standard KOH solution against a
phenolphthalein
indicator, of less than about 6.5.
The acid value is preferably less than or equal to about 5, more preferably
less
than about 3. Indeed, the lower the AV, the better softness performance is
obtained.
The acid value is determined by titration of the condensation product with a
standard KOH solution against a phenolphthalein indicator according to
ISO#53402. The
AV is expressed as mg KOH/g of the condensation product.
For optimum softness benefit, it is preferred that the reactants are present
in a
molar ratio of fatty acid fraction to triethanolamine of from about 1:1 to
about 2.5:1.
It has also been found that the optimum softness performance is also affected
by
the detergent carry-over laundry conditions, and more especially by the
presence of the
anionic surfactant in the solution in which the softening composition is used.
Indeed, the
presence of anionic surfactant that is usually carried over from the wash will
interact with
the softener compound, thereby reducing its performance. Thus, depending on
usage
conditions, the mole ratio of fatty acid/ triethanolamine can be critical.
Accordingly,
where no rinse occurs between the wash cycle and the rinse cycle containing
the
softening compound, a high amount of anionic surfactant will be carried over
in the rinse
cycle containing the softening compound. In this instance, it has been found
that a fatty
acid fraction/triethanolamine mole ratio of about 1.4:1 to about 1.8:1 is
preferred. By
high amount of anionic surfactant, it is meant that the presence of anionic in
the rinse
cycle at a level such that the molar ratio anionic surfactant/cationic
softener compound of
the invention is at least about 1/10.
These fabric softener compounds for use herein are typically mixtures of
materials. The weight percentages of compounds wherein one (monoester), two
(diester), or three (triester) of the triethanolamine hydroxy groups is
esterified with a
fatty acyl group are as follows: Monoester - from about 12% to about 22%;
diester -
from about 43% to about 57%; and triester - from about 13% to about 28%. These
compounds, as formed and used in the formulation of fabric softener
compositions,
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typically contain from about 6% to about 20°~o by weight of solvent,
e.g., from about 3%
to about 10% of a lower molecular alcohol like ethanol and from about 3% to
about 10%
of solvent that is more hydrophobic, like hexylene glycol.
A method of treating fabrics comprises the step of contacting the fabrics in
an
aqueous medium containing the above softener compounds or softening
composition
wherein the fatty acid /triethanolamine mole ratio in the softener compound is
from about
1.4:1 to about 1.8:1, preferably about 1.5:1 and the aqueous medium comprises
a molar
ratio of anionic surfactant to said softener compound of the invention of at
least about
1:10.
When an intermediate rinse cycle occurs between the wash and the later rinse
cycle, less anionic surfactant, i.e. less than about 1:10 of a molar ratio
anionic surfactant
to cationic compound of the invention, will then be carried over. Accordingly,
it has been
found that a fatty acid / triethanolamine mole ratio of about 1.8:1 to about
2.2:1 is then
preferred. Le., then the method of treating fabrics comprises the step of
contacting the
fabrics in an aqueous medium containing the softener compound of the invention
or
softening composition thereof wherein the fatty acid/triethanolamine mole
ratio in the
softener compound is from about 1.8:1 to about 2:1, preferably about 2.0:1,
and most
preferably about 1.9, and the aqueous medium comprises a molar ratio of
anionic
surfactant to said softener compound of the invention of less than about 1:10.
In a preferred embodiment the fatty acid fraction and the triethanolamine are
present in a molar ratio of from about 1:1 to about 2.5:1.
Preferred cationic, preferably biodegradable quaternary, ammonium fabric
softening compounds can contain the group -(O)CR1 which is derived from animal
fats,
unsaturated, and polyunsaturated, fatty acids, e.g., oleic acid, and/or
partially
hydrogenated fatty acids, derived from vegetable oils and/or partially
hydrogenated
vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil,
corn oil,
soybean oil, tall oil, rice bran oil, etc. Non-limiting examples of fatty
acids (FA) are
listed in U.S. Pat. No. 5,759,990 at column 4, lines 45-66.
Mixtures of fatty acids, and mixtures of FAs that are derived from different
fatty
acids can be used, and are preferred. Nonlimiting examples of FA's that can be
blended,
to form FA's of this invention are as follows:
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Fattv Acvl GroupFA 1 FA2 FA3
C,4 0 U 1
C,6 3 11 25
C, 8 3 4 20
C14:1 0 0 0
C16:1 1 1 0
C 18:1 79 27 45
C18:2 13 50 6
C18:3 1 7 0
Unknowns 0 0 3
Total 100 100 100
IV 99 125-138 56
cis/trans (C 5 - 6 Not Available 7
18:1 )
TPU 14 5 7 6
FA1 is a partially hydrogenated fatty acid prepared from canola oil, FA2 is a
fatty acid prepared from soy bean oil, and FA3 is a slightly hydrogenated
tallow fatty
acid.
Prefen;ed softener actives contain an effective amount of molecules containing
two
ester linked hydrophobic groups [R1C(CO)O-], said actives being referred to
hereinafter
as "DEQA's", are those that are prepared as a single DEQA from blends of all
the
different fatty acids that are represented (total fatty acid blend), rather
than from blends
of mixtures of separate finished DEQA's that are prepared from different
portions of the
total fatty acid blend.
It is preferred that at least a majority of the fatty acyl groups are
unsaturated, e.g.,
from about 50% to 100%, preferably from about 55% to about 99%, more
preferably
from about 60% to about 98%, and that the total level of active containing
polyunsaturated fatty acyl groups (TPU) be preferably from 0% to about 30%.
The
cis/trans ratio for the unsaturated fatty acyl groups is usually important,
with the cis/trans
ratio being from about 1:1 to about 50:1, the minimum being about 1:1,
preferably at
least about 3:1, and more preferably from about 4:1 to about 20:1. (As used
herein, the
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"percent of softener active" containing a given R 1 group is the same as the
percentage of
that same R1 group is to the total RI groups used to form all of the softener
actives.)
The unsaturated, including the preferred polyunsaturated, fatty acyl and/or
alkylene groups, discussed hereinbefore and hereinafter, surprisingly provide
effective
softening, but also provide better rewetting characteristics, good antistatic
characteristics,
and especially, superior recovery after freezing and thawing.
The highly unsaturated materials are also easier to formulate into
concentrated
premixes that maintain a low viscosity for the neat product composition and
are therefore
easier to process, e.g., pump, mixing, etc. These highly unsaturated materials
(total level
of active containing polyunsaturated fatty acyl groups (TPU) being typically
from about
3% to about 30%, with only the low amount of solvent that normally is
associated with
such materials, i.e., from about 5% to about 20%, preferably from about 8% to
about
25%, more preferably from about 10% to about 20%, weight of the total
softener/solvent
mixture, are also easier to formulate into concentrated, stable compositions
of the present
invention, even at ambient temperatures. This ability to process the actives
at low
temperatures is especially important for the polyunsaturated groups, since it
minimizes
degradation. Additional protection against degradation can be provided when
the
compounds and softener compositions contain effective antioxidants, chelants,
and/or
reducing agents, as disclosed hereinafter.
It will be understood that substituents R and R1 can optionally be substituted
with
various groups such as alkoxyl or hydroxyl groups, and can be straight, or
branched so
long as the RI groups maintain their basically hydrophobic character.
A preferred long chain DEQA is the DEQA prepared from sources containing high
levels of polyunsaturation, i.e., N,N-di(acyl-oxyethyl)-N,N-
methylhydroxyethylammonium methyl sulfate, where the acyl is derived from
fatty acids
containing sufficient polyunsaturation, e.g., mixtures of tallow fatty acids
and soybean
fatty acids. Another preferred long chain DEQA is the dioleyl (nominally)
DEQA, i.e.,
DEQA in which N,N-di(oleoyl-oxyethyl)-N,N-methylhydroxyethylammonium methyl
sulfate is the major ingredient. Preferred sources of fatty acids for such
DEQAs are
vegetable oils, and/or partially hydrogenated vegetable oils, with high
contents of
unsaturated, e.g., oleoyl groups.
As used herein, when the DEQA diester (m=2) is specified, it can include the
monoester (m=1) and/or triester {m=3) that are present. Preferably, at least
about 30% of
the DEQA is in the diester form, and from 0% to about 30% can be DEQA
monoester,
e.g., there are three R groups and one R1 group. For softening, under nollow
detergent
carry-over laundry conditions the percentage of monoester should be as low as
possible,
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preferably no more than about 15%. However, under high, anionic detergent
surfactant
or detergent builder carry-over conditions, some monoester can be preferred.
The overall
ratios of diester "quaternary ammonium active" (quat) to monoester quat are
from about
2.5:1 to about 1:1, preferably from about 2.3:1 to about 1.3:1. Under high
detergent
carry-over conditions, the di/manoester ratio is preferably about 1.3:1. The
level of
monoester present can be controlled in manufacturing the DEQA by varying the
ratio of
fatty acid, or fatty acyl source, to triethanolamine. The overall ratios of
diester quat to
triester quat are from about 10:1 to about 1.5:1, preferably from about 5:1 to
about 2.8:I .
The above compounds can be prepared using standard reaction chemistry. In one
synthesis of a di-ester variation of DTDMAC, triethanolamine of the formula
N(CH2CH20H)3 is esterified, preferably at two hydroxyl groups, with an acid
chloride
of the formula R1C(O)Cl, to form an amine which can be made cationic by
acidification
(one R is H) to be one type of softener, or then quaternized with an alkyl
halide, RX, to
yield the desired reaction product (wherein R and R1 are as defined
hereinbefore).
However, it will be appreciated by those skilled in the chemical arts that
this reaction
sequence allows a broad selection of agents to be prepared.
In preferred DEQA (1) and DEQA (2) softener actives, each R1 is a hydrocarbyl,
or substituted hydrocarbyl, group, preferably, alkyl, monounsaturated alkenyl,
and
polyunsaturated alkenyl groups, with the softener active containing
polyunsaturated
alkenyl groups being preferably at least about 3%, more preferably at least
about 5%,
more preferably at least about 10%, and even more preferably at least about
15%, by
weight of the total softener active present; the actives preferably containing
mixtures of
R1 groups, especially within the individual molecules.
The DEQAs herein can also contain a low level of fatty acid, which can be from
unreacted starting material used to form the DEQA and/or as a by-product of
any partial
degradation (hydrolysis) of the softener active in the finished composition.
It is preferred
that the level of free fatty acid be low, preferably below about 15%, mare
preferably
below about 10%, and even more preferably below about 5%, by weight of the
softener
actwe.
The fabric softener actives herein are preferably prepared by a process
wherein a
chelant, preferably a diethylenetriaminepentaacetate (DTPA) and/or an ethylene
diamine-
N,N~-disuccinate (EDDS) is added to the process. Another acceptable chelant is
tetrakis-
(2-hydroxylpropyl) ethylenediamine (TPED). Also, preferably, antioxidants are
added to
the fatty acid immediately after distillation and/or fractionation and/or
during the
esterification reactions and/or post-added to the finished softener active.
The resulting
softener active has reduced discoloration and malodor associated therewith.
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WO 99/27050 PCTNS98/25079
13
The total amount of added chelating agent is preferably within the range of
from
about 10 ppm to about 5,000 ppm, more preferably within the range of from
about 100
ppm to about 2500 ppm by weight of the formed softener active. The source of
triglyceride is preferably selected from the group consisting of animal fats,
vegetable
oils, partially hydrogenated vegetable oils, and mixtures thereof. More
preferably, the
vegetable oil or partially hydrogenated vegetable oil is selected from the
group consisting
of canola oil, partially hydrogenated canola oil, safflower oil, partially
hydrogenated
safflower oil, peanut oil, partially hydrogenated peanut oil, sunflower oil,
partially
hydrogenated sunflower oil, corn oil, partially hydrogenated corn oil, soybean
oil,
partially hydrogenated soybean oil, tall oil, partially hydrogenated tall oil,
rice bran oil,
partially hydrogenated rice bran oil, and mixtures thereof. Most preferably,
the source of
triglyceride is canola oil, partially hydrogenated canola oil, and mixtures
thereof. The
process can also include the step of adding from about 0.01 % to about 2% by
weight of
the composition of an antioxidant compound to any or all of the steps in the
processing
of the triglyceride up to, and including, the formation of the fabric softener
active.
The above processes produce a fabric softener active with reduced coloration
and
malodor.
Preparation of a fabric softening premix composition comprises preparing a
fabric
softening active as described above and mixing the fabric softener active,
optionally
containing a low molecular weight solvent, with a principal solvent having a
ClogP, as
described hereinafter, of from about -2.0 to about 2.6 thereby forming a
fabric softener
premix. The premix can comprise from about 55% to about 85% by weight of
fabric
softening active and from about 10% to about 30% by weight of principal
solvent.
Again, the process can also include the step of adding from about 0.01 % to
about 2% by
weight of the composition of an antioxidant compound to any or all of the
processing
steps.
Other Softener Actives
The compositions can also contain other, usually supplementary, fabric
softener
active(s), usually in minor amounts, typically from 0% to about 35%,
preferably from
about 1 % to about 20%, more preferably from about 2% to about 10%, said other
fabric
softener active being selected from:
( 1 ) softener having the formula:
(R4_m - N(+) - R 1 m~ A-
wherein each m is 2 or 3, each R 1 is a C6-C22, preferably C 14-C20, but no
more than
one being less than about C 12 and then the other is at least about 16,
hydrocarbyl, or
CA 02310612 2000-OS-18
PCT/US98/25079
WO 99/27050
14
substituted hydrocarbyl substituent, preferably C 10-C2p alkyl or alkenyl
(unsaturated
alkyl, including polyunsaturated alkyl, also referred to sometimes as
"alkylene"), most
preferably C12-Clg alkyl or alkenyl, and where the Iodine Value (hereinafter
referred to
as "IV") of a fatty acid containing this R1 group is from about 70 to about
140, more
preferably from about 80 to about 130; and most preferably from about 90 to
about 115
(as used herein, the term "Iodine Value" means the Iodine Value of a "parent"
fatty acid,
or "corresponding" fatty acid, which is used to define a level of unsaturation
for an R1
group that is the same as the level of unsaturation that would be present in a
fatty acid
containing the same RI group) with, preferably, a cis/trans ratio of from
about 1:1 to
about 50:1, the minimum being 1:1, preferably from about 2:1 to about 40:1,
more
preferably from about 3:1 to about 30:1, and even more preferably from about
4:1 to
about 20:1; each R1 can also preferably be a branched chain C 14-C22 alkyl
group,
preferably a branched chain C 16-C 1 g group; each R is H or a short chain C 1-
C6,
preferably C1-C3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred),
ethyl,
propyl, hydroxyethyl, and the like, benzyl, or (R2 O)2_4H where each R2 is a C
1 _6
alkylene group; and A- is a softener compatible anion, preferably, chloride,
bromide,
methylsulfate, ethylsulfate, sulfate, and nitrate, more preferably chloride
and methyl
sulfate;
(2) softener having the formula:
N CH2
Rl C _
O
\ N+ CH2
Rl C G R2~
R
wherein each R, R1, and A- have the definitions given above; each R2 is a C1-6
alkylene
group, preferably an ethylene group; and G is an oxygen atom or an -NR- group;
(3) softener having the formula:
N-CHI
Ri-C
O N-CH2
Rl-C-G-R
wherein R1, R2 and G are defined as above;
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WO 99/27050 PCTNS98/25079
(4) reaction products of substantially unsaturated and/or branched chain
higher fatty acids with dialkylenetriamines in, e.g., a molecular ratio of
about 2:I, said
reaction products containing compounds of the formula:
R1--~(O~--NH RZ--NH R3 NH--C(O~-R1
wherein R 1, R~ are defined as above, and each R3 is a C 1-6 alkylene group,
preferably
an ethylene group;
(5) softener having the formula:
[R1--C(O~--NR-RZ-N(R)2--R3 NR-~(O}--R1]+ A-
wherein R, R 1, R~, R3 and A- are defined as above;
(6) the reaction product of substantially unsaturated and/or branched chain
higher fatty acid with hydroxyalkylalkylenediamines in a molecular ratio of
about 2:1,
said reaction products containing compounds of the formula:
R 1-C(O)-NH-R2-N(R30H)-C(O)-R 1
wherein R 1, R~ and R3 are defined as above;
(7) softener having the formula:
R R
N-R2-N
N~ N ZAO
R1 R'
wherein R, R1, R2, and A- are defined as above; and
(8) mixtures thereof.
Other optional but highly desirable cationic compounds which can be used in
combination with the above softener actives are compounds containing one long
chain
acyclic Cg-C22 hydrocarbon group, selected from the group consisting of:
(8) acyclic quaternary ammonium salts having the formula:
[R1 N(RS)~_R6]+ A-
wherein R5 and R6 are C1-C4 alkyl or hydroxyalkyl groups, and R1 and A- are
defined
as herein above;
(9) substituted imidazolinium salts having the formula:
CA 02310612 2000-OS-18
WO 99127050 PCT/US98/2507~
16
O
~N-CH2
Ri-C ~ AO
N-CH2
R7~ ~H
wherein R~ is hydrogen or a C1-C4 saturated alkyl or hydroxyalkyl group, and
R1 and
A- are defined as hereinabove;
(10) substituted imidazolinium salts having the formula:
_ O
RI-C N CHZ Ao
N-CHI
HO-R2 ~ ERs
wherein RS is a C 1-C4 alkyl or hydroxyalkyl group, and R 1, R2, and A- are as
defined
above;
( 11 ) alkylpyridinium salts having the formula:
O
Ra-N ~ A
wherein R4 is an acyclic aliphatic Cg-C22 hydrocarbon group and A' is an
anion; and
(12) alkanamide alkylene pyridinium salts having the formula:
O O
Rl-C-NH-Rz-N O A~
wherein R1, R2 and A- are defined as herein above; and mixtures thereof.
Examples of Compound (8) are the monoalkenyltrimethylammonium salts such
as monooleyltrimethylammonium chloride, monocanolatrimethylammonium chloride,
and soyatrimethylammonium chloride. Monooleyltrimethylammonium chloride and
monocanolatrimethylammonium chloride are preferred. Other examples of Compound
(8) are soyatrimethylammonium chloride available from Witco Corporation under
the
trade name Adogen~ 415, erucyltrimethylammonium chloride wherein R1 is a C22
CA 02310612 2000-OS-18
WO 99/27050 PCTNS98/25079
17
hydrocarbon group derived from a natural source; soyadimethylethylammonium
ethylsulfate wherein R 1 is a C I 6-C 1 g hydrocarbon group, RS is a methyl
group, R6 is an
ethyl group, and A- is an ethylsulfate anion; and methyl bis(2-
hydroxyethyl)oleylammonium chloride wherein R I is a C 1 g hydrocarbon group,
RS is a
2-hydroxyethyl group and R6 is a methyl group.
Additional fabric softeners that can be used herein are disclosed, at least
generically for the basic structures, in U.S. Pat. Nos. 3,861,870, Edwards and
Diehl;
4,308,151, Cambre; 3,886,075, Bernardino; 4,233,164, Davis; 4,401,578,
Verbruggen;
3,974,076, Wiersema and Rieke; and 4,237,016, Rudkin, Clint, and Young, all of
said
patents being incorporated herein by reference. The additional softener
actives herein are
preferably those that are highly unsaturated versions of the traditional
softener actives,
i.e., di-long chain alkyl nitrogen derivatives, normally cationic materials,
such as
dioleyldimethylammonium chloride and imidazolinium compounds as described
hereinafter. Examples of more biodegradable fabric softeners can be found in
U.S. Pat.
Nos. 3,408,361, Mannheimer, issued Oct.29, 1968; 4,709,045, Kubo et al.,
issued
Nov. 24, 1987; 4,233,451, Pracht et al., issued Nov. 11, 1980; 4,127,489,
Pracht et al.,
issued Nov. 28, 1979; 3,689,424, Berg et al., issued Sept. 5, 1972; 4,128,485,
Baumann
et al., issued Dec. 5, 1978; 4, I 61,604, Elster et al., issued July 17, 1979;
4,189,593,
Wechsler et al., issued Feb. 19, 1980; and 4,339,391, Hoffman et al., issued
July 13,
1982, said patents being incorporated herein by reference.
Examples of Compound (1) are dialkylenedimethylammonium salts such as
dicanoladimethylammonium chloride, dicanoladimethylammonium methylsulfate,
di(partially hydrogenated soybean, cis/trans ratio of about 4:1
)dimethylammonium
chloride, dioleyldimethylammonium chloride. Dioleyldimethylammonium chloride
and
di(canola)dimethylammonium chloride are preferred. An example of commercially
available dialkylenedimethylammonium salts usable in the present invention is
dioleyldimethylammonium chloride available from Witco Corporation under the
trade
name Adogen~ 472.
An example of Compound (2) is 1-methyl-1-oleylamidoethyl-2-
oleylimidazolinium methylsulfate wherein R 1 is an acyclic aliphatic C I S-C
17
hydrocarbon group, R2 is an ethylene group, G is a NH group, RS is a methyl
group and
A- is a methyl sulfate anion, available commercially from the Witco
Corporation under
the trade name Varisoft~ 3690.
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WO 99/Z7050 PCT/US98/25079
18
An example of Compound (3) is 1-oleylamidoethyl-2-oleylimidazoline wherein R1
is an acyclic aliphatic C 15-C 17 hydrocarbon group, R2 is an ethylene group,
and G is a
NH group.
An example of Compound (4) is reaction products of oleic acids with
diethylenetriamine in a molecular ratio of about 2:1, said reaction product
mixture
containing N,N"-dioleoyldiethylenetriamine with the formula:
- R1-C(O)-NH-CH2CH2-NH-CH2CH2-NH-C(O)-R1
wherein R1-C(O) is oleoyl group of a commercially available oleic acid derived
from a
vegetable or animal source, such as Emersol~ 223LL or Emersol~ 7021, available
from
Henkel Corporation, and R2 and R3 are divalent ethylene groups.
An example of Compound (5) is a difatty amidoamine based softener having the
formula:
[R1-C(O)-NH-CH2CH2-N(CH3)(CH2CH20H)-CH2CH2-NH-C(O)-R1]+ CH3S04-
wherein R1-C(O) is oleoyl group, available commercially from the Witco
Corporation
under the trade name Varisoft~ 222LT.
An example of Compound (6) is reaction products of oleic acids with N-2-
hydroxyethylethylenediamine in a molecular ratio of about 2:1, said reaction
product
mixture containing a compound of the formula:
R1-C(O)-NH-CH2CH2-N(CH2CH20H)-C(O)-R1
wherein R1-C(O) is oleoyl group of a commercially available oleic acid derived
from a
vegetable or animal source, such as Emersol~ 223LL or Emersol~ 7021, available
from
Henkel Corporation.
An example of Compound (7) is the diquaternary compound having the formula:
CH3 CH3~
N-CH2CH2-N I 2CH3S040
N ~N
R1 R'
wherein R1 is derived from oleic acid, and the compound is available from
Witco
Company.
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WO 99/27050 PCT/US98125079
19
An example of Compound ( 11 ) is 1-ethyl-1-(2-hydroxyethyl)-2-
isoheptadecylimidazolinium ethylsulfate wherein R1 is a C17 hydrocarbon group,
R2 is
an ethylene group, RS is an ethyl group, and A- is an ethylsulfate anion.
Anion A
In the cationic nitrogenous salts herein, the anion A- , which is any softener
compatible anion, provides electrical neutrality. Most often, the anion used
to provide
electrical neutrality in these salts is from a strong acid, especially a
halide, such as
chloride, bromide, or iodide. However, other anions can be used, such as
methylsulfate,
ethylsulfate, acetate, formate, sulfate, carbonate, and the like. Chloride and
methylsulfate
are preferred herein as anion A. The anion can also, but less preferably,
carry a double
charge in which case A- represents half a group.
B. PRINCIPAL SOLVENT SYSTEM
The principal solvent is typically used at an effective level up to about 40%
by
weight, preferably from about 1 % to about 25%, more preferably from about 3 %
to
about 8 %, by weight of the composition. An advantage of the high electrolyte
level
and/or the phase stabilizers disclosed herein is that lower levels of
principal solvents
and/or a wider range of principal solvents can be used to provide clarity.
E.g., without
the high level of electrolyte, the ClogP of the principal solvent system as
disclosed
hereinafter would typically be limited to a range of from about 0.15 to about
0.64 as
disclosed in said '443 patent. It is known that higher ClogP compounds, up to
about 1
can be used when combined with other solvents as disclosed in copending
provisional
application Serial No. 60/047,058, filed May 19, 1997 in the names of H. B.
Tordil, E. H.
Wahl, T. Trinh, M. Okarnoto, and D. L. Duval (now PCT/LJS98/10167 filed May
18,
1998), or with nonionic surfactants, and especially with the phase stabilizers
disclosed
herein as previously disclosed in Docket No. 7039P, filed March 2, 1998,
Provisional
Application S.N. 60/076,564, the inventors being D.L. DuVal, G.M. Frankenbach,
E.H.
Wahl, T. Trinh, H.J.M. Demeyere, J.H. Shaw and M. Nogami. Title: Concentrated,
Stable, Translucent or Clear Fabric Softening Compositions, both of said
applications
being incorporated herein by reference. With the electrolyte present, the
level of
principal solvent can be less and/or the ClogP range that is usable is
broadened to include
from about -2.0 to about 2.6 , more preferably from about -1.7 to about 1.6,
and even
more preferably from about -1.0 to about 1Ø
With the electrolyte present, levels of principal solvent that are
substantially less
than about 15% by weight of the composition can be used, which is preferred
for odor,
safety and economy reasons. The phase stabilizer as defined hereinafter, in
combination
CA 02310612 2000-05-18
WO 99127050 PCTNS98125079
with a very low level of principal solvent is sufficient to provide good
clarity and/or
stability of the composition when the electrolyte is present. In preferred
compositions,
the level of principal solvent is insufficient to provide the required degree
of clarity
and/or stability and the addition of the electrolyte and/or the phase
stabilizer provides the
desired clarity/stability. Said electrolyte and/or said phase stabilizer can
be used to either
make a composition translucent or clear, or can be used to increase the
temperature range
at which the composition is translucent or clear.
Thus one can use the principal solvent, at the previously indicated levels, in
a
method in which the said principal solvent is added to a composition that is
not
translucent, or clear, or which has a temperature where phase instability
occurs that is too
high, to make the composition translucent or clear, or, when the composition
is clear,
e.g., at ambient temperature, or down to a specific temperature, to reduce the
temperature
at which phase instability occurs, preferably by at least about 5°C,
more preferably by at
least about IO°C. The principal solvent is efficient in that it
provides the maximum
advantage for a given weight of solvent. It is understood that "solvent", as
used herein,
refers to the effect of the principal solvent and not to its physical form at
a given
temperature, since some of the principal solvents are solids at ambient
temperature.
Principal solvents that can be present are selected to minimize solvent odor
impact in the composition and to provide a low viscosity to the final
composition. For
example, isopropyl alcohol is flammable 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 clarity/stability, especially when used as part of a
principal solvent
system to minimize their odor. The alcohols 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
50°F (about
10°C), more preferably down to about 40°F (about 4.4°C)
and are able to recover after
storage down to about 20°F (about 6.7°C).
Other suitable solvents can be selected based upon their octanol/water
partition
coe~cient (P). Octanol/water partition coefficient of a solvent is the ratio
between its
equilibrium concentration in octanol and in water. The partition coe~cients of
the
solvent ingredients of this invention are conveniently given in the form of
their logarithm
to the base 10, loge.
The loge of many ingredients has been reported; for example, the Pomona92
database, available from Daylight Chemical Information Systems, Inc. (Daylight
CIS),
Irvine, California, contains many, along with citations to the original
literature.
However, the loge values are most conveniently calculated by the "CLOGP"
program,
CA 02310612 2000-OS-18
WO 99/27050 PCT/US98/25079
21
also available from Daylight CIS. This program also lists experimental loge
values
when they are available in the Pomona92 database. The "calculated loge"
(ClogP) is
determined by the fragment approach of Hansch and Leo (cf., A. Leo, in
Comprehensive
Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A.
Ramsden, Eds., p. 295, Pergamon Press, 1990, incorporated herein by
reference). The
fragment approach is based on the chemical structure of each ingredient, and
takes into
account the numbers and types of atoms, the atom connectivity, and chemical
bonding.
The ClogP values, which are the most reliable and widely used estimates for
this
physicochemical property, are preferably used instead of the experimental loge
values in
the selection of the principal solvent ingredients which are useful in the
present
invention. Other methods that can be used to compute ClogP include, e.g.,
Crippen's
fragmentation method as disclosed in J. Chem. Inf. Comput. Sci., 27, 21
(1987);
Viswanadhan's fragmentation method as disclose in J. Chem. In~ Comput. Sci.,
29, 163
( 1989); and Broto's method as disclosed in Eur. J. Med. Chem. - Chim. Theor.,
19, 71
(1984).
The principal solvents herein are selected from those having a CIogP of from -
2.0
to 2.6, preferably from -1.7 to 1.6, and more preferably from -1.0 to 1Ø,
The most preferred solvents can be identified by the appearance of the dilute
treatment compositions used to treat fabrics. These dilute compositions 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 solvents have been disclosed, listed under various listings, e.g.,
aliphatic
and/or alicyclic diols with a given number of carbon atoms; monols;
derivatives of
glycerine; alkoxylates of diols; and mixtures of all of the above can be found
in said U.S.
Pats. Nos. 5,759,990 and 5,747,443 and PCT application WO 97/03169 published
on 30
January 1997, said patents and application being incorporated herein by
reference, the
most pertinent disclosure appearing at pages 24-82 and 94-108 (methods of
preparation)
of the said WO 97/03169 specification and in columns 11-54 and 66-78 (methods
of
preparation) of the '443 patent. The '443 and PCT disclosures contain
reference
numbers to the Chemical Abstracts Service Registry numbers (CAS No.) for those
compounds that have such a number and the other compounds have a method
described,
that can be used to prepare the compounds. Some inoperable solvents listed in
the '443
disclosure can be used in mixtures with operable solvents and/or with the high
electrolyte
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WO 99/27050 PCT/US98I25079
22
levels and/or phase stabilizers, to make concentrated fabric softener
compositions that
meet the stability/clarity requirements set forth herein.
Many diol solvents that have the same chemical formula can exist as many
stereoisomers and/or optical isomers. Each isomer is normally assigned with a
different
CAS No. For examples, different isomers of 4-methyl-2,3-hexanediol are
assigned to at
least the following CAS Nos: 146452-51-9; 146452-50-8; 146452-49-5; 146452-48-
4;
123807-34-1; 123807-33-0; 123807-32-9; and 123807-31-8.
In the '443 and PCT specifications, each chemical formula is listed with only
one
CAS No. This disclosure is only for exemplification and is su~cient to allow
the
practice of the invention. The disclosure is not limiting. Therefore, it is
understood that
other isomers with other CAS Nos, and their mixtures, are also included. By
the same
token, when a CAS No. represents a molecule which contains some particular
isotopes,
e.g., deuterium, tritium, carbon-13, etc., it is understood that materials
which contain
naturally distributed isotopes are also included, and vice versa.
There is a clear similarity between the acceptability (formulatability) of a
saturated diol and its unsaturated homologs, or analogs, having higher
molecular
weights. The unsaturated homologs/analogs have the same formulatability as the
parent
saturated solvent with the condition that the unsaturated solvents have one
additional
methylene (viz., CH2) group for each double bond in the chemical formula. In
other
words, there is an apparent "addition rule" in that for each good saturated
solvent of this
invention, which is suitable for the formulation of clear, concentrated fabric
softener
compositions, there are suitable unsaturated solvents where one, or more, CH2
groups
are added while, for each CH2 group added, two hydrogen atoms are removed from
adjacent carbon atoms in the molecule to form one carbon-carbon double bond,
thus
holding the number of hydrogen atoms in the molecule constant with respect to
the
chemical formula of the "parent" saturated solvent. This is due to a
surprising fact that
adding a -CH2- group to a solvent chemical formula has an effect of increasing
its CIogP
value by about 0.53, while removing two adjacent hydrogen atoms to form a
double bond
has an effect of decreasing its ClogP value by about a similar amount, viz.,
about 0.48,
thus about compensating for the -CH2- addition. Therefore one goes from a
preferred
saturated solvent to the preferred higher molecular weight unsaturated
analogs/homologs
containing at least one more carbon atom by inserting one double bond for each
additional CH2 group, and thus the total number of hydrogen atoms is kept the
same as
in the parent saturated solvent, as long as the CIogP value of the new solvent
remains
within the effective range. The following are some illustrative examples:
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WO 99/27050 PCT/US98/25079
23
It is possible to substitute for part of the principal solvent mixture a
secondary
solvent, or a mixture of secondary solvents, which by themselves are not
operable as a
principal solvent of this invention, as long as an effective amount of the
operable
principal solvents of this invention is still present in the liquid
concentrated, clear fabric
softener composition. An effective amount of the principal solvents of this
invention is
at least greater than about 1 %, preferably more than about 3%, more
preferably more
than about 5% of the composition, when at least about 15% of the softener
active is also
present.
Principal solvents preferred for improved clarity at 50 °F are 1,2-
hexanediol; 1,2-
pentanediol; hexylene glycol; 1,2-butanediol; 1,4-cyclohexanediol; pinacol;
1,5-
hexanediol; 1,6-hexanediol; and/or 2,4-dimethyl-2,4-pentanediol.
C. ELECTROLYTE
The use of electrolyte, especially in large amounts in a clear fabric softener
formulation would not be expected to provide a beneft. Electrolytes and high
levels of
water insoluble compounds would be expected to be incompatible. The
compositions of
this invention contain a relatively high level of electrolyte, e.g., from
about 0.5% to
about 10%, preferably from about 0.75% to about 3%, and more preferably from
about
1 % to about 2%, by weight of the composition. Increasing the electrolyte
level provides
at least one benefit selected from {a) lowers the amount of principal solvent
having a
CIogP of from about 0.15 to about 0.64 or 1, which is required to provide
clarity (It can
eliminate the need for such a principal solvent completely.); (b) modifies the
viscosity/elasticity profile on dilution, to provide lower viscosity and/or
elasticity; and
(c) modifies the range of ClogP of acceptable principal solvents that will
provide
clarity/translucency. U.S. Pat. No. 5,759,990, incorporated herein by
reference, discloses
that the principal solvent should have a ClogP of from about 0.15 to about
0.64. A high
electrolyte level allows the use of principal solvents with a ClogP within
ranges having
progressively more preferred lower limits of: -2.0; -1.7; -1.0; and 0.15 and
having
progressively more preferrred upper limits of 2.6; 2.0; 1.6; 1.0; and 0.64..
This is a
totally unobvious and very important benefit, since many of the solvents that
are
included in this broader range are more readily available, have lower odors,
and can be
more effective. The existing principal solvents are also more effective with
the high
electrolyte level, thus allowing one to use less of such principal solvents.
Above a ClogP
of about 1.6, the use of additional solvents and/or other materials to aid in
clarification is
highly desirable.
It is believed that electrolytes significantly modify the microstructures
and/or
alter the phases that the products dilute through compared to products with no
or lowered
CA 02310612 2000-OS-18
WO 99/27050 PCTJUS98/25079
24
levels of electrolyte. Cryogenic Transmission Electron Microscopy and Freeze-
Fracture
Transmission Electron Microscopy methods show that in products which gel or
have an
unacceptable increase in viscosity upon dilution, a highly concentrated,
tightly packed
dispersion of vesicles can be formed. Such vesicular dispersions are shown to
have high
elasticity using Theological measurements. It is believed that since these
solutions have
high elasticity, they resist the mechanical stress that can lead to effective
mixing with
water and thus good dilution.
It is therefore believed that fabric softener compositions with highly
preferred
dilution and dispensing behaviors can be identified by evaluating the visco-
elastic
behavior of a series of water dilutions of the fabric softener composition, or
alternatively,
by evaluating the visco-elastic properties of the maximum viscosity peak in
the dilution
series. The visco-elastic behavior of the fabric softening composition
provides
information on the tendency of the fabric softener composition to flow and
disperse in a
desirable manner when used by the consumer. Viscosity measures the ability of
a fluid
to flow (ie. dissipate heat) when energy is applied, represented by G", the
loss modulus.
Elasticity, which is commonly denoted by the storage modulus G', measures the
tendency of the fabric softener composition to be easily deformed as energy is
applied.
G' and G" are generally measured as functions of applied strain or stress. For
the
purposes of this invention, G' and G" are measured over a range of energy
inputs which
encompasses energies likely to be applied in common consumer practices (e.g.,
machine
wash and hand wash processes, pre-dilution steps by hand and machine, machine
dispenser use and machine-independent dispenser use). Measuring G' and G" on
diluted
compositions with maximum viscosity adequately distinguishes fabric softener
compositions that have preferred and highly preferred dilution and dispersion
behaviors
from fabric softener compositions which have less preferred behavior. Further
details on
Theological parameters as well as well as guidance for choosing
instrumentation and
making Theological measurements is available in the article on Rheolo~
Measurements
in the Kirk-Othmer Encyclonedia of Chemical Technology 3'd Ed., 1982, John
Wiley &
Sons Publ.; Rheology of Liquid Detergents by R.S. Rounds in Surfactant Series
Vol. 67:
Liquid Detergents ed. K.-Y. Lai, Marcel Dekker, Inc. 1997; and Introduction to
Rheolo~y, Elsevier, 1989, H.A. Barnes, J.F. Hutton, and K. Waiters.
It was discovered that there was a previously unrecognized problem that
appeared
when some clear formulas were diluted. Previously it was believed that the
principal
solvents promoted facile dilution of clear concentrated formulas to less
concentrated
dispersions in the rinse liquor. However, when some formulas, especially those
with
lower levels of principal solvent, or formulas based on solvents which are not
principal
CA 02310612 2000-OS-18
WO 99/27050 PCT/US98/25079
solvents, are diluted, they have unacceptable viscosity/elasticity profiles.
Rheological
parameters which describe preferred formulations are as follows: preferred G'
<_ about 20
Pa and G" <_ about 6 Pa sec; more preferred G' S about 3 Pa and G" 5 about 2
Pa sec;
even more preferred G' <_ about 1 Pa G" <_ about 1 Pa, as measured on diluted
formulations with maximum viscosity. Dilutions of preferred, more preferred,
and yet
even more preferred formulas must maintain stated G' and G" values over a
range of
applied strains from about 0.1 to about 1.
Microscopy shows again that high electrolyte levels allow the creation of
formulas at much. lower solventlsoftener levels that dilute through different
microstructures and/or phases which have much lower visco-elasticity. It is
believed that
microstructures with much lower elasticity, easily yield to slight stresses
caused by
agitating water in a washing machine, automatic washing machine dispenser, or
automatic dispensing device not affixed to the machine agitator such as the
Downy~
'Ball'. This leads to good mixing with water and consequently good dispersion
of the
fabric softener composition and thus reduced fabric staining potential, less
fabric softener
composition residue left behind in machine or machine-independent dispensing
devices,
less build-up of fabric softener residue in dispensers, more fabric softener
available in the
rinse increasing deposition on clothes, more uniform deposition over the
surface of all
clothes.
The electrolytes herein include the usual ones found in opaque, dispersion-
type,
liquid fabric softener compositions and others that are not normally used in
such
compositions. It was previously believed that principal solvents were
increasing the
flexibility of both the fabric softener domain and the water domain and thus
promoting
the formation of a highly fluid, optically clear, compositions containing a
bicontinuous
fabric softener active phase. Unexpectedly, it is now found that electrolytes
seem to
provide the function of increasing the flexibility of the water domain through
breaking up
the hydrogen bond interactions via complexation with the water molecules. This
appears
to be the mechanism by which the use of high electrolyte allows the use of
lower
amounts of principal solvents and increases the range of operable principal
solvents.
Although it is believed that electrolytes function by complexing with water
and
breaking the hydrogen bond structure of water, it is also believed that the
head groups of
the fabric softener active and the phase stabilizer must be able to complex
with water to
increase the steric repulsion that will prevent coalescence of the separate
bicontinuous
phases of fabric softener actives, thus improving the stability of the typical
bicontinuous
phase that is present when the fabric softener active is in a clear
composition.
Electrolytes that have anions that are termed "soft" or "polarizable" anions
as discussed
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WO 99/27050 PCT/US98/25079
26
in Surfactants and Interfacial Phenomena, Second Edition, M. J. Rosen, pp. 194-
5, are
more preferred than "hard" or "less polarizable" anions because the
polarizable anions
are believed to be effective at breaking up the water structure without
dehydrating the
head groups of the fabric softeners and the phase stabilizers. An additional
reason for
preferring soft, polarizable anions is that these complex less strongly than
the hard ions
with the fabric softener canon and so we believe a stronger cationic charge is
maintained
on the fabric softener head groups in the presence of the soft anions. A
stronger cationic
charge on the fabric softener should also help stabilize the bicontinuous
phase by
preventing coalescence through maintaining greater electrostatic repulsion. A
typical
series of anions from soft to hard is: iodide; bromide; isocyanate;
orthophosphate;
chloride; sulfate; hydroxide; and fluoride. The harder anions lower the cloud
point of
conventional ethoxylated nonionic detergent surfactants more, showing that the
harder
anions tend to dehydrate the head groups of the ethoxylated surfactants used
as phase
stabilizers.
For example, salts that lower the cloud point of a 1 % solution of Neodol~ 91-
8 to
less than about 65°C are less preferred in the fabric softener
compositions described
herein because the fabric softener compositions made with these salts tend to
be cloudy
at ambient temperatures. Typical approximate cloud points for such a solution
are:
sodium sulfate - about 54.1 °C; potassium sulfate - 64.4°C;
ammonium sulfate - about
64.4°C; calcium sulfate (no change - insoluble); magnesium sulfate -
about 58.7°C;
sodium chloride - about 63- 66.9°C; potassium chloride - about
73.4°C; ammonium
chloride - about 73.8°C; calcium chloride - about 73.$°C; and
magnesium chloride -
about 69.8°C. Potassium acetate provides a cloud point of about about
69.8°C, thus
placing the acetate anion somewhere between the chloride and sulfate anions.
Inorganic salts suitable for reducing dilution viscosity include MgI2, MgBr2,
MgCl2, Mg(N03)2, Mg3(P04)2, Mg2Pz0,, MgSO,, magnesium silicate, NaI, NaBr,
NaCI,
NaF, Na3(P04), NaSO~, NazS04, NazS03, NaN03, NaI03, Na3(PO,), Na4Pz0,, sodium
silicate, sodium metasilicate, sodium tetrachloroaluminate, sodium
tripolyphosphate
(STPP), NazSi30,, sodium zirconate, CaF2, CaClz, CaBr2, CaIz, CaS04, Ca(N03)2,
Ca, KI,
KBr, KCI, KF, KN03, KI03, KzS04, KZS03, K3(P04), K4(P,O,), potassium
pyrosulfate,
potassium pyrosulfite, LiI, Liar, LiCI, LiF, LiN03, A1F3, AlCl3, AlBr3, AlI3,
Ah(S04)s,
AI(P04), Al(N03)3, aluminum silicate; including hydrates of these salts and
including
combinations of these salts or salts with mixed cations e.g. potassium alum
A1K(S04)2
and salts with mixed anions, e.g. potassium tetrachloroaluminate and sodium
tetrafluoroaluminate. Salts incorporating cations from groups IIIa, IVa, Va,
VIa, VIIa,
VIII, Ib, and IIb on the periodic chart with atomic numbers > 13 are also
useful in
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WO 99/27050 PCTNS98/25079
27
reducing dilution viscosity but less preferred due to their tendency to change
oxidation
states and thus they can adversely affect the odor or color of the formulation
or lower
weight efficiency. Salts with cations from group Ia or IIa with atomic numbers
> 20 as
well as salts with canons from the lactinide or actinide series are useful in
reducing
dilution viscosity, but less preferred due to lower weight efficiency or
toxicity. Mixtures
of above salts are also useful.
Organic salts useful in this invention include, magnesium, sodium, lithium,
potassium, zinc, and aluminum salts of the carboxylic acids including formate,
acetate,
proprionate, pelargonate, citrate, gluconate, lactate aromatic acids e.g.
benzoates,
phenolate and substituted benzoates or phenolates, such as phenolate,
salicylate,
polyaromatic acids terephthalates, and polyacids e.g. oxylate, adipate,
succinate,
benzenedicarboxylate, benzenetricarboxylate. Other useful organic salts
include
carbonate and/or hydrogencarbonate (HC03-') when the pH is suitable, alkyl and
aromatic sulfates and sulfonates e.g. sodium methyl sulfate, benzene
sulfonates and
derivatives such as xylene sulfonate, and amino acids when the pH is suitable.
Electrolytes can comprise mixed salts of the above, salts neutralized with
mixed cations
such as potassium/sodium tartrate, partially neutralized salts such as sodium
hydrogen
tartrate or potassium hydrogen phthalate, and salts comprising one cation with
mixed
anions.
Generally, inorganic electrolytes are preferred over organic electrolytes for
better
weight efficiency and lower costs. Mixtures of inorganic and organic salts can
be used.
Typical levels of electrolyte in the compositions are less than about 10%.
Preferably
from about 0.5 % to about 5% by weight, more preferably from about 0.75 % to
about
2.5 %, and most preferably from about 1 % to about 2 % by weight of the fabric
softener
composition.
D. PHASE STABILIZER
Phase stabilizers are highly desirable, and can be essential, to formulating a
clear
or translucent fabric softener composition (product) with high electrolyte
levels. It is
believed that clear and translucent products are comprised of surfactants
structured in
bilayers with an aqueous domain between these bilayers. Oily materials, such
as
hydrophobic perftunes, can be incorporated within the bilayers between the
surfactant
tails. In fact, these oily materials can act to stabilize the bilayers if the
amount present is
not excessive. Water soluble compounds, such as the electrolytes described
above tend
to stay in the aqueous domain between the bilayers.
It is believed that in cationic softener products with no or low electrolyte
levels,
the surfactant structure is normally stabilized by the electrostatic repulsion
between the
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WO 99/27050 PCTNS98/25079
28
bilayers. Electrostatic repulsion prevents the surfactant bilayers from
coalescing and thus
splitting into separate phases. When a high level of electrolyte is added to
the formula, it
is believed that the electrostatic repulsion between bilayers is diminished
and this can
promote coalescence of the surfactant bilayers. If this coalescence occurs,
one, or more,
phase stabilizers is added to the formula to provide more stability, e.g., by
steric
repulsion between the bilayers.
Typical levels of phase stabilizer in the softening compositions are from an
effective amount up to about 15% by weight, preferably from about 0.1% to
about 7% by
weight, more preferably from about 1% to about 5% by weight of the
composition.
The phase stabilizer compounds described herein differ from the principal
solvents described hereinbefore by their ability to provide steric repulsion
at the
interface. These phase stabilizers are not principal solvents as defined
herein.
The phase stabilizers useful in the compositions of the present invention are
selected surface actives materials commonly comprise of hydrophobic and
hydrophilic
moieties. A preferred hydrophilic moiety is polyalkoxylated group , preferably
polyethoxylated group.
Preferred phase stabilizers are nonionic surfactants derived from saturated
and/or
unsaturated primary, secondary, and/or branched, amine, amide, amine-oxide
fatty
alcohol, fatty acid, alkyl phenol, and/or alkyl aryl carboxylic acid
compounds, each
preferably having from about 6 to about 22, more preferably from about 8 to
about 18,
carbon atoms in a hydrophobic chain, more preferably an alkyl or alkylene
chain,
wherein at least one active hydrogen of said compounds is ethoxylated with <_
50,
preferably <_ 30, more preferably from about S to about 15, and even more
preferably
from about 8 to about 12, ethylene oxide moieties to provide an HLB of from
about 8 to
about 20, preferably from about 10 to about 18, and more preferably from about
11 to
about 15.
Suitable phase stabilizers also include nonionic surfactants with bulky head
groups selected from:
a. surfactants having the formula
R'-C(O)-Y'-[C(RS)]m-CH20(Rz0)ZH
wherein R~ is selected from the group consisting of saturated or unsaturated,
primary,
secondary or branched chain alkyl or alkyl-aryl hydrocarbons; said hydrocarbon
chain
having a length of from about 6 to about 22; Y' is selected from the following
groups: -
O-; -N(A)-; and mixtures thereof; and A is selected from the following groups:
H; R'; -
(RZ-O)Z H; -(CHz)XCH3; phenyl, or substituted aryl, wherein 0 <_ x 5 about 3
and z is from
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29
about 5 to about 30; each Rz is selected from the following groups or
combinations of the
following groups: -(CHZ)~- wherein n is from about 1 to about 4 and/or -
[CH(CH3)CHzJ-;
and each RS is selected from the following groups: -OH; and -O(R20)Z H ; and m
is from
about 2 to about 4;
b. surfactants having the formulas:
R5 Y" R5 R~ _ _.. R5
R5 \R5 R° Rs
R'
wherein Y" = N or O; and each RS is selected independently from the following:
-H, -OH, -(CHz)xCH3, -O(ORZ)Z H, -OR', - OC(O)R', and -CH(CHz-(ORZ)Z.-H)-CHZ-
(OR')Z.-C(O) R', x and R' are as defined above and 5 _< z, z', and z" <_ 20,
more
preferably 5 <_ z + z' + z" < 20~ ~d most preferably, the heterocyclic ring is
a five
member ring with Y" = O, one RS is -H, two R' are -O-(R20)z-H, and at least
one RS is
the following structure -CH(CHz-(ORz)Z.-H)-CHz-(ORZ)Z.-C(O) R' with 8 _< z +
z' + z" <
20 and R' is a hydrocarbon with from 8 to 20 carbon atoms and no aryl group;
c. polyhydroxy fatty acid amide surfactants of the formula:
R2-C(O)-N(Rl)-Z
wherein: each R1 is H, Cl-C4 hydrocarbyl, C1-C4 alkoxyalkyl, or hydroxyalkyl;
and R2
is a CS-C31 hydrocarbyl moiety; and each Z is a polyhydroxyhydrocarbyl moiety
having
a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the
chain, or an
ethoxylated derivative thereof; and each R' is H or a cyclic mono- or poly-
saccharide, or
alkoxylated derivative thereof; and
d. mixtures thereof.
Suitable phase stabilizers also include surfactant complexes formed by one
surfactant ion being neutralized with surfactant ion of opposite charge or an
electrolyte
ion that is suitable for reducing dilution viscosity and block copolymer
surfactants
comprising polyethylene oxide moieties and propylene oxide moieties
Examples of representative phase stabilizers include:
( 1 )- Alkyl or alkyl-aryl alkoxylated nonionic surfactants
Suitable alkyl alkoxylated nonionic surfactants are generally derived from
saturated or unsaturated primary, secondary, and branched fatty alcohols,
fatty acids,
alkyl phenols, or alkyl aryl (e.g., benzoic) carboxylic acid, where the active
hydrogen(s)
CA 02310612 2000-OS-18
WO 99/27050 PCT/US98/25079
is alkoxylated with <_ about 30 alkylene, preferably ethylene, oxide moieties
(e.g.
ethylene oxide and/or propylene oxide). These nonionic surfactants for use
herein
preferably have from about 6 to about 22 carbon atoms on the alkyl or alkenyl
chain, and
are in either straight chain or branched chain configuration, preferably
straight chain
configurations having from about 8 to about 18 carbon atoms, with the alkylene
oxide
being present, preferably at the primary position, in average amounts of <_
about 30 moles
of alkylene oxide per alkyl chain, more preferably from about 5 to about 15
moles of
alkylene oxide, and most preferably from about 8 to about 12 moles of alkylene
oxide.
Preferred materials of this class also have pour points of about 70°F
and/or do not
solidify in these clear formulations. Examples of alkyl alkoxylated
surfactants with
straight chains include Neodol~ 91-8, 25-9, 1-9, 25-12, 1-9, and 45-13 from
Shell,
Plurafac~' B-26 and C-17 from BASF, and Brij~ 76 and 35 from ICI Surfactants.
Examples of branched alkyl alkoxylated surfactants include Tergitol~ 15-S-12,
15-S-15,
and 15-S-20 from Union Carbide and Emulphogene~ BC-720 and BC-840 from GAF.
Examples of alkyl-aryl alkoxylated surfactants include Igepal~ CO-620 and CO-
710,
from Rhone Poulenc, Triton~ N-11 l and N-150 from Union Carbide, Dowfax~ 9N5
from
Dow and Lutensol~ AP9 and AP14, from BASF.
(2)- Alkyl or alkyl-aryl amine or amine oxide nonionic aIkoxylated surfactants
Suitable alkyl alkoxylated nonionic surfactants with amine functionality are
generally derived from saturated or unsaturated, primary, secondary, and
branched fatty
alcohols, fatty acids, fatty methyl esters, alkyl phenol, alkyl benzoates, and
alkyl benzoic
acids that are converted to amines, amine-oxides, and optionally substituted
with a
second alkyl or alkyl-aryl hydrocarbon with one or two alkylene oxide chains
attached at
the amine functionality each having _< about 50 moles alkylene oxide moieties
(e.g.
ethylene oxide and/or propylene oxide) per mole of amine. The amine or amine-
oxide
surfactants for use herein have from about 6 to about 22 carbon atoms, and are
in either
straight chain or branched chain configuration, preferably there is one
hydrocarbon in a
straight chain configuration having about 8 to about 18 carbon atoms with one
or two
alkylene oxide chains attached to the amine moiety, in average amounts of <_
50 about
moles of alkylene oxide per amine moiety, more preferably from about 5 to
about 15
moles of alkylene oxide, and most preferably a single alkylene oxide chain on
the amine
moiety containing from about 8 to about 12 moles of alkylene oxide per amine
moiety.
Preferred materials of this class also have pour points about 70°F
and/or do not solidify
in these clear formulations. Examples of ethoxylated amine surfactants include
Berol~
397 and 303 from Rhone Poulenc and Ethomeens~ C/20, C25, T/25, S/20, S/25 and
Ethodumeens~ T/20 and T25 from Akzo.
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31
Preferably, the compounds of the alkyl or alkyl-aryl alkoxylated surfactants
and
alkyl or alkyl-aryl amine and amine-oxide alkoxylated have the following
general
formula:
R'm - Y - [(RZ-O)Z - H]p
wherein each R~ is selected from the group consisting of saturated or
unsaturated,
primary, secondary or branched chain alkyl or alkyl-aryl hydrocarbons; said
hydrocarbon
chain preferably having a length of from about 6 to about 22, more preferably
from about
8 to about 18 carbon atoms, and even more preferably from about 8 to about 15
carbon
atoms, preferably, linear and with no aryl moiety; wherein each R' is selected
from the
following groups or combinations of the following groups: -(CHZ)n- and/or -
[CH(CH3)CHz]-; wherein about 1 < n < about 3; Y is selected from the following
groups:
_O_~ _N(A)a-~ _C(O)O_~ _ (Of-)N(A)q ; -B-R3-O-; -B_Rs_N(A)q ; -B-R3-C(O)O_; -B-
R'_
N(-~O)(A)-; and mixtures thereof; wherein A is selected from the following
groups: H;
R'; -(R'-O)Z H; -(CHZ)XCH3; phenyl, or substituted aryl, wherein 0 _< x <_
about 3 and B is
selected from the following groups: -O-; -N(A)-; -C(O)O-;and mixtures thereof
in
which A is as defined above; and wherein each R3 is selected from the
following groups:
R'; phenyl; or substituted aryl. The terminal hydrogen in each alkoxy chain
can be
replaced by a short chain C,~ alkyl or acyl group to "cap" the alkoxy chain. z
is from
about 5 to about 30. p is the number of ethoxylate chains, typically one or
two,
preferably one and m is the number of hydrophobic chains, typically one or
two,
preferably one and q is a number that completes the structure, usually one.
Preferred structures are those in which m = 1, p = 1 or 2, and S <_ z <_ 30,
and q
can be 1 or 0, but when p = 2, q must be 0; more preferred are structures in
which m = 1,
p = 1 or 2, and 7 <_ z <_ 20; and even more preferred are structures in which
m = I, p = I
or 2, and 9 <_ z <_ 12. The preferred y is 0.
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32
(3)- Alkoxylated and non-alkox~,ated nonionic surfactants with bulky head
groups
Suitable alkoxylated and non-alkoxylated phase stabilizers with bulky head
groups are generally derived from saturated or unsaturated, primary,
secondary, and
branched fatty alcohols, fatty acids, alkyl phenol, and alkyl benzoic acids
that are
derivatized with a carbohydrate group or heterocyclic head group. This
structure can
then be optionally substituted with more alkyl or alkyl-aryl alkoxylated or
non-
alkoxylated hydrocarbons. The heterocyclic or carbohydrate is alkoxylated with
one or
more alkylene oxide chains (e.g. ethylene oxide and/or propylene oxide) each
having <_
about 50, preferably < about 30, moles per mole of heterocyclic or
carbohydrate. The
hydrocarbon groups on the carbohydrate or heterocyclic surfactant for use
herein have
from about 6 to about 22 carbon atoms, and are in either straight chain or
branched chain
configuration, preferably there is one hydrocarbon having from about 8 to
about 18
carbon atoms with one or two alkylene oxide chains carbohydrate or
heterocyclic moiety
with each alkylene oxide chain present in average amounts of <_ about 50,
preferably <
about 30, moles of carbohydrate or heterocyclic moiety, more preferably from
about 5 to
about 15 moles of alkylene oxide per alkylene oxide chain, and most preferably
between
about 8 and about 12 moles of alkylene oxide total per surfactant molecule
including
alkylene oxide on both the hydrocarbon chain and on the heterocyclic or
carbohydrate
moiety. Examples of phase stabilizers in this class are Tween~ 40, 60, and 80
available
from ICI Surfactants.
Preferably the compounds of the alkoxylated and non-alkoxylated nonionic
surfactants with bulky head groups have the following general formulas:
R~-C(O)-Y'-[C(RS)Jm-CHzO(Rz0)ZH
wherein Rl is selected from the group consisting of saturated or unsaturated,
primary,
secondary or branched chain alkyl or alkyl-aryl hydrocarbons; said hydrocarbon
chain
having a length of from about 6 to about 22; Y' is selected from the following
groups: -
O-; -N(A)-; and mixtures thereof; and A is selected from the following groups:
H; R'; -
(RZ-O)Z H; -(CHZ)XCH3; phenyl, or substituted aryl, wherein 0 <_ x <_ about 3
and z is from
about 5 to about 30; each Rz is selected from the following groups or
combinations of the
following groups: -(CHZ)~- and/or -[CH(CH3)CHZ]-; and each RS is selected from
the
following groups: -OH; and -O(Rz0)Z H ; and m is from about 2 to about 4;
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WO 99/27050 PCT/US98/25079
33
Another useful general formula for this class of surfactants is
R~ Y" R5 R5 _ _.. Rs
R5 \R5 R~ R5
R'
wherein Y" = N or O; and each RS is selected independently from the following:
-H, -OH, -(CH,)xCH3, -(ORz)Z H, -OR', - OC(O)R', and -CHZ(CHZ-(ORz)Z.-H)-CHz-
(OR'')Z.-C(O) R'. With x, R~, and RZ as defined above in section D above and
z, z', and
z" are all from about 5 _< to <_ about 20, more preferably the total number of
z + z' + z"
is from about 5 <_ to <_ about 20. In a particularly preferred form of this
structure the
heterocyclic ring is a five member ring with Y" = O, one RS is -H, two RS are -
O-(Rz0)Z
H, and at least one RS has the following structure -CH(CHz-(OR')Z.-H)-CHZ-
(OR'')Z.-
OC(O) R' with the total z + z' + z" = to from about 8 _< to <_ about 20 and R'
is a
hydrocarbon with from about 8 to about 20 carbon atoms and no aryl group.
Another group of surfactants that can be used are polyhydroxy fatty acid amide
surfactants of the formula:
R6 - C(O) - N(R~) - Z
wherein: each R~ is H, Cl-C4 hydrocarbyi, Cl-C4 alkoxyalkyl, or hydroxyalkyl,
e.g., 2-
hydroxyethyl, 2-hydroxypropyl, etc., preferably C 1-C4 alkyl, more preferably
C 1 or C2
alkyl, most preferably C 1 alkyl (i.e., methyl) or methoxyalkyl; and R6 is a
CS-C31
hydrocarbyl moiety, preferably straight chain C~-C19 alkyl or alkenyl, more
preferably
straight chain Cg-C 1 ~ alkyl or alkenyl, most preferably straight chain C 11-
C 1 ~ alkyl or
alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl moiety having a
linear
hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain,
or an
alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z
preferably
will be derived from a reducing sugar in a reductive amination reaction; more
preferably
Z is a glycityl moiety. Z preferably will be selected from the group
consisting of -CH2-
(CHOH)n-CH20H, -CH(CH20H)-(CHOH)n-CH20H, -CH2_
(CHOH)2(CHOR')(CHOH)-CH20H, where n is an integer from 3 to 5, inclusive, and
R'
is H or a cyclic mono- or poly- saccharide, and alkoxylated derivatives
thereof. Most
preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)q.-CH20.
Mixtures of
the above Z moieties are desirable.
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WO 99/27050 PCTNS98I25079
34
R6 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-
isobutyl, N-2-hydroxyethyl, N-1-methoxypropyl, or N-2-hydroxypropyl.
R6-CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide,
myristamide, capricamide, palmitamide, tallowamide, etc.
Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl,
1-
deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
(4)- Alkoxylated cationic quaternary ammonium surfactants
Alkoxylated cationic quaternary ammonium surfactants suitable for this
invention
are generally derived from fatty alcohols, fatty acids, fatty methyl esters,
alkyl
substituted phenols, alkyl substituted benzoic acids, and/or alkyl substituted
benzoate
esters, and/or fatty acids that are converted to amines which can optionally
be further
reacted with another long chain alkyl or alkyl-aryl group; this amine compound
is then
alkoxylated with one or two alkylene oxide chains each having <_ about 50
moles
alkylene oxide moieties (e.g. ethylene oxide and/or propylene oxide) per mole
of amine.
Typical of this class are products obtained from the quaternization of
aliphatic saturated
or unsaturated, primary, secondary, or branched amines having one or two
hydrocarbon
chains from about 6 to about 22 carbon atoms alkoxylated with one or two
alkylene
oxide chains on the amine atom each having less than <_ about 50 alkylene
oxide
moieties. The amine hydrocarbons for use herein have from about 6 to about 22
carbon
atoms, and are in either straight chain or branched chain configuration,
preferably there is
one alkyl hydrocarbon group in a straight chain configuration having about 8
to about 18
carbon atoms. Suitable quaternary ammonium surfactants are made with one or
two
alkylene oxide chains attached to the amine moiety, in average amounts of _<
about 50
moles of alkylene oxide per alkyl chain, more preferably from about 3 to about
20 moles
of alkylene oxide, and most preferably from about 5 to about 12 moles of
alkylene oxide
per hydrophobic, e.g., alkyl group. Preferred materials of this class also
have a pour
points below about 70°F and/or do not solidify in these clear
formulations. Examples of
suitable phase stabilizers of this type include Ethoquad~ 18/25, C/25, and
O/25 from
Akzo and Variquat~-66 (soft tallow alkyl bis(polyoxyethyl) ammonium ethyl
sulfate with
a total of about 16 ethoxy units) from Witco.
Preferably, the compounds of the ammonium alkoxylated cationic surfactants
have
the following general formula:
~R~m - Y - URz-O) - H~ }+ x
wherein R~ and Rz are as defined previously in section D above;
CA 02310612 2000-OS-18
wo 99n~oso Pc~rius98nso~9
Y is selected from the following groups: = N+-(A)q; -(CHZ)~-N+-(A)q; -B-(CH~)~-
N~-(A)2; -(phenyl)-N+-(A)q; -(B-phenyl)-N+-(A)q; with n being from about 1 to
about 4, m
is 1 or2,pis 1 or2,andm+p+q=4,
Each A is independently selected from the following groups: H; R'; -(R20)Z H; -
(CHZ)xCH3; phenyl, and substituted aryl; where 0 <_ x 5 about 3; and B is
selected from
the following groups: -O-; -NA-; -NA2; -C(O)O-; and -C(O)N(A)-; wherein RZ is
defined
as hereinbefore; q = 1 or 2; and
X- is an anion which is compatible with fabric softener actives and adjunct
ingredients.
Preferred structures are those in which m = 1, p = 1 or 2, and about 5 <_ z <
about
50, more preferred are structures in which m = 1, p = 1 or 2, and about 7 <_ z
_< about 20,
and most preferred are structures in which m = 1, p = 1 or 2, and about 9 5 z
_< about 12.
(5)- Surfactant complexes
Surfactant complexes are considered to be surfactant ions neutralized with a
surfactant ion of opposite charge or a surfactant neutralized with an
electrolyte that is
suitable for reducing dilution viscosity, an ammonium salt, or a polycationic
ammonium
salt. For the purpose of this invention, if a surfactant complex is formed by
surfactants
of opposite charge, it is preferable that the surfactants have distinctly
different chain
lengths e.g. a long-chain surfactant complexed with a short-chain surfactant
to enhance
the solubility of the complex and it is more preferable that the that the long
chain
surfactant be the amine or ammonium containing surfactant. Long chain
surfactants are
defined as containing alkyl chains with from about 6 to about 22 carbon atoms.
These
alkyl chains can optionally contain a phenyl or substituted phenyl group or
alkylene
oxide moieties between the chain and the head group. Short chain surfactants
are defined
as containing alkyl chains with less than 6 carbons and optionally these alkyl
chains
could contain a phenyl or substituted phenyl group or alkylene oxide moieties
between
the alkyl chain and the head group. Examples of suitable surfactant complexes
include
mixtures of Armeen~ APA-10 and calcium xylene sulfonate, Armeen APA-10 and
magnesium chloride, lauryl carboxylate and triethanoi amine, linear alkyl
benzene
sulfonate and CS-dimethyl amine, or alkyl ethoxylated sulfate and tetrakis
N,N,N'N' (2-
hydroxylpropyl) ethylenediamine.
Preferably, long-chain surfactants for making complexes have the following
general formula:
R'-Y'-
wherein R' is as hereinbefore from section D above and Yz can be chosen from
the following structures: -N(A)2; -C(O)N(A)2; -(O~)N(A)2; -B-R3-N(A)z; -B-R3-
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36
C(O)N(A)Z; -B-R'-N(-~O)(A)2; -COZ ; -S03'-; -OS03 z; -O(RZO)XCOZ ; -O(R20)xS03-
'-;
and -O(R20)XOS03'; with B and R3 as is hereinbefore section D above and 0 < x
<_ 4 .
Preferably, short-chain surfactants for making complexes have the following
general formula:
Ra-Yz
wherein R', R3, B, and Y2are as hereinbefore and RQ can be chosen from the
following: -(CH2)YCH3; -(CHZ)y-phenyl or -(CHZ)y substituted phenyl with 0 <_
y _< 6
(6)- Block copolymers obtained by copolymerization of ethylene oxide and
nronylene
oxide
Suitable polymers include a copolymer having blocks of terephthalate and
polyethylene oxide. More specifically, these polymers are comprised of
repeating units
of ethylene andlor propylene terephthalate and polyethylene oxide
terephthalate at a
preferred molar ratio of ethylene terephthalate units to polyethylene oxide
terephthalate
units of from about 25:75 to about 35:65, said polyethylene oxide
terephthalate
containing polyethylene oxide blocks having molecular weights of from about
300 to
about 2000. The molecular weight of this polymer is in the range of from about
5,000 to
about 55,000.
Another preferred polymer is a crystallizable polyester with repeat units of
ethylene terephthalate units containing from about 10% to about 15% by weight
of
ethylene terephthalate units together with from about 10% to about 50% by
weight of
polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of
average
molecular weight of from about 300 to about 6,000, and the molar ratio of
ethylene
terephthalate units to polyoxyethylene terephthalate units in the
crystallizable polymeric
compound is between 2:1 and 6:1. Examples of this polymer include the
commercially
available materials Zelcon~ 4780 (from DuPont) and Milease~ T (from ICI).
Highly preferred polymers have the generic formula:
X-(OCH2CH2)n-CO-C(O)-R1-C(O)-O-R2)uU0-C(O)-R1-C(O)-O)-(CH2CH20)n-X (1)
in which X can be any suitable capping group, with each X being selected from
the
group consisting of H, and alkyl or acyl groups containing from about 1 to
about 4
carbon atoms, preferably methyl, n is selected for water solubility and
generally is from
about 6 to about 113, preferably from about 20 to about 50, and a is critical
to
formulation in a liquid composition having a relatively high ionic strength.
There
should be very little material in which a is greater than 10. Furthermore,
there should be
at least 20%, preferably at least 40%, of material in which a ranges from
about 3 to
about 5.
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37
The R1 moieties are essentially 1,4-phenylene moieties. As used herein, the
term
"the R1 moieties are essentially 1,4-phenylene moieties" refers to compounds
where the
RI moieties consist entirely of 1,4-phenylene moieties, or are partially
substituted with
other arylene or alkarylene moieties, alkylene moieties, alkenylene moieties,
or mixtures
thereof. Arylene and alkarylene moieties which can be partially substituted
for
1,4-phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-
naphthylene,
2,2-biphenylene, 4,4-biphenylene and mixtures thereof. Alkylene and alkenylene
moieties which can be partially substituted include ethylene, 1,2-propylene,
1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene,
1,8-octamethylene, 1,4-cyclohexylene, and mixtures thereof.
For the R1 moieties, the degree of partial substitution with moieties other
than
1,4-phenylene should be such that the desired properties of the compound are
not
adversely affected to any great extent. Generally, the degree of partial
substitution
which can be tolerated will depend upon the backbone length of the compound,
i.e.,
longer backbones can have greater partial substitution for 1,4-phenylene
moieties.
Usually, compounds where the RI comprise from about 50% to about 100%
1,4-phenylene moieties (from 0 to about 50% moieties other than 1,4-phenylene)
are
adequate. Preferably, the R I moieties consist entirely of (i.e., comprise I
00%)
1,4-phenylene moieties, i.e., each R 1 moiety is 1,4-phenylene.
For the R2 moieties, suitable ethylene or substituted ethylene moieties
include
ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1,2-propylene
and
mixtures thereof. Preferably, the R2 moieties are essentially ethylene
moieties,
1,2-propylene moieties or mixture thereof. Surprisingly, inclusion of a
greater
percentage of 1,2-propylene moieties tends to improve the water solubility of
the
compounds.
Therefore, the use of 1,2-propylene moieties or a similar branched equivalent
is
desirable for incorporation of any substantial part of the polymer in the
liquid fabric
softener compositions. Preferably, from about 75% to about 100%, more
preferably
from about 90% to about 100%, of the R2 moieties are 1,2-propylene moieties.
The value for each n is at least about 6, and preferably is at least about 10.
The
value for each n usually ranges from about 12 to about 113. Typically, the
value for
each n is in the range of from about 12 to about 43.
A more complete disclosure of these polymers is contained in European Patent
Application 185,427, Gosselink, published June 25, 1986, incorporated herein
by
reference.
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38
Other preferred copolymers include surfactants, such as the
polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO} reverse block
polymers.
The copolymer can optionally contain propylene oxide in an amount up to about
15% by weight. Other preferred copolymer surfactants can be prepared by the
processes
described in U.S. Patent 4,223,163, issued September 16, 1980, Builloty,
incorporated
herein by reference.
Suitable block polyoxyethylene-polyoxypropylene polymeric compounds that
meet the requirements described hereinbefore include those based on ethylene
glycol,
propylene glycol, glycerol, trimethylolpropane and ethylenediamine as
initiator reactive
hydrogen compound. Certain of the block polymer surfactant compounds
designated
PLURONIC~ and TETRONIC~ by the BASF-Wyandotte Corp., Wyandotte, Michigan,
are suitable in compositions of the invention.
A particularly preferred copolymer contains from about 40% to about 70% of a
polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend
comprising
about 75%, by weight of the blend, of a reverse block copolymer of
polyoxyethylene and
polyoxypropylene containing 17 moles of ethylene oxide and 44 moles of
propylene
oxide; and about 25%, by weight of the blend, of a block copolymer of
polyoxyethylene
and polyoxypropylene initiated with trimethylolpropane and containing 99 moles
of
propylene oxide and 24 moles of ethylene oxide per mole of trimethylolpropane.
Suitable for use as copolymer are those having relatively high hydrophilic-
lipophilic balance (HLB).
Other polymers useful herein include the polyethylene glycols having a
molecular
weight of from about 950 to about 30,000 which can be obtained from the Dow
Chemical Company of Midland, Michigan. Such compounds for example, have a
melting point within the range of from about 30oC to about 100oC, can be
obtained at
molecular weights of 1,450, 3,400, 4,500, 6,000, 7,400, 9,500, and 20,000.
Such
compounds are formed by the polymerization of ethylene glycol with the
requisite
number of moles of ethylene oxide to provide the desired molecular weight and
melting
point of the respective polyethylene glycol.
Other of block copolymers include the polyalkylene oxide polysiloxanes having
a
dimethyl polysiloxane hydrophobic moiety and one or more hydrophilic
polyalkylene side
chains, and having the general formula:
R1-(CH3)2Si0-[(CH3)2Si0]a-[(CH3)(Rl )Si0]h---Si(CH3)2--Rl
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39
wherein a + b are from about I to about S0, preferably from about 3 to about
30 , more
preferably from about 10 to about 2S, and each RI is the same or different and
is selected
from the group consisting of methyl and a poly(ethyleneoxide/propyleneoxide)
copolymer
group having the general formula:
-(CH2)n O(C2 H4 O)c (C3 H6 O)d R2
with at least one R I being a poly(ethyleneoxy/propyleneoxy) copolymer group,
and
wherein n is 3 or 4, preferably 3; total c (for all polyalkyleneoxy side
groups) has a value
of from I to about 100, preferably from about 6 to about 100; total d is from
0 to about 14,
preferably from 0 to about 3; and more preferably d is U; total c+d has a
value of from
about S to about 1 S0, preferably from about 9 to about 100 and each R2 is the
same or
different and is selected from the group consisting of hydrogen, an alkyl
having 1 to 4
carbon atoms, and an acetyl group, preferably hydrogen and methyl group. Each
polyalkylene oxide polysiloxane has at least one RI group being a
poly(ethyleneoxide/propyleneoxide) copolymer group.
Nonlimiting examples of this type of surfactants are the Silwet~ surfactants
which
are available OSi Specialties, Inc., Danbury, Connecticut. Representative
Silwet
surfactants which contain only ethyleneoxy (C2H40) groups are as follows.
Name Average MW Average a+b Average total
c
L-7608 600 1 9
L-7607 1,000 2 17
L-77 600 1 9
L-7605 6,000 20 99
L-7604 4,000 21 53
L-7600 4,000 11 6g
L-7657 5,000 20 76
L-7602 3,000
20 29
L-7622 10,000 88 7S
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WO 99/27050 PCTNS98/25079
Nonlimiting examples of surfactants which contain both ethyleneoxy (C2 H4 O)
and propyleneoxy (C3 H6 O) groups are as follows.
Name Average MW EO/PO ratio
Silwet L-720 12,000 50/50
Silwet L-7001 20,000 40/60
Silwet L-7002 8,000 SO/50
Silwet L-7210 13,000 20/80
Silwet L-7200 19,000 75/25
Silwet L-7220 17,000 20/80
The molecular weight of the polyalkyleneoxy group (RI) is less than or equal
to
about 10,000. Preferably, the molecular weight of the polyalkyleneoxy group is
less than
or equal to about 8,000, and most preferably ranges from about 300 to about
5,000. Thus,
the values of c and d can be those numbers which provide molecular weights
within these
ranges. However, the number of ethyleneoxy units (-C2H40) in the polyether
chain (RI)
must be sufficient to render the polyalkylene oxide polysiloxane water
dispersible or water
soluble. If propyleneoxy groups are present in the polyalkylenoxy chain, they
can be
distributed randomly in the chain or exist as blocks. Surfactants which
contain only
propyleneoxy groups without ethyleneoxy groups are not preferred. Preferred
Silwet
surfactants are L-7600, L-7602, L-7604, L-7605, L-7657, and mixtures thereof.
Besides
surface activity, polyalkylene oxide polysiloxane surfactants can also provide
other
benefits, such as antistatic benefits, lubricity and softness to fabrics.
The preparation of polyalkylene oxide polysiloxanes is well known in the art.
Polyalkylene oxide polysiloxanes of the present invention can be prepared
according to
the procedure set forth in U.S. Pat. No. 3,299,112, incorporated herein by
reference.
Typically, polyalkylene oxide polysiloxanes of the surfactant blend of the
present
invention are readily prepared by an addition reaction between a hydrosiloxane
(i.e., a
siloxane containing silicon-bonded hydrogen) and an alkenyl ether (e.g., a
vinyl, allyl, or
methallyl ether) of an alkoxy or hydroxy end-blocked polyalkylene oxide). The
reaction
conditions employed in addition reactions of this type are well known in the
art and in
general involve heating the reactants (e.g., at a temperature of from about
85° C. to 110°
C.) in the presence of a platinum catalyst (e.g., chloroplatinic acid) and a
solvent (e.g.,
toluene).
(7)- Alkyl amide alkoxylated nonionic surfactants
Suitable surfactants have the formula:
R - C(O) - N(R')~ - [(R'O)x(RzO)5.R3]m
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41
wherein R is C,_2, linear alkyl, C,_2, branched alkyl, C,_,, linear aIkenyl,
C,_2,
branched alkenyl, and mixtures thereof. Preferably R is Cg_,g linear alkyl or
alkenyl.
R' is -CH,-CH2- , RZ is C3-C4 linear alkyl, C3-C4 branched alkyl, and mixtures
thereof; preferably RZ is -CH(CH3)-CHZ-. Surfactants which comprise a mixture
of R1
and R2 units preferably comprise from about 4 to about 12 -CH,-CH2- units in
combination with from about 1 to about 4 -CH(CH3)-CHZ- units. The units may be
alternating or grouped together in any combination suitable to the formulator.
Preferably
the ratio of R' units to RZ units is from about 4 : 1 to about 8 : 1.
Preferably an RZ unit
(i.e. -C(CH3)H-CHZ-) is attached to the nitrogen atom followed by the balance
of the
chain comprising from about 4 to 8 -CHz-CH,- units.
R3 is hydrogen, C,-C4 linear alkyl, C3-C4 branched alkyl, and mixtures
thereof;
preferably hydrogen or methyl, more preferably hydrogen.
R4 is hydrogen, C,-C4 linear alkyl, C3-C4 branched alkyl, and mixtures
thereof;
preferably hydrogen. When the index m is equal to 2 the index n must be equal
to 0 and
the R4 unit is absent.
The index m is 1 or 2, the index n is 0 or l, provided that m + n equals 2;
preferably m is equal to l and n is equal to 1, resulting in one -
[(R'O)X(R20)~R3) unit and
R4 being present on the nitrogen. The index x is from 0 to about S0,
preferably from
about 3 to about 25, more preferably from about 3 to about 10. The index y is
from 0 to
about 10, preferably 0, however when the index y is not equal to 0, y is from
1 to about
4. Preferably all the alkyleneoxy units are ethyleneoxy units.
Examples of suitable ethoxylated alkyl amide-su~factants are Rewopal~ C6 from
Witco, Amidox~ CS from Stepan, and Ethomid~ O / 17 and Ethomid~ HT / 60 from
Akzo.; and
(8).- Mixtures thereof.
In terms of principal solvent reduction, with the invention compositions, a
reduction of at least 30% can be made without impairing the performance of the
composition compared to compositions without the phase stabilizers
hereinbefore
described. Using a preferred sub-class, a reduction of more than 50% is
possible. These
phase stabilizers provide an improved range of temperatures at which the
compositions
are clear and stable. They also allow more electrolyte to be used without
instability.
Finally, they can reduce the amount of principal solvent needed to achieve
clarity and/or
stability.
In order to reduce the amount of principal solvent used, the preferred phase
stabilizers are alkoxylated alkyls, alkoxylated acyl amides, alkoxylated alkyl
amines or
alkoxylated quaternary alkyl ammonium salts, surfactant complexes, and
mixtures
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42
thereof. The various stabilizers have different advantages. For example,
alkoxylated
cationic materials or cationic surfactant complexes improve softness and
provide
enhanced wrinkle release benefits.
For systems where the softener active compound is di(acyloxyethyl)(2-
hydroxyethyl)methyl ammonium methyl sulfate, where the acyl group is derived
from
partially hydrogenated canola fatty acid, it has been found that the preferred
level of
stabilizer for optimum clarity and stability increases with increasing level
of principal
solvent and optional perfume, and decreases with increasing levels of softener
active.
Fabric softener compositions with highly preferred dilution and dispensing
behaviors can be identified as disclosed hereinbefore.
OPTIONAL INGREDIENTS
(a). Perfume
The present invention can contain any softener compatible perfume.
Suitable perfumes are disclosed in U.S. Pat. Nos. 5,500,138 and 5,652,206,
Bacon
et al., issued March 19, 1996 and July 29, 1997 respectively, said patents
being
incorporated herein by reference.
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.
Examples of perfume ingredients useful in the perfumes of the present
invention compositions include, but are not limited to, those materials
disclosed in
said patents.
The perfumes useful in the present invention compositions are preferably
substantially free of halogenated materials and nitromusks.
Suitable solvents, diluents or carriers for perfumes ingredients mentioned
above are for examples, ethanol, isopropanol, diethylene glycol, monoethyl
ether,
dipropylene glycol, diethyl phthalate, triethyl citrate, etc. The amount of
such
solvents, diluents or carriers incorporated in the perfumes is preferably kept
to the
minimum needed to provide a homogeneous perfume solution.
Perfume can be present at a level of from 0% to about 15%, preferably from
about 0.1 % to about 8%, and more preferably from about 0.2% to about 5%, by
weight
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of the finished composition. Fabric softener compositions of the present
invention
provide improved fabric perfume deposition.
(b). Principal Solvent Extender
The compositions of the present invention can optionally include a principal
solvent extender to enhance stability and clarity of the formulations and in
certain
instances provide increased softness benefits. The solvent extender is
typically
incorporated in amounts ranging from about 0.05% to about 10%, more preferably
from
about 0.5% to about 5% and most preferably from about 1 % to about 4% by
weight of
the composition.
The principal solvent extender may include a range of materials with proviso
that
the material provide stability and clarity to a compositions having reduced
principal
solvent levels and typically reduced perfume or fragrance levels. Such
materials
typically include hydrophobic materials such as polar and non-polar oils, and
more
hydrophilic materials like hydrotropes and electrolytes as disclosed above,
e.g.
electrolytes of groups IIB, III and IV of the periodic table in particular
electrolytes of
groups IIB and IIIB such as aluminum, zinc, tin chloride electrolytes, sodium
EDTA,
sodium DPTA, and other electrolytes used as metal chelators.
Polar hydrophobic oils may be selected from emollients such as fatty esters,
e.g.
methyl oleates, Wickenols~, derivatives of myristic acid such as isopropyl
myristate, and
triglycerides such as canola oil; free fatty acids such as those derived from
canola oils,
fatty alcohols such as oleyl alcohol, bulky esters such as benzyl benzoate and
benzyl
salicylate, diethyl or dibutyl phthalate; bulky alcohols or diols; and perfume
oils
particularly low-odor perfume oils such as linalool; mono or poly sorbitan
esters; and
mixtures thereof. Non-polar hydrophobic oils may be selected from petroleum
derived
oils such as hexane, decane, penta decane, dodecane, isopropyl citrate and
perfume bulky
oils such as limonene, and mixtures thereof. In particular, the free fatty
acids such as
partially hardened canola oil may provide increased softness benefits.
Particularly preferred hydrophobic oils include the polar hydrophobic oils. In
particular, polar hydrophobic oils which have a freezing point, as defined by
a 20%
solution of the extender in 2,2,4-trimethyl-1,3-pentanediol, of less than
about 22°C and
more preferably less than about 20°C. Preferred oils in this class
include methyl oleate,
benzyl benzoate and canola oil.
Suitable hydrotropes include sulfonate electrolytes particularly alkali metal
sulfonates
and carboxylic acid derivatives such as isopropyl citrate. In particular,
sodium and
calcium cumene sulfonates and sodium toluene sulfonate. Alternative
hydrotropes
include benzoic acid and its derivatives, electrolytes of benzoic acid and its
derivatives.
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(c). Cationic Charge Boosters ,
Cationic charge boosters may be added to the rinse-added fabric softening
compositions of the present invention if needed. Some of the charge boosters
serve other
functions as described hereinbefore. Typically, ethanol is used to prepare
many of the
below listed ingredients and is therefore a source of solvent into the final
product
formulation. The formulator is not limited to ethanol, but instead can add
other solvents
inter alia hexyleneglycol to aid in formulation of the final composition.
The preferred cationic charge boosters of the present invention are described
herein
below.
(i) C~uaternary Ammonium Compounds
A preferred composition of the present invention comprises at least about
0.2%,
preferably from about 0.2% to about 10%, more preferably from about 0.2% to
about 5% by
weight, of a cationic charge booster having the formula:
R2
+ -
Rl -N R3
X
R4
wherein R1, R2, R3, and R4 are each independently CI-C22 alkyl, C3-C22
alkenyl, RS-Q-
(CH2)m-, wherein RS is C1-C22 alkyl, and mixtures thereof, m is from 1 to
about 6; X is an
anion.
Preferably R1 is C6-C22 alkyl, C6-C22 aikenyl, and mixtures thereof, more
preferably C 11-C 1 g alkyl, C 11-C 1 g alkenyl, and mixtures thereof; R2, R3,
and R4 are each
preferably C1-C4 alkyl, more preferably each R2, R3, and R4 are methyl.
The formulator may similarly choose R1 to be a RS-Q-(CH2)m- moiety wherein RS
is an alkyl or alkenyl moiety having from 1 to 22 carbon atoms, preferably the
alkyl or
alkenyl moiety when taken together with the Q unit is an acyl unit derived
preferably
derived from a source of triglyceride selected from the group consisting of
tallow, partially
hydrogenated tallow, lard, partially hydrogenated lard, vegetable oils and/or
partially
hydrogenated vegetable oils, such as, canola oil, safflower oil, peanut oil,
sunflower oil, corn
oil, soybean oil, tall oil, rice bran oil, etc. and mixtures thereof.
An example of a fabric softener cationic booster comprising a RS-Q-(CH2)m-
moiety has the formula:
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WO 99/27050 PCT/US98/25079
O ~ Hs
~ +N-CH3
C1 t
CH3
wherein RS-Q- is an oleoyl units and m is equal to 2.
X is a softener compatible anion, preferably the anion of a strong acid, for
example,
chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures
thereof, more
preferably chloride and methyl sulfate.
(ii) Polyvinyl Amines
A preferred composition according to the present invention contains at feast
about
0.2%, preferably from about 0.2% to about 5%, more preferably from about 0.2%
to about
2% by weight, of one or more polyvinyl amines having the formula
CH2-CH
NH2
wherein y is from about 3 to about 10,000, preferably from about 10 to about
5,000, more
preferably from about 20 to about 500. Polyvinyl amines suitable for use in
the present
invention are available from BASF.
Optionally, one or more of the polyvinyl amine backbone -NHS unit hydrogens
can
be substituted by an alkyleneoxy unit having the formula:
(RI O)xR2
wherein R1 is C2-C4 alkylene, R2 is hydrogen, C1-C4 alkyl, and mixtures
thereof; x is from
1 to 50. In one embodiment or the present invention the polyvinyl amine is
reacted first
with a substrate which places a 2-propyleneoxy unit directly on the nitrogen
followed by
reaction of one or more moles of ethylene oxide to form a unit having the
general formula:
CH3
-(CH2CH0)-(CH2CH20)xH
wherein x has the value of from 1 to about S0. Substitutions such as the above
are
represented by the abbreviated formula PO-EOx-. However, more than one
propyleneoxy
unit can be incorporated into the alkyleneoxy substituent.
Polyvinyl amines are especially preferred for use as cationic charge booster
in liquid
fabric softening compositions since the greater number of amine moieties per
unit weight
CA 02310612 2000-OS-18
WO 99!27050 PCTNS98/25075
46
provides substantial charge density. In addition, the cationic charge is
generated in situ and
the level of cationic charge can be adjusted by the formulator.
(iii) Polyalkyleneimines
A preferred composition of the present invention comprises at least about
0.2%,
preferably from about 0.2% to about 10%, more preferably from about 0.2% to
about 5% by
weight, of a polyalkyleneimine charge booster having the formula:
H
(H2N-RJn+1-fN-RJm-fN-RJri NH2
wherein the value of m is from 2 to about 700 and the value of n is from 0 to
about 350.
Preferably the compounds of the present invention comprise polyamines having a
ratio of m
n that is at least 1:1 but may include linear polymers (n equal to 0) as well
as a range as
high as 10:1, preferably the ratio is 2:1. When the ratio of m:n is 2:1, the
ratio of
primaryaecondaryaertary amine moieties, that is the ratio of -RNH2, -RNH, and -
RN
moieties, is 1:2:1.
R units are C2-Cg alkylene, C3-Cg alkyl substituted alkylene, and mixtures
thereof,
preferably ethylene, 1,2-propylene, 1,3-propylene, and mixtures thereof, more
preferably
ethylene. R units serve to connect the amine nitrogens of the backbone.
Optionally, one or more of the polyvinyl amine backbone -NH2 unit hydrogens
can
be substituted by an alkyleneoxy unit having the formula:
-~l O)xR2
wherein R1 is C2-C4 alkylene, R2 is hydrogen, C1-C4 alkyl, and mixtures
thereof; x is from
I to 50. In one embodiment or the present invention the polyvinyl amine is
reacted first
with a substrate which places a 2-propyleneoxy unit directly on the nitrogen
followed by
reaction of one or more moles of ethylene oxide to form a unit having the
general formula:
CH3
(CH~CHO)-(CH~CH20)xH
wherein x has the value of from I to about S0. Substitutions such as the above
are
represented by the abbreviated formula PO-EOx-. However, more than one
propyleneoxy
unit can be incorporated into the alkyleneoxy substituent.
The preferred polyamine cationic charge boosters suitable for use in rinse-
added
fabric softener compositions comprise backbones wherein less than 50% of the R
groups
comprise more than 3 carbon atoms. The use of two and three carbon spacers as
R moieties
CA 02310612 2000-05-18
WO 99/27050 PCT/US98/25079
47
between nitrogen atoms in the backbone is advantageous for controlling the
charge booster
properties of the molecules. More preferred embodiments of the present
invention comprise
less than 25% moieties having more than 3 carbon atoms. Yet more preferred
backbones
comprise less than 10% moieties having more than 3 carbon atoms. Most
preferred
backbones comprise 100% ethylene moieties.
The cationic charge boosting polyamines of the present invention comprise
homogeneous or non-homogeneous polyamine backbones, preferably homogeneous
backbones. For the purpose of the present invention the term "homogeneous
polyamine
backbone" is defined as a polyamine backbone having R units that are the same
{i.e., all
ethylene). However, this sameness definition does not exclude polyamines that
comprise
other extraneous units comprising the polymer backbone that are present due to
an artifact of
the chosen method of chemical synthesis. For example, it is known to those
skilled in the art
that ethanolamine may be used as an "initiator" in the synthesis of
polyethyleneimines,
therefore a sample of polyethyleneimine that comprises one hydroxyethyl moiety
resulting
from the polymerization "initiator" would be considered to comprise a
homogeneous
polyamine backbone for the purposes of the present invention.
For the purposes of the present invention the term "non-homogeneous polymer
backbone" refers to polyamine backbones that are a composite of one or more
alkylene or
substituted alkylene moieties, for example, ethylene and 1,2-propylene units
taken together
as R units
However, not all of the suitable charge booster agents belonging to this
category of
polyamine comprise the above described polyamines. Other polyamines that
comprise the
backbone of the compounds of the present invention are generally
polyalkyleneamines
(PAA's), polyalkyleneimines (PAI's), preferably polyethyleneamine (PEA's), or
polyethyleneimines (PEI's). A common polyalkyleneamine (PAA) is
tetrabutylenepentamine. PEA's are obtained by reactions involving ammonia and
ethylene
dichloride, followed by fractional distillation. The common PEA's obtained are
triethylenetetramine (TETA) and tetraethylenepentamine (TEPA). Above the
pentamines,
i.e., the hexamines, heptamines, octamines and possibly nonamines, the
cogenerically
derived mixture does not appear to separate by distillation and can include
other materials
such as cyclic amines and particularly piperazines. There can also be present
cyclic amines
with side chains in which nitrogen atoms appear. See U.S. 2,792,372,
Dickinson, issued
May 14, 1957, which describes the preparation of PEA's.
The PEI's which comprise the preferred backbones of the charge boosters of the
present invention can be prepared, for example, by polymerizing ethyleneimine
in the
presence of a catalyst such as carbon dioxide, sodium bisulfate, sulfuric
acid, hydrogen
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WO 99/27050 PCT/US98/25079
48
peroxide, hydrochloric acid, acetic acid, etc,. Specific methods for preparing
PE1's are
disclosed in U.S. 2,182,306, Ulrich et al., issued December 5, 1939; U.S.
3,033,746, Mayle
et al., issued May 8, 1962; U.S. 2,208,095, Esselmann et al., issued July 16,
1940; U.S.
2,806,839, Crowther, issued September 17, 1957; and U.S. 2,553,696, Wilson,
issued May
21, 1951 (all herein incorporated by reference). In addition to the linear and
branched PEI's,
the present invention also includes the cyclic amines that are typically
formed as artifacts of
synthesis. The presence of these materials may be increased or decreased
depending on the
conditions chosen by the formulator.
(iv) Poly-Quaternar~Ammonium Compounds
A preferred composition of the present invention comprises at least about
0.2%,
preferably from about 0.2% to about 10%, more preferably from about 0.2% to
about 5% by
weight, of a cationic charge booster having the formula:
R1 R1
+I I+ _
R2-N-R-N-R2 2 X
Rl R1
wherein R is substituted or unsubstituted C2-C 12 alkylene, substituted or
unsubstituted C2-
C12 hydroxyalkylene; each R1 is independently C1-C4 alkyl, each R2 is
independently C1-
C22 alkyl, C3-C22 alkenyl, RS-Q-(CH2)m-, wherein R5 is C1-C22 alkyl, C3-C22
alkenyl,
and mixtures thereof; m is from 1 to about 6; Q is a carbonyl unit as defined
hereinabove;
and mixtures thereof; X is an anion.
Preferably R is ethylene; R1 is methyl or ethyl, more preferably methyl; at
least one
R2 is preferably C1-C4 alkyl, more preferably methyl. Preferably at least one
R2 is C11-
C22 alkyl, C 11-C22 alkenyl, and mixtures thereof.
The formulator may similarly choose R2 to be a RS-Q-(CH2)m- moiety wherein RS
is an alkyl moiety having from 1 to 22 carbon atoms, preferably the alkyl
moiety when taken
together with the Q unit is an acyl unit derived preferably derived from a
source of
triglyceride selected from the group consisting of tallow, partially
hydrogenated tallow, lard,
partially hydrogenated lard, vegetable oils and/or partially hydrogenated
vegetable oils, such
as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean
oil, tall oil, rice bran
oil, etc. and mixtures thereof.
An example of a fabric softener cationic booster comprising a RS-Q-(CH2)m-
moiety has the formula:
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WO 99/27050 PCT/US98/25079
49
Cf CH3
- O~ CHj~N-CH3
+N 1
O Cf CH CH3
3
wher
ein R1 is methyl, one R2 units is methyl and the other R2 unit is RS-Q-(CH2)m-
wherein RS-
Q- is an oleoyl unit and m is equal to 2.
X is a softener compatible anion, preferably the anion of a strong acid, for
example,
chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures
thereof, more
preferably chloride and methyl sulfate.
w). Cationic Polymers
Composition herein can contain from about 0.001 % to about 10%, preferably
from about 0.01 % to about 5%, more preferably from about 0.1 % to about 2%,
of
cationic polymer, typically having a molecular weight of from about 500 to
about
1,000,000, preferably from about I,000 to about 500,000, more preferably from
about
1,000 to about 250,000, and even more preferably from about 2,000 to about
100,000 and
a charge density of at least about 0.01 meq/gm., preferably from about 0.1 to
about 8
meq/gm., more preferably from about 0.5 to about 7, and even more preferably
from
about 2 to about 6.
The cationic polymers of the present invention can be amine salts or
quaternary
ammonium salts. Preferred are quaternary ammonium salts. They include cationic
derivatives of natural polymers such as some polysaccharide, gums, starch and
certain
cationic synthetic polymers such as polymers and copo~mers of cationic vinyl
pyridine or
vinyl pyridinium halides. Preferably the polymers are water soluble, for
instance to the
extent of at least 0.5% by weight at 20oC. Preferably they have molecular
weights of from
about 600 to about 1,000,000, more preferably from about 600 to about 500,000,
even
more preferably from about 800 to about 300,000, and especially from about
1000 to
10,000. As a general rule, the lower the molecular weight the higher the
degree of
substitution (D.S.) by cationic, usually quaternary groups, which is
desirable, or,
correspondingly, the lower the degree of substitution the higher the molecular
weight
which is desirable, but no precise relationship appears to exist. In general,
the cationic
polymers should have a charge density of at least about 0.01 meq/gm.,
preferably from
about 0.1 to about 8 meq/gm., more preferably from about 0.5 to about 7, and
even more
preferably from about 2 to about 6.
Suitable desirable cationic polymers are disclosed in "CTFA International
Cosmetic
Ingredient Dictionary, Fourth Edition, J. M. Nikitakis, et al, Editors,
published by the
CA 02310612 2000-OS-18
WO 99127050 PCTNS98/2507Q
Cosmetic, Toiletry, and Fragrance Association, 1991, incorporated herein by
reference.
The list includes the following:
Of the polysaccharide gums, guar and locust bean gums, which are galactomannam
gums are available commercially, and are preferred. Thus guar gums are
marketed under
Trade Names CSAA M/200, CSA 200/50 by Meyhall and Stein-Hall, and
hydroxyalkylated guar gums are available from the same suppliers. Other
polysaccharide
gums commercially available include: Xanthan Gum; Ghatti Gum; Tamarind Gum;
Gum
Arabic; and Agar.
Cationic guar gums and methods for making them are disclosed in British Pat.
No.
1,136,842 and U.S. Pat. No. 4,031,307. Preferably they have a D.S. of from 0.1
to about
0.5.
An effective cationic guar gum is Jaguar C-13S (Trade Name--Meyhall). Cationic
guar gums are a highly preferred group of cationic polymers in compositions
according to
the invention and act both as scavengers for residual anionic surfactant and
also add to the
softening effect of cationic textile softeners even when used in baths
containing little or no
residual anionic surfactant. The other polysaccharide-based gums can be
quaternized
similarly and act substantially in the same way with varying degrees of
effectiveness.
Suitable starches and derivatives are the natural starches such as those
obtained from
maize, wheat, barley etc., and from roots such as potato, tapioca etc., and
dextrins,
particularly the pyrodextrins such as British gum and white dextrin.
Some very effective individual cationic polymers are the following: Polyvinyl
pyridine, molecular weight about 40,000, with about-60% of the available
pyridine
nitrogens quaternized.; Copolymer of 70/30 molar proportions of vinyl
pyridine/styrene,
molecular weight about 43,000, with about 45% of the available pyridine
nitrogens
quaternized as above; Copolymers of 60/40 molar proportions of vinyl
pyridine/acrylamide, with about 35% of the available pyridine nitrogens
quaternized as
above. Copolymers of 77/23 and 57/43 molar proportions of vinyl
pyridine/methyl
methacrylate, molecular weight about 43,000, with about 97% of the available
pyridine
nitrogens quaternized as above.
These cationic polymers are effective in the compositions at very low
concentrations
for instance from 0.001 % by weight to 0.2% especially from about 0.02% to 0.1
%. In
some instances the effectiveness seems to fall off, when the content exceeds
some
optimum level, such as for polyvinyl pyridine and its styrene copolymer about
0.05%.
Some other effective cationic polymers are: Copolymer of vinyl pyridine and N-
vinyl pyrrolidone (63/37) with about 40% of the available pyridine nitrogens
quaternized.;
Copolymer of vinyl pyridine and acrylonitrile (60/40), quaternized as above.;
Copolymer
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WO 99/27050 PCT/US98I25079
51
of N,N-dimethyl amino ethyl methacrylate and styrene (55/45) quaternized as
above at
about 75% of the available amino nitrogen atoms. Eudragit E (Trade Name of
Rohm
GmbH) quaternized as above at about 75% of the available amino nitrogens.
Eudragit E is
believed to be copolymer of N,N-dialkyl amino alkyl methacrylate and a neutral
acrylic
acid ester, and to have molecular weight about 100,000 to 1,000,000.;
Copolymer of N-
vinyl pyrrolidone and N,N-diethyl amino methyl methacrylate (40/50),
quaternized at
about 50% of the available amino nitrogens.; These cationic polymers can be
prepared in
a known manner by quaternising the basic polymers.
Yet other cationic polymeric salts are quaternized polyethyleneimines. These
have at
least 10 repeating units, some or all being quaternized. Commercial examples
of polymers
of this class are also sold under the generic Trade Name Alcostat by Allied
Colloids.
Typical examples of polymers are disclosed in U.S. Pat. No. 4,179,382,
incorporated
herein by reference.
Each polyamine nitrogen whether primary, secondary or tertiary, is further
defined as being a member of one of three general classes; simple substituted,
quaternized or oxidized.
The polymers are made neutral by water soluble anions such as chlorine (C1-),
bromin~ (Br-), iodine (I-) or any other negatively charged radical such as
sulfate (S042-)
and methosulfate (CH3503-).
Specific polyamine backbones are disclosed in U.S. Patent 2,182,306, Ulrich et
al., issued December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May
8, 1962;
U.S. Patent 2,208,095, Esselmann et al., issued July 16, 1940; U.S. Patent
2,806,839,
Crowther, issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued
May
21, 1951; all herein incorporated by reference.
An example of modified polyamine cationic polymers of the present invention
comprising PEI's comprising a PEI backbone wherein all substitutable nitrogens
are
modified by replacement of hydrogen with a polyoxyalkyIeneoxy unit, -
(CH2CH20)7H.
Other suitable polyamine cationic polymers comprise this molecule which is
then
modified by subsequent oxidation of all oxidizable primary and secondary
nitrogens to
N-oxides and/or some backbone amine units are quaternized, e.g. with methyl
groups.
Of course, mixtures of any of the above described cationic polymers can be
employed, and the selection of individual polymers or of particular mixtures
can be used to
control the physical properties of the compositions such as their viscosity
and the stability
of the aqueous dispersions.
(d). Bri hteners
CA 02310612 2000-OS-18
WO 99127050 PCT/US98125079
52
The compositions herein can also optionally contain from about 0.005% to about
5% by weight of certain types of hydrophilic optical brighteners which also
provide a
dye transfer inhibition action. If used, the compositions herein will
preferably comprise
from about 0.001 % to about 1 % by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those
described in said U. S. Pat. No. 5,759,990 at column 21, lines 1 ~-60.
(e). Mono-Alkyl Cationic Quaternary Ammonium Compound
When the mono-long chain alkyl cationic quaternary ammonium compound is
present, it is typically present at a level of from about 2% to about 25%,
preferably from
about 3% to about 17%, more preferably from about 4% to about 15%, and even
more
preferably from about S% to about 13% by weight of the composition, the total
mono-
alkyl cationic quaternary ammonium compound being at least at an effective
level to
improve softening in the presence of anionic surfactant.
Such mono-alkyl cationic quaternary ammonium compounds useful in the present
invention are, preferably, quaternary ammonium salts of the general formula:
~R4N+(RS)3~ A_
wherein
R4 is Cg-C22 alkyl or alkenyl group, preferably C 10-C 1 g alkyl or alkenyl
group; more
preferably C 10-C 14 or C 16-C 1 g alkyl or alkenyl group;
each RS is a C1-C6 alkyl or substituted alkyl group (e.g., hydroxy alkyl),
preferably C1-
C3 alkyl group, e.g., methyl (most preferred), ethyl, propyl, and the like, a
benzyl group,
hydrogen, a polyethoxylated chain with from about 2 to about 20 oxyethylene
units,
preferably from about 2.5 to about 13 oxyethylene units, more preferably from
about 3 to
about 10 oxyethylene units, and mixtures thereof; and
A- is as defined hereinbefore for (Formula (I)).
Especially preferred are monolauryl trimethyl ammonium chloride and
monotallow trimethyl ammonium chloride available from Witco under the trade
name
Varisoft~ 471 and monooleyl trimethyl ammonium chloride available from Witco
under
the tradename Varisoft~ 417.
The R4 group can also be attached to the cationic nitrogen atom through a
group
containing one, or more, ester, amide, ether, amine, etc., linking groups.
Such linking
groups are preferably within from about one to about three carbon atoms of the
nitrogen
atom.
Mono-alkyl cationic quaternary ammonium compounds also include Cg-C22
alkyl choline esters. The preferred compounds of this type have the formula:
~R1C(O)-O-CH2CH2N+(R)3 ~ A-
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WO 99/27050 PCT/US98/25079
53
wherein Rl, R and A- are as defined previously.
Highly preferred compounds include C 12-C 14 coco choline ester and C 16-C 18
tallow choline ester.
Suitable biodegradable single-long-chain alkyl compounds containing an ester
linkage in the long chains are described in U.S. Pat. No. 4,840,738, Hardy and
Walley,
issued June 20, 1989, said patent being incorporated herein by reference.
Suitable mono-long chain materials correspond to the preferred biodegradable
softener actives disclosed above, where only one RI group is present in the
molecule.
The R 1 group or YR 1 group, is replaced normally by an R group.
These quaternary compounds having only a single long alkyl chain, can protect
the cationic softener from interacting with anionic surfactants and/or
detergent builders
that are carried over into the rinse from the wash solution. It is highly
desirable to have
sufficient single long chain quaternary compound, or cationic polymer to tie
up the
anionic surfactant. This provides improved softness and vvrinkie control. The
ratio of
fabric softener active to single long chain compound is typically from about
100:1 to
about 2:1, preferably from about 50:1 to about 5:1, more preferably from about
13:1 to
about 8:1. Under high detergent carry-over conditions, the ratio is preferably
from about
5:1 to about 7:1. Typically the single long chain compound is present at a
level of about
ppm to about 25 ppm in the rinse.
(f). 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,
preferably, from
about 0.01 % to about 0.2% for reductive agents. These assure good odor
stability under
long term storage conditions. Antioxidants and reductive agent stabilizers are
especially
critical for unscented or low scent products (no or low perfume).
Examples of antioxidants that can be added to the compositions and in the
processing of this invention include a mixture of ascorbic acid, ascorbic
palmitate, propyl
gallate, available from Eastman Chemical Products, Inc., under the trade names
Tenox~
PG and Tenox~ S-1; a mixture of BHT (butylated hydroxytoluene), BHA (butylated
hydroxyanisole), propyl galiate, and citric 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-1/GT-2; and
butylated
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WO 99/27050 PCT/US98/25079
54
. _ hydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chain esters
(C8-C22)
of gallic acid, e.g., dodecyl gallate; Irganox~ 1010; Irganox~ 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 or mixed with citric acid and/or other chelators such as
isopropyl
citrate, Dequest~ 2010, available from Monsanto with a chemical name of 1-
hydroxyethylidene-l, 1-diphosphonic acid (etidronic acid), and Tiron~,
available from
Kodak with a chemical name of 4,5-dihydroxy-m-benzene-sulfonic acid/sodium
salt, and
DTPA~, available from Aldrich with a chemical name of
diethylenetriaminepentaacetic
acid.
(g). Soil Release Agent
Suitable soil release agents are disclosed in the U.S. Pat. No. 5,759,990 at
column
23, line 53 through column 25, line 41. The addition of the soil release agent
can occur
in combination with the premix, in combination with the acid/water seat,
before or after
electrolyte addition, or after the final composition is made. The softening
composition
prepared by the process of the present invention herein can contain from 0% to
about
10%, preferably from 0.2% to about 5%, of a soil release agent. Preferably,
such a soil
release agent is a polymer. Polymeric soil release agents useful in the
present invention
include copolymeric blocks of terephthalate and polyethylene oxide or
polypropylene
oxide, and the like.
A preferred soil release agent is a copolymer having blocks of terephthalate
and
polyethylene oxide. More specifically, these polymers are comprised of
repeating units
of ethylene terephthalate and polyethylene oxide terephthalate at a molar
ratio of
ethylene terephthalate units to polyethylene oxide terephthalate units of from
25:75 to
about 35:65, said polyethylene oxide terephthalate containing polyethylene
oxide blocks
having molecular weights of from about 300 to about 2000. The molecular weight
of
this polymeric soil release agent is in the range of from about 5,000 to about
55,000.
Another preferred polymeric soil release agent is a crystallizable polyester
with
repeat units of ethylene terephthalate units containing from about 10% to
about 1 S% by
weight of ethylene terephthalate units together with from about 10% to about
SO% by
weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene
glycol of
average molecular weight of from about 300 to about 6,000, and the molar ratio
of
ethylene terephthalate units to polyoxyethylene terephthalate units in the
crystallizable
polymeric compound is between 2:1 and 6:1. Examples of this polymer include
the
commercially available materials Zelcon 4780~ (from Dupont) and Milease T~
(from
ICI).
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WO 99/27050 PCTNS98/25079
These soil release agents can also act as a scum dispersant.
(h). 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 name
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 name Kathon about 1 to about
1,000
ppm by weight of the agent.
(i). Chelating Agents
The compositions and processes herein can optionally employ one or more
copper and/or nickel chelating agents ("chelators"). Such water-soluble
chelating agents
can be selected from the group consisting of amino carboxylates, amino
phosphonates,
polyfunctionally-substituted aromatic chelating agents and mixtures thereof,
all as
hereinafter defined. The whiteness and/or brightness of fabrics are
substantially
improved or restored by such chelating agents and the stability of the
materials in the
compositions are improved.
The chelating agents disclosed in said U. S. Pat. No. 5,759,990 at column 26,
line
29 through column 27, line 38 are suitable.
The chelating agents are typically used in the present rinse process at levels
from
about 2 ppm to about 25 ppm, for periods from 1 minute up to several hours'
soaking.
A preferred EDDS chelator that can be used herein (also known as
ethylenediamine-N,N'-disuccinate) is the material described in U.S. Patent
4,704,233,
cited hereinabove, and has the formula (shown in free acid fonw):
HN(L)C2H4N(L)H
wherein L is a CH2(COOH)CH2(COOH) group.
A wide variety of chelators can be used herein. Indeed, simple
polycarboxylates
such as citrate, oxydisuccinate, and the like, can also be used, although such
chelators are
not as effective as the amino carboxylates and phosphonates, on a weight
basis.
Accordingly, usage levels may be adjusted to take into account differing
degrees of
chelating effectiveness. The chelators herein will preferably have a stability
constant (of
the fully ionized chelator) for copper ions of at least about 5, preferably at
least about 7.
Typically, the chelators will comprise from about 0.5% to about 10%, more
preferably
from about 0.75% to about 5%, by weight of the compositions herein, in
addition to
those that are stabilizers. Preferred chelators include DETMP, DETPA, NTA,
EDDS,
TPED, and mixtures thereof.
(j). Color Care Agent
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56
The composition can optionally comprise from about 0.1% to about 50% of by
weight of
the composition of a color care agent having the formula:
(R1 )(R2)N(CX2)nN(R3)(R4)
wherein X is selected from the group consisting of hydrogen, linear or
branched,
substituted or unsubstituted alkyl having from 1 to 10 carbons atoms and
substituted or
unsubstituted aryl having at least 6 carbon atoms; n is an integer from 0 to
6; R1, R2, R3,
and R4 are independently selected from the group consisting of alkyl; aryl;
alkaryl;
arylalk; hydroxyalkyl; polyhydroxyalkyl; polyalkylether having the formula -
((CH2)y0)zR~ where R~ is hydrogen or a linear, branched, substituted or
unsubstituted
alkyl chain having from 1 to 10 carbon atoms and where y is an integer from 2
to 10 and
z is an integer from 1 to 30; alkoxy; polyalkoxy having the formula: -
(O(CH2)y)zR~; the
group -C(O)Rg where Rg is alkyl; alkaryl; arylalk; hydroxyalkyl;
polyhydroxyalkyl and
polyalkyether as defined in R1, R2, R3, and R4; (CX2)nN(R5)(R6) with no more
than
one of R1, R2, R3, and R4 being (CX2)~N(RS)(R6) and wherein RS and R6 are
alkyl;
alkaryl; arylalk; hydroxyalkyl; polyhydroxyalkyl; polyalkylether; alkoxy and
polyalkoxy
as defined in R1, R2, R3, and R4; and either of R1 + R3 or R4 or R2 + R3 or R4
can
combine to form a cyclic substituent.
Preferred agents include those where R1, R2, R3, and R4 are independently
selected from the group consisting of alkyl groups having from 1 to 10 carbon
atoms and
hydroxyalkyl groups having from 1 to S carbon atoms, preferably ethyl, methyl,
hydroxyethyl, hydroxypropyl and isohydroxypropyl. The color care agent has
more than
about 1 % nitrogen by weight of the compound, and preferably more than 7%. A
preferred agent is tetrakis-(2-hydroxylpropyl) ethylenediamine (TPED).
(k). Silicones
The silicone herein can be either a polydimethyl siloxane (polydimethyl
silicone
or PDMS), or a derivative thereof, e.g., amino silicones, ethoxylated
silicones, etc. The
PDMS, is preferably one with a low molecular weight, e.g., one having a
viscosity of
from about 2 to about 5000 cSt, preferably from about 5 to about 500 cSt, more
preferably from about 25 to about 200 cSt Silicone emulsions can conveniently
be used
to prepare the compositions of the present invention. However, preferably, the
silicone is
one that is, at least initially, not emulsified. Le., the silicone should be
emulsified in the
composition itself. In the process of preparing the compositions, the silicone
is
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57
preferably added to the "water seat", which comprises the water and,
optionally, any
other ingredients that normally stay in the aqueous phase.
Low molecular weight PDMS is preferred for use in the fabric softener
compositions of this invention. The low molecular weight PDMS is easier to
formulate
without pre-emulsification.
Silicone derivatives such as amino-functional silicones, quaternized
silicones, and
silicone derivatives containing Si-OH, Si-H, and/or Si-CI bonds, can be used.
However,
these silicone derivatives are normally more substantive to fabrics and can
build up on
fabrics after repeated treatments to actually cause a reduction in fabric
absorbency.
When added to water, the fabric softener composition deposits the
biodegradable
cationic fabric softening active on the fabric surface to provide fabric
softening effects.
However, in a typical laundry process, using an automatic washer, cotton
fabric water
absorbency can be appreciably reduced at high softener levels and/or after
multiple
cycles. The silicone improves the fabric water absorbency, especially for
freshly treated
fabrics, when used with this level of fabric softener without adversely
affecting the fabric
softening performance. The mechanism by which this improvement in water
absorbency
occurs is not understood, since the silicones are inherently hydrophobic. It
is very
surprising that there is any improvement in water absorbency, rather than
additional loss
of water absorbency.
The amount of PDMS needed to provide a noticeable improvement in water
absorbency is dependent on the initial rewettabiiity performance, which, in
turn, is
dependent on the detergent type used in the wash. Effective amounts range from
about 2
ppm to about 50 ppm in the rinse water, preferably from about 5 to about 20
ppm. The
PDMS to softener active ratio is from about 2:100 to about 50:100, preferably
from about
3:100 to about 35:100, more preferably from about 4:100 to about 25:100. As
stated
hereinbefore, this typically requires from about 0.2% to about 20%, preferably
from
about 0.5% to about 10%, more preferably from about 1% to about 5% silicone.
The PDMS also improves the ease of ironing in addition to improving the
rewettability characteristics of the fabrics. When the fabric care composition
contains an
optional soil release polymer, the amount of PDMS deposited on cotton fabrics
increases
and PDMS improves soil release benefits on polyester fabrics. Also, the PDMS
improves the rinsing characteristics of the fabric care compositions by
reducing the
tendency of the compositions to foam during the rinse. Surprisingly, there is
little, if
any, reduction in the softening characteristics of the fabric care
compositions as a result
of the presence of the relatively large amounts of PDMS.
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The present invention can include other optional components conventionally
used
in textile treatment compositions, for example: colorants; preservatives;
surfactants; anti-
shrinkage agents; fabric crisping agents; spotting agents; germicides;
fungicides; anti-
corrosion agents; enzymes such as proteases, cellulases, amylases, lipases,
etc; and the
Like.
The present invention can also include other compatible ingredients, including
those disclosed U.S. Pat. No. 5,686,376, Rusche, et al.; issued November 11,
1997,
Shaw, et al.; and U.S. Pat. No. 5,536,421, Hartman, et al., issued 3uly 16,
1996, said
patents being incorporated herein by reference.
All parts, percentages, proportions, and ratios herein are by weight unless
otherwise specified and all numerical values are approximations based upon
normal
confidence limits. All documents cited are, in relevant part, incorporated
herein by
reference.
The following is an example of a softener compound useful in the present
invention:
TEA Di-ester Quat: Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl
sulfate
where the acyl group is derived from partially hydrogenated canola fatty acid
1 )-Esterification:
About 536 grams of partly hydrogenated tallow fatty acid with an IV of about
98,
a cis/trans ratio (C 18:1 ) and an Acid Value of about 198.5, a special grade
of Industrene
fatty acid available from Witco Corporation, is added into the reactor, the
reactor is
flushed with N2 and about 149 grams of triethanolamine is added under
agitation. The
molar ratio of fatty acid to triethanol amine is of about 1.9:1. The mixture
is heated
above about 150° C and the pressure is reduced to remove the water of
condensation.
The reaction is prolonged until an Acid Value of about 4 is reached.
2 ~uaternization:
To about 645 grams of the product of condensation, about 122 grams of
dimethylsulfate is added under continuous agitation. The reaction mixture is
kept above
about 50° C and the reaction is followed by verifying the residual
amine value. 767
grams of softener compound is obtained.
The quaternized material is optionally diluted with e.g. about 68 g of ethanol
and
about 68 g of hexylene glycol which lowers the melting point of the material
thereby
providing a better handling of the material. Additional ingredients can be
added to the
material at this time including chelants, antioxidants, perfume, etc.
Disclosures of such
materials and the benefits of including them can be found in U.S. Pat.
5,747.443, Wahl,
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59
Trinh, Gosselink, Letton, and Sivik, issued May 5, 1998 and in U.S. Pat.
5,686,376,
Rusche, Baker, and Maashlein, issued Nov. 11, 1997, said patents being
incorporated
herein by reference.
The above synthesized softener compound is also exemplified below in the non-
limiting fabric softening composition examples.
The following non-limiting Examples show clear, or translucent, products
with acceptable viscosities. The compositions in the Examples below are made
by first
preparing an oil seat of softener active at ambient temperature. The softener
active can
be heated, if necessary, to melting, if the softener active is not fluid at
room temperature.
The softener active is mixed using an IKA RW 25~ mixer for about ?. to about 5
minutes
at about 150 rpm. Separately, a water seat is prepared, i.e., with deionized
(DI) water at
ambient temperature and with optional acid if needed to adjust pH. If the
softener active
and/or the principal solvents) are not fluid at room temperature and. need to
be heated,
the acid/water seat should also be heated to a suitable temperature, e.g.,
about 100°F
(about 38°C) and maintaining said temperature with a water bath. The
principal
solvents) (melted at suitable temperatures if their melting points are above
room
temperature) are added to the softener premix and said premix is mixed for
about ~
minutes. Then the optional phase stabilizers) are added and mixed for about
one
minute. Then the electrolyte is added and mixed for about one minute. The
water seat is
then added to the softener premix and mixed for about 20 to about 30 minutes
or until the
composition is clear and homogeneous. Last, the perfume is added and mixed
until the
composition is clear and homogeneous. The composition is allowed to air cool
to
ambient temperature.
Alternatively, for systems where all components are liquids at room
temperature,
the compositions are prepared as follows. The components are added in the
following
order, with thorough mixing after each addition by hand, or with, for example,
a
Lightnin~ 77 mixer for about 2 to about 5 minutes at about 150 rpm: softener
active,
principal solvent, optional phase stabilizer, water, perfume, and electrolyte
(as
concentrated aqueous solution).
Table 1. Efficiency of Alkyl Ethox~rlated Surfactants as Phase Stabilizers
Component Wt% 1 2 3 4 5 6 7 g
TEA Di-ester 30 30 30 30 30 30 30 30
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Quat. '
i
Ethanol from 2.47 2.47 2.47 2.47 2.47 2.47 2.47 2.47
~
softener active
Hexylene Glycol 2.65 2.65 2.65 2.65 2.65 2.65 2.65 2.65
from softener
active
TMPDZ 6 6 6 6 6 6 6 6
Neodol~ 23-12 91-8 25-9 1-7 91-6 45-7 1-5 23-5
Identification3
HLB value 14.6 13.9 13.1 12.9 12:4 11.6 11.2 10.7
of Neodol 3.66 4.18 4.4 4.88 5 5.5 6.87 7.75
required
MgClz 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75
Perfume 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8
Deionized water Bal. Bal. Bal. Bal. Bal. Bal. Bal. Bal.
' Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate where the
acyl group is derived from partially hydrogenated canola fatty acid.
2,2,4-trimethyl-1,3-pentanediol
Alkyl alkoxylated surfactants trademarked by Shell
The efficiency of the alkyl ethoxylated surfactants such as Neodols~
correlates
well with the HLB (Hydrophilic/Lipophilic Balance) value. The higher the HLB
value,
the lower the weight percent of Neodol~ that is necessary for the composition.
Table 2. Fabric Softener Compositions with Various Fabric Softener Levels and
Solvent Systems
1 I 2 I 3 I 4 I 5 I 6 I 7 I 8 I 9
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TEA Di-ester30 35 30 30 30 30 35 30 35
Quat '
Ethanol 2.47 2.88 2.47 2.47 2.47 2.47 2.88 2.47 2.88
(from
active)
Hexylene 2.7 3.1 2.7 2.7 2.7 2.7 3.1 2.7 3.1
Glycol
(from
active)
TMPD 4 5 -- -- 5 5 -- _ __
Hexylene -- -- 6 6 -- __ _
10 -
Glycol
EHD Z __ __ __ __ __ __ __ 6 __
eodol~ 5 6 4 4 6 6 S 5 5
91-8
3
Pluronic'~1 I I __ 1 I 1 I I
L-
35
HCl 0-0.250-0.250-0.250-0.250-0.250-0.250-0.250-0.250-0.25
MgCI 1.75 1.75 2.00 2.00 1.75 1.75 2.20 1.50 1.75
Perfume 2.2 2.5 2.5 2.5 2 2.5 3 2 2
DTPA 5 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Blue Dye 0.00030.00030.00030.00030.00030.00030.00030.00030.0003
DeionizedBal. Bal. Bal. Bal. Bal. Bal. Bal. Bal. Bal.
Water
' Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate where the
acyl group is derived from partially hydrogenated canola fatty acid.
2-Ethyl-1,3-Hexanediol
Ethoxylated alkyl alcohol, trademarked by Shell
polyoxylethylene, polyoxypropylene block copolymer, trademarked by BASF
diethylene triamine pentaacetate
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Table 3 Weight Efficienc~of Various Phase Stabilizers
Component Wt 1 2 3 4 5
%
TEA Di-ester 30 30 30 30 30
Quat.'
Ethanol (from 2.47 2.47 2.47 2.47 2.47
softener active)
Hexylene Glycol 2.65 2.65 2.65 2.65 2.65
(from softener
active)
TMPD 6 6 6 6 --
E~ - __ -_ __ 6
Hexylene Glycol --
Phase StabilizerNeodol Tween~ Ethoquad~Ethomeen Rewopal
91-8 20 C/25 ~ C/25 C6 b
'- 3 " 5
Stabilizer 5 8 5 5 7.8
MgCh 2 1.75 1.75 1.5 1.75
Perfume 1.8 1.8 2.0 2.0 1.8
DTPA '~ 0.01 -- -- -- --
Deionized H,O Bal. Bal. Bal. Bal. Bal.
Table 3 (continued). Weight Efficiency of Various Phase Stabilizers
Component 6 7 8 9 10
Wt%
TEA Di-ester 30 30 30 30 30
Quat. '
Ethanol from 2.47 2.47 2.47 2.47 2.47
softener active
Hexylene Glycol2.65 2.65 2.65 2.65 2.65
from softener
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63
active
TMPD - 2 3 -- --
EHD 6 4 3 -- --
Hexylene glycol 6 6
Phase StabilizerEthoduo-Variquat~Tergitol~Tergitol~Tergitol
meen 66 g 15512 15512 ~ 15599
T/25 9 9
'
Phase Stabilizer4.2 4.47 4.7 4.6 5
Electrolyte MgCI, MgCI, MgCI, MgCl2 gCI,
M
Electrolyte 1.8 1.75 1.75 2.0 2.0
Perfume -- 1.8 1.8 2.5 2.5
DTPA ''- -- -- -- 0.01 0.01
Deionized H,O Bal. Bal. Bal. Bal. Bal.
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Table 3 (continuedl. Weight Efficiency of Various Phase Stabilizers
' Component 11 12 13 14
'~ Wt%
TEA Di-ester 30 30 30 30
Quat. '
Ethanol from 2.47 2.47 2.47 2.47
softener active
Hexylene Glycol2.65 2.65 2.65 2.65
from softener
active
TMPD 3 4 6 6
EHD 3 2 -- --
Hexylene Glycol-' -- -- --
Phase StabilizerIgepal~ Igepal~ Armeen~ Armeen~
CO-530' CO-730' APA 10" APA 10
Phase Stabilizer7 4.3 3 3
Electrolyte MgClz MgCI, MgCl2 Calcium
Xylene
Sulfonate
Electrolyte 1.75 1.75 1.5 2.25
Perfume 1.8 1.8 1.8 1.8
DTPA ''
Deionized H~O Bal. Bal. Bal. Bal.
Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate where the
acyl group is derived from partially hydrogenated canola fatty acid.
Ethoxylated alkyl alcohol, trademarked by Shell
Ethoxylated sorbitan ester, trademarked by ICI Americas
° Ethoxylated alkyl ammonium chloride, trademarked by Akzo Nobel
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Ethoxylated alkyl amine, trademarked by Akzo Nobel
Ethoxylated alkyl amide, trademarked by Witco
' Ethoxylated alkyl aminopropyl amine, trademarked by Akzo Nobel
Ethoxylated monoalkyl ammonium ethylsulfate, trademarked by Witco
Ethoxylated alkyl alcohol, trademarked by Union Carbide
'° Ethoxylated alkyl phenol, trademarked by GAF
" Alkyl amido propyl amine, trademarked by Akzo Nobel
'' Diethylene triamine pentaacetate
Table 4. 30% MDEA auat softener with different solvent systems
Component Wt % 1 2 3 II
MDEA Diester Quat.' 30 30 30
Ethanol (from softener active) 2.47 2.47 2.47
Hexylene Glycol (from softener 2.65 2.65 2.65
active)
TMPD 12 - -
EHD - 12 -
Hexylene Glycol - - 20
Neodol~ 91-8 2 5 6 3
MgCl2 3.56 4 1.75
Perfume 1.8 1.8 1.8
De-ionized Water Bal. Bal. Bal.
Di(acyloxyethyl)dimethyl ammonium chloride where the acyl group is derived
from partially hydrogenated canola fatty acid.
' Ethoxylated alkyl alcohol, trademarked by Shell
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66
Table 5 Fabric Softener Comuositions with Low Solvent Levels and Various
Principal Solvents.
Component Wt% 1 2 3 4 5 6
TEA Di-ester 30 30 45 40 45 30
Quat. '
Ethanol (from 2.47 2.47 3.71 3.29 3.71 2.47
softener
active)
Hexylene Glycol 2.65 2.65 3.97 3.53 3.97 2.65
(from softener
active)
Principal Solvent
TMPD 5 5 - - - 4
1,2-Hexanediol - - 1 - - -
1,2-Pentanediol - - - 1 - -
1,2-Butanediol - - - - 3 -
Phase Stabilizer
Neodol~ 91-8 5 5 - - - 5
z
Rewopal~ C6 3 - - 2.9 2.9 2.9 -
Pluronic~ L35 I 1 0.5 I - 1
4
I MgCh 1.75 - - - - 1.75
CaCl2 - 1.75 1 1 1 -
Perfume 1.8 2.0 I.5 1.5 1.5 2.2
De-ionized WaterBal. Bal. Bal. Bal. Bal. Bal.
' Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate where the
acyl group is derived from partially hydrogenated canola fatty acid.
Ethoxylated alkyl alcohol, trademarked by Shell
' Ethoxylated alkyl amide, trademarked by Witco
polyoxylethylene - polyoxypropylene block copolymer, trademarked by BASF
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Table 6. Fabric Softening Compositions with 45% Fabric Softener Active and
Various Electrolytes and Solvent Systems
Component 1 2 3 4 5
Wt%
TEA Di-ester 45 45 45 45 45 45 45
Quat.'
Ethanol (from 7 3.71 3.71 3.71 3.71 3.71 3.71
active)
Hexylene Glycol-- 3.97 3.97 3.97 3.97 3.97 3.97
(from active)
Pinacol -- 3 __ __ __ __ --
Neopentyl -- -- 3 ~ -- __ -_ __
Glycol
Methyl Lactate-- -- -- 3 -_ _- __
1,5-Hexanediol-- -- __ __ 3 -- --
Isopropanol -- -- __ __ __ 3 -_
Butyl Carbitol-- -- -- -- -- -- 3.1
Rewopal~ C6 3 3 3 3 3 3 3.6
2
Electrolyte KCl KC1 CaClz Methyl K CitrateCaCI, CaCl2
lactate
of Electrolyte1 1 1 3 2 1 1.2
Perfume 1.5 1.5 1.5 1.5 1.5 1.5 2
De-ionized Bal. Bal. Bal. Bal. Bal. Bal. Bal.
Water
' Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate where the
acyl group is derived from partially hydrogenated canola fatty acid.
Ethoxylated alkyl amide, trademarked by Witco
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Table 7. Fabric Softening Compositions with Hexylene Glycol as Principal
Solvent
and Rewopal~ C-6 as Phase Stabilizer.
I Component Wt% 1 2 3 4 5 6 ? 8
TEA Di-ester Quat.' 45 45 45 45 45 45 36 30
Ethanol (from active) 3.7 3.7 3.7 3.7 3.7 -- 3.3 2.5
Hexylene Glycol (from 4 4 4 4 4 3.97-- 2.7
active)
Hexylene Glycol 3 6 9 7.3 3 2.0~6.5 9.0
Rewopal~ C6 2 3.5 2.5 1.5 3.1 2.9 3.0 1.8 3.0
CaCI, 1.1 1.1 0.8 2 1 1 1.2 0.95
Perfume 2.0 2.0 2.0 2.0 1.5 1.5 1.2 1.5
De-ionized Water Bal.Bal. Bal.Bal. Bal. Bal.Bal. Bal.
Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate where the
acyl group is derived from partially hydrogenated canola fatty acid
Ethoxylated alkyl amide, trademarked by Witco
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Table 8. Fabric softener compositions with Hexylene Glycol as Principal
Solvent
and Neodol~ 91-8 as Phase Stabilizer
Component Wt% I 2 3 4 5 6 7
TEA Di-ester Quat.l 28 32 32 30 30 30 30
Ethanol (from active) 2.3 2.6 2.6 2.5 2.5 2.5 2.5
Hexylene Glycol (from 2.5 2.8 2.8 2.7 2.? 2.7 2.7
active)
Hexylene Glycol 3 3.3 6.1 6 6 6 6.3
Neodol~ 91-8 z 3.1 3.0 4.9 4 S 4.6 4.5
MgCI, -- -- -- 2 2 2 1.5
CaCl2 2.1 2 I -- -- __ __
' Perfume 1.0 1.1 3.2 2.2 2.5 2.7 2.5
De-ionized Water Bal.Bal. Bal.Bal. Bal. Bal.Bal.
' Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate where the
acyl group is derived from partially hydrogenated canola fatty acid
Ethoxylated alkyl alcohol, trademarked by Shell
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Table 9. Fabric Softening Compositions with Hexylene Glvcol as Principal
Solvent
and Hvdrotroee
I~I Component Wt% 1 2 3 4 5 6
TEA Di-ester Quat.' 36 30 30 30 30 30
Ethanol (from active) 3.3 2.5 2.5 2.5 2.5 2.5
Hexylene Glycol (from -- 2.7 2.7 2.7 2.7 2.7
active)
Hexylene Glycol 6.5 6 6 6 6 6
Rewopal~ C6 2 1.8 -- -- -- -- --
Neodol~ 91-8 3 -- 5 5 5 5 5
MgCl2 -- -- 1 1.7 1 1
Sodium Cumene Sulfonate1 -- -- -- -- --
Sodium Xylene Sulfonate-- 2 1 1.250.5 1.25
Perfiune 1.2 2.5 2.5 2.5 2.6 2.5
De-ionized Water Bal.Bal. Bal. Bal.Bal. Bal.
'
Di(acyloxyethyl){2-hydroxyethyl)methyl ammonium methyl sulfate where the
acyl group is derived from partially hydrogenated canola fatty acid
Ethoxylated alkyl amide, trademarked by Witco
Ethoxylated alkyl alcohol, trademarked by Shell
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Table i0: Fabric Softener Compositions with Blended Principal Solvent Systems
Component Wt% 1 2 3 4 5 6 7
TEA Di-ester 30 30 30 30 30 30 30
Quat.'
Ethanol (from 2.S 2.S 2.S 2.S 2.S 2..5 2.S
active)
Hexylene Glycol2.7 2.7 2.7 2.7 2.7 2.7 2.7
(from active)
TMPD __ __ __ 3 __ __~ 3
Hexylene GlycolS.S S 4.0 3 S.S 5 3
EHD O.S 1.0 2.0 -- -- __ __
Propylene carbonate-- -- -- -- O.S 1.0 --
Neodol" 91-8 4.0 4.0 4.0 S 4.0 4.0 S.0
'
MgClz 2.0 2.0 2.0 2 2.0 2.0 2.0
DTPA 3 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Perfume 2.0 2.0 2.0 2.S 2.0 2.S 2.S
i
Dye 0.0008 0.00080.0008 0.00080.0008 0.00080.0008
De-ionized WaterBal. Bal. Bal. Bal. Bal. Bal. BaI.
' Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate where the
acyl group is derived from partially hydrogenated canola fatty acid
Ethoxylated alkyl alcohol, trademarked by Shell
diethylene triamine pentaacetate
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Table 11: Fabric Softening Compositions
Component Wt% 1 2 ~ 3 4
TEA Di-ester Quat.'30 30 45 4~
Ethanol (from active)2.5 2.5 3.7 3.7
Hexylene Glycol 2.7 2.7 4.0 4.0
(from active)
Hexylene Glycol 6 6 -- 10
TMPD -- -- 10 --
Neodol~ 91-8 2 4.5 4.5 -- --
Tergitol l S S9 -- -- 2.6 2.6
3
CaCI, - - 0.75 0.75
MgCI, 1.5 1.5 -- --
DTPA 4 _- 0.2 __ __
Ammonium chloride 0.1 0.1 -- --
TPED 5 -- -- 0.2 0.2
Perfume 2.5 2.5 2.5 2.5
De-ionized Water Bal. Bal. Bal. Bal.
' Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate where the
acyl group is derived from partially hydrogenated canola fatty acid
Ethoxylated alkyl alcohol, trademarked by Shell
Ethoxylated alkyl alcohol, trademarked by Union Carbide
Diethylene triamine pentaacetate
tetrakis-(2-hydroxylpropyl) ethylenediamine
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Table 12. Data Demonstrating Lower Fabric Softener Residue in the Dispenser
for
High Eiectrolyte Formula vs Low Electrolyte Formula
Fabric Softener Composition Average Amt. Composition
and + Water Left in Dispenser
Dilution (Average % of Total Composition
Weight ratio of High Electrolyte
Composition to Water + Water Left in Dispenser)
1:1 High Electrolyte/Water 2.32 g (3.9 %)
1:1 Low Electrolyte/ Water 23.08 g (38.5 %)
i :2 High Electrolyte/Water 7.38g (6.2 %)
1:2 Low Electrolyte/ Water 12.52 g ( 10.4 %)
1:S High Electrolyte/Water 1.1 g (0.7 %)
l :S Low Electrolyte/ Water 3.07g (1.7 %)
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Table 13 Data Demonstrating Lower Fabric Staining Incidence for High
Electrolyte Formula vs. Low Electrolyte Formula.
Fabric Softener Composition Average Number of
and Dilution Fabric Stains per Cycle
1: 1 High Electrolyte/Water 1.6
1:1 Low Electrolyte/Water 0.6
1: 2 High Electrolyte/Water 1.2
1: 2 Low Electrolyte/Water 0.2
1: 5 High Electrolyte/Water 1.2
1: 5 Low Electrolyte/Water 0.4
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Table 14. Fabric Softener Compositions with Various Fabric Softener Levels and
Solvent stems
Component 1 2 3 4 5 6 7 8 9
(VVt%)
TEA Di-ester30 35 30 30 30 35 30 35
Quat'
TEA Di-ester 45
Quat2
Ethanol 2.47 2.88 2.47 2.47 2.47 2.88 2.47 2.88
(from active)
Hexylene 2.7 3.1 2.7 2.7 2.7 3.1 2.7 3.1 -
Glycol
(from active)
TMPD 4 5 - 5 5 -. __ __ _
Hexylene -- -- 6 -- -- 10 -- 2 _
Glvcol
EHD' __ __ __ __ __ __ 6 __ _
Isopropylalcohol- - _ _ _ _ - - 5
1-Heptanol _ _ _ - - - - - 1
eodolm 91-8 5 6 4 6 6 5 5 5 5
Pluronicm 1 1 1 1 1 1 I 1 1
L-35 5
HCl 0-0.250-0.250-0.250-0.250-0.25 0-0.25 0-0.250-0.250-0.25
MgCh 1,75 1.75 2.00 1.75 1.75 2.20 1.50 1.75 4.1
Perfume 2.2 2.5 2.5 2 2.5 3 2 2 2
DTPA 6 0.01 U.OI 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Dye 0.00025-.00025-0.00025-0.00025-0.00025-0.00025-0.00025-00025-
.00021-
0.000950.000950.000950.000950.000950.000950.000950.000950.00091
Deionized Bal. Bal. Bal. Bal. Bal. Bal. Bal. Bal. Bal.
Water
' Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate where the
acyl group is derived from partially hydrogenated canola fatty acid.
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' Di(oleoyloxyethyl) (2-hydroxyethyl) methyl ammonium methyl sulfate.
2-Ethyl-1,3-Hexanediol
Ethoxylated alkyl alcohol, trademarked by Shell
polyoxylethylene, polyoxypropylene block copolymer, trademarked by BASF
diethylene triamine pentaacetate
For commercial purposes, the above compositions are introduced into
containers,
specifically bottles, and more specifically clear bottles (although
translucent bottles can
be used), made from polypropylene (although glass, oriented polyethylene,
etc., can be
substituted), the bottle having a light blue tint to compensate for any yellow
color that is
present, or that may develop during storage (although, for short times, and
perfectly clear
products, clear containers with no tint, or other tints, can be used), and
having an
ultraviolet light absorber in the bottle to minimize the effects of
ultraviolet light on the
materials inside, especially the highly unsaturated actives (the absorbers can
also be on
the surface). The overall effect of the clarity and the container being to
demonstrate the
clarity of the compositions, thus assuring the consumer of the quality of the
product. The
clarity and odor of the fabric softener are critical to acceptance, especially
when higher
levels of the fabric softener are present.
