Note: Descriptions are shown in the official language in which they were submitted.
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AQUEOUS FABRIC SOFTENER COMPOSITIONS CONTAINING HIGHLY UNSATURATED ACTIVE
AND CHELANT
TECHNICAL FIELD
The present invention relates to fabric softener compositions, including clear
or
translucent fabric softener compositions that contain highly unsaturated
fabric softener
compounds.
BACKGROUND OF THE INVENTION
Concentrated clear compositions containing ester and/or amide linked fabric
softening actives 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, Gosselink, 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.
The long term use of fabric softeners containing highly unsaturated chains,
particularly when tri-polyunsaturated chains are present (especially when the
tripolyunsaturate is present at levels above about 1.5%, can cause low levels
of loss of
whiteness and/or discoloration, e.g., yellowing, to occur. This long term
effect was
highly surprising and unanticipated.
SUMMARY OF THE INVENTION
The 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
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about 65%, by weight of the composition, of fabric softener active, preferably
having a
phase transition temperature of less than about 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 0°C, more preferably biodegradable fabric softener actives as
disclosed hereinafter,
having an Iodine Value (IV) of at least about 40, the level of
polyunsaturation preferably
being at least about 2%, with the level of C 18:3 acyl groups in the starting
fatty acyl
source feedstock for making the said compounds preferably being less than
about 1 % by
weight;
B Whiteness Preservative
from at least about 0.01%, preferably at least about 0.05%, more preferably at
least about
0.10%, even more preferably about 0.5%, and most preferably at least about
0.75% and
less than about 10%, preferably less than about 5.0% and more preferably less
than about
1.0% by weight of a metal chelating agent, preferably a fabric substantive
metal chelating
agent, more preferably a fabric substantive metal chelating agent with amine
functionality, and most preferably a fabric substantive metal chelating agent
with tertiary
amine functionality. A highly preferred, but nonlimiting example is tetrakis-
(2-
hydroxylpropyl) ethylenediamine (TPED).
C. optionally, but highly preferred for clear/translucent compositions, 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
8% by
weight of the composition;
D optionally, but preferably, from about 0.1 % 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;
E optionally, but preferably, from 0% to about 15%, 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,
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and even more preferably from about 11 to about 15, and more preferably as
described
hereinafter;
F. optionally, but preferably auxiliary whiteness preservative ingredient
chosen from
the group below:
1) from at least about 0.005%, preferably at least about 0.01%, more
preferably at least
about 0.05%, even more preferably at least about 0.1%, still more preferably
at least
about 0.17% and less than about S%, preferably less than about 3%, more
preferably less
than about 2% and most preferably less than about 1 % of an agent known as an
optical
brightening agent (brightener); 2) Bluing agents are typically included at
levels of at least
about 0.0005%, more preferably at 0.001% even more preferably at 0.005% and
most
preferably at least about 0.01% and less than about 10%, preferably less than
about 5%,
and more preferably less than about 1% by weight of the composition.; 3) UV
absorbers
are included at levels of at least about 0.005% preferably at least about
0.05% and less
than about 10%, preferably less than about 5% by weight of the composition;4)
Oxidative
stabilizers, which includes antioxidants and reductive agents, can be 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; and S) combinations of the above; and
G. the balance water, minor ingredients and/or water soluble solvents.
The compositions, especially the clear, or translucent liquid fabric softener
compositions can optionally also contain:
(a) preferably, from 0.001% 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 extender;
(c) cationic charge booster;
(d) other optional ingredients such as brighteners, chemical stabilizers, soil
release agents, bactericides, chelating agents, silicones; 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
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from about 40% to about 60%, water. These products (compositions) are usually
not
translucent or clear without principal solvent.
The preferred principal solvent and/or electrolyte levels, as well as the
identity of
the principal solvent, are selected normally according to the level and
identity of the
softener. Preferred levels and identity of principal solvent, electrolyte, and
phase
stabilizer which will yield clear stable compositions are taught in copending
U.S. Patent
Application Serial No. 09/309,128, incorporated herein by reference.
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 1% to 80% by weight, preferably from 5% to
75%,
more preferably from 15% to 70%, and even more preferably from 19% to 65%, by
weight of the composition. The fabric softener compound preferably has a phase
transition temperature of less than about 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 0°C,
and preferably is biodegradable as disclosed hereinafter. The IV is from about
40 to
about 140, preferably from about 50 to about 120 and even more preferably from
about
85 to about 105. It 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.
Preferred Diester Quaternary Ammonium Fabric Softening Active Compound (DEQA)
(1) The first type of DEQA preferably comprises, as the principal active,
[DEQA
(1)) compounds of the formula
{R4_m - N+ - [(~H2)n - Y ' R1 ~m~ X-
wherein each R substituent is either hydrogen, a short chain C1-C6, preferably
C1-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
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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 R1, plus one
when Y is
-O-(O)C- or -NR-C(O) -, is C 12-C22, preferably C 14-C20, with each R1 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 R1 group is based upon taking a percentage of the total
active based
upon the percentage that the given R1 group is, of the total R1 groups
present.);
(2) A second type of DEQA active [DEQA (2)] has the general formula:
[R3N+CH2CH(YR1)(CH2YR1)] X_
wherein each Y, R, R1, and X- have the same meanings as before. Such compounds
include those having the formula:
[CH3]3 N(+)[CH2CH(CH20(O)CR1)O(O)CR1] C1(-)
wherein each R is a methyl or ethyl group and preferably each R1 is in the
range of C 15
to C 19. 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 FA1
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
8% to about 70%, more preferably from about 13% to about 65%, and even more
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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 C 1 _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 C18:1
component) is at least
about 1:1, 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-pentanediol 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
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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
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 - < I; 1,3,5-trioxane - 5; 2,2'-
ethylidenebis(oxy)-
bispropane - < 1; C6 methyl ester - < I; C$ Methyl ester - < I; and Coo Methyl
ester - < 1.
odorant
The acceptable level of each odorant is as follows: isopropyl acetate should
be
less than about 5, preferably less than about 3, and more preferably less than
about 2,
nanograms per liter (rlg/L.); 2,2'-ethylidenebis(oxy)bis-propane should be
less than about
200, preferably less than about I00, more preferably less than about I0, and
even more
preferably less than about S, nanograms per liter (~g/L.); 1,3,5-trioxane
should be less
than about S0, preferably less than about 20, more preferably less than about
10, and even
more preferably less than about 7, nanograms per liter (rlg/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_I2, 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 the triethanolamine reactant 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
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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.
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
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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.
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
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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:
Fatty Act GroupFA1 FA2 FA3
C 14 0 0 1
C~6 3 11 25
C~8 3 4 20
C14:1 0 0 0
C16:1 1 1 0
C18:1 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 57 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.
Preferred 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
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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
"percent of softener active" containing a given R1 group is the same as the
percentage of
that same R1 group is to the total R1 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.
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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 R1 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 rriethyl
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 no/low
detergent
carry-over laundry conditions the percentage of monoester should be as low as
possible,
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/monoester 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 2.8:1.
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(CHZCHZOH)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
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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%, more
preferably
below about 10%, and even more preferably below about 5%, by weight of the
softener
acrive.
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.
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
13
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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.
3) Polyquaternary ammonium compounds.
The following polyquaternary ammonium compounds are disclosed by reference
herein
as suitable for use in this invention:
European Patent Application EP 0,803,498, A1, Robert O. Keys and Floyd E.
Friedli, filed April 25, 1997; British Pat. 808,265, issued Jan. 28, 1956 to
Arnold
Hoffman & Co., Incorporated; British Pat. 1,161,552, Koebner and Potts, issued
Aug. 13,
1969; DE 4,203,489 Al, Henkel, published Aug. 12, 1993; EP 0,221,855, Topfl,
Heinz,
and Jorg, issued Nov. 3, 1986; EP 0,503,155, Rewo, issued Dec. 20, 1991; EP
0,507,003,
Rewo, issued Dec. 20, 1991; EPA 0,803,498, published October 29, 1997; French
Pat.
2,523,606, Marie-Helene Fraikin, Alan Dillarstone, and Marc Couterau, filed
Mar. 22,
1983; Japanese Pat. 84-273918, Terumi Kawai and Hiroshi Kitamura, 1986;
Japanese Pat.
2-011,545, issued to Kao Corp., Jan. 16, 1990; U.S. Pat. 3,079,436, Hwa,
issued Feb. 26,
1963; U.S. Pat. 4,418,054, Green et al., issued Nov. 29, 1983; U.S. Pat.
4,721,512, Topfl,
14
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WO 01/34743 PCT/US00/30232
Abel, and Binz, issued Jan. 26, 1988; U.S. Pat. 4,728,337, Abel, Topfl, and
Riehen,
issued Mar. 1, 1988; U.S. Pat. 4,906,413, Topfl and Binz, issued Mar. 6, 1990;
U.S. Pat.
5,194,667, Oxenrider et al., issued Mar. 16, 1993; U.S. Pat. 5,235,082, Hill
and Snow,
issued Aug. 10, 1993; U.S. Pat. 5,670,472, Keys, issued Sep. 23, 1997; Weirong
Miao,
Wei Hou, Lie Chen, and Zongshi Li, Studies on Multifunctional Finishing
Agents,
Riyong Huaxue Gonye, No. 2, pp. 8-10, 1992; Yokagaku, Vol. 41, No. 4 (1992);
and
Disinfection, Sterilization, and Preservation, 4'h Edition, published 1991 by
Lea &
Febiger, Chapter 13, pp. 226-30. All of these references are incorporated
herein, in their
entirety, by reference. The products formed by quaternization of reaction
products of
fatty acid with N,N,N',N', tetraakis(hydroxyethyl)-1,6-diaminohexane are also
disclosed
as suitable for this invention. Some nonlimiting structural examples produced
by this
reaction are given below:
0
OH OH
o~R
O
O + ~ R Ow./~ I ~N~OH
R O~NjW~ O R R O~N~ I ~O R O N I
I O 2 (CH30y~SOi 2 (CHaOIzSOz
O 2(CH~OhSOz R O R' _O
R"O ~O
O
O
OH OH OH
O
II
R O I R O I' HOfN/~/ ~N~OH
~ f p~R ./~N I W./~OH I
~
N I y SO
O '0I 2 (CH
Oy
z
2 (CH30)ySOi 2 (CH~O)zSOyOH ~
~
OH OH
O OH OH
O" R
O O
I fl
R N R ~R
O ~ O~ ~
~
+ ~ ~N~ ~O N O
R O~N~ NfO R ~ R ~ I
O O (CH
O)
SO
,
(CH~O~SOy' Z
i
O (CH,O)xSOiR O Ru
II
R O O
O
OH OH
OH
O
R N~OH R ~O~N~ I~OH R ~ O R
O~N~ O~NjW
~ O
IOI SO O~S02 O
CH (CH H
0) O
SO
i R ~ ~
( )2
3 Z
z (
R OH
O O
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OH OH OH
R O~N ~N~OH R~~N~ I~OH HO~N~ N~OH
O O
' SOp
(CH
Oy
(CH~OhSOz (CH~OhSOp ~
~
OH
O
~ OH OH
O" R
O
O~ N~ R O~N ~N~OH
~ R
R
R~O~N~ N~O R N O O
~
OO ~
1O1 ~ O R
R O
R O II II
O
O
O
OH OH OH
O
R O~ ~ O R R ~N ~N~OH HO~N~ N~OH
N O
O
OH
and R is defined as R' as described above.
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(+) - Rlm~ A_
wherein each m is 2 or 3, each R1 is a C6-C22, preferably C14-C20, but no more
than
one being less than about C 12 and then the other is at least about 16,
hydrocarbyl, or
substituted hydrocarbyl substituent, preferably C 10-C20 alkyl or alkenyl
(unsaturated
alkyl, including polyunsaturated alkyl, also referred to sometimes as
"alkylene"), most
preferably C 12-C 1 g alkyl or alkenyl, and where the Iodine Value
(hereinafter referred to
as "IV") of a fatty acid containing this Rl 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
16
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WO 01/34743 PCT/US00/30232
containing the same R1 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 C14-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
C1-6
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 C- l
Rl C A _
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-CH2
Rl-
4 N-CH2
Rl-C-G-R
wherein R1, R2 and G are defined as above;
(4) reaction products of substantially unsaturated and/or branched chain
higher fatty acids with dialkylenetriamines in, e.g., a molecular ratio of
about 2:1, said
reaction products containing compounds of the formula:
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WO 01/34743 PCT/US00/30232
R1-C(O~NH-R2 NH-R3 NH--C(O)-R1
wherein R1, R2 are defined as above, and each R3 is a C1-6 alkylene group,
preferably an
ethylene group;
(5) softener having the formula:
[R1--C(O~NR-R~N(R)z-R3 NR---C(O~R1]+ A-
wherein R, R1, R2, 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)-R1
wherein R1, R2 and R3 are defined as above;
(7) softener having the formula:
R R
\N-R2-N
N N 2A~
Ri Ri
wherein R, R1, R2, and A- are defined as above; and
15 (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:
20 [R1 N(RS)2-R6]+ A
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WO 01/34743 PCT/US00/30232
wherein RS 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:
O
N-CH2
Rm~ I 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
N-CH2
RL-~ I AO
N-CH2
HO-R2 ~ ERs
wherein RS is a C1-C4 alkyl or hydroxyalkyl group, and R1, R2, and A- are as
defined
above;
(11) alkylpyridinium salts having the formula:
O+
R4-N ~ . AO
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 ~ AO
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WO 01/34743 PCT/US00/30232
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
hydrocarbon group derived from a natural source; soyadimethylethylammonium
ethylsulfate wherein R1 is a C 16-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 R1 is a Clg 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; 4,161,604, 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,
CA 02387385 2002-04-11
WO 01/34743 PCT/US00/30232
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 R1 is an acyclic aliphatic C15-C17 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~
3 690.
An example of Compound (3) is 1-oleylamidoethyl-2-oleylimidazoline wherein R1
is an acyclic aliphatic C15-C17 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.
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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
Ri Ri
10 wherein R1 is derived from oleic acid, and the compound is available from
Witco
Company.
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.
15 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,
20 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.
It will be understood that all combinations of softener structures disclosed
above
are suitable for use in this invention.
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WO 01/34743 PCT/US00/30232
B. Whiteness Preservative
Suprisingly, it was found that over time and especially in cases where clothes
are
exposed to excessive heat (e.g. as in extensive drying or drying in commercial
dryers)
and/or confined to an enclosed space after treating, an undesirable yellowish
cast begins
to be apparent on white items. This yellowing will be perceived as a negative
by
consumers. Not to be bound by theory, but the yellowing is believed to be
caused by the
auto-oxidation of unsaturated materials in the composition, particularly
polyunsaturated
materials which are known to catalyze auto-oxidation. Under some conditions
some level
of polyunsaturate is desirable in the composition, since the raw material is
cheaper and
easier to produce if the supplier is not constrained to minimizing or
eliminating
polyunsaturate. Some level of polyunsaturate is also desirable for preserving
the clarity
of the composition, especially when the composition is exposed to low
temperatures
(40°F or below). Therefore, it is not acceptable in all cases to
eliminate the yellowing
problem by simply removing all polyunsaturated softener compositions. Attempts
to
eliminate polyunsaturated fatty acyl groups and specifically, the C18:3
species can reduce
the overall cis/trans isomer ratio , resulting in poorer clarity at lower
temperatures, i.e.,
40°F or lower. Instead, it is surprisingly found that the yellowing can
be significantly
mitigated without removing polyunsaturated softeners by introducing materials
that
control the auto-oxidation reaction and/or, optionally, optically mask the
yellow cast.
Metal Chelatin~ Agent.
Metals present in fabrics, products, water supply or arriving from other
sources,
especially transition metals and particularly copper and iron, can act to
catalyze auto-
oxidation of unsaturated materials, which can produce colored compounds.
Therefore,
metal chelating agents, that are preferably fabric substantive are added to
the composition
to control and reduce, or eliminate, catalysis of auto-oxidation reactions by
metals.
Preferred metal chelating agents contain amine and especially tertiary amine
moieties
since these tend to be fabric substantive and very effectively chelate copper
and iron as
well as other metals. Aldehydes are produced by the auto-oxidation reactions,
these are
easily oxidized, and are believed to propagate the auto-oxidation reactions.
Therefore
amine-based metal chelating agents, and especially tertiary amine moieties,
are also
preferred since these react with aldehydes to terminate the auto-oxidation
reactions. Low
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WO 01/34743 PCT/US00/30232
molecular weight amine-based oligomers and/or polymers are also useful in
modifying
visco-elastic properties of formulations herein. Formulations tend to get hung-
up in
plastic containers such as the product bottle or the machine dispensers or
machine-
independent dosing devices such as the Downy° Ball. Adding a small
amount of low
molecular weight amine-based chelator, especially, tetrakis-(2-hydroxylpropyl)
ethylenediamine (TPED), improves flow of the product out of these vessels,
thus
improving the performance and use experience.
The product contains at least about 0.01%, preferably at least about 0.05%,
more
preferably at least about 0.10% even more preferably about 0.5%, and most
preferably at
least about 0.75% and less than about 10%, preferably less than about 5.0% and
more
preferably less than about 1.0% by weight of a metal chelating agent. Levels
below 1.0%
are especially preferred in this formulation, since higher levels of metal
chelating agents
lead to instability in the formulation. Metal chelating agents may also be
added at any
point during the process of making fabric softener raw materials where
polyunsaturated
moieties would be present e.g. these could be added into oils used to make
fatty acids,
during fatty acid making and/or storage during fabric softener active making
and/or
storage.
The structural description of a preferred amine-based metal chelating compound
for use in this composition is given below:
(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;
arylalkyl; hydroxyalkyl; polyhydroxyalkyl; polyalkylether having the formula -
((CH2)y0)zR7 where R7 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)zR7; the
group -C(O)Rg where Rg is alkyl; alkaryl; arylalkyl; hydroxyalkyl;
polyhydroxyalkyl and
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CA 02387385 2002-04-11
WO 01/34743 PCT/US00/30232
polyalkyether as defined in R1, R2, R3, and R4; (CX2)"N(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;
arylalkyl; 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 5 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).
Other suitable 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 chelating
agents disclosed in said U. S. Pat. No. 5,759,990 at column 26, line 29
through column
27, line 38 are suitable.
A suitable amine-based metal chelator, EDDS, 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 form):
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 S, preferably at
least about 7.
Typically, the chelators will comprise from about 0.05% to about 10%, more
preferably
from about 0.75% to about 5%, by weight of the compositions herein, in
addition to those
CA 02387385 2002-04-11
WO 01/34743 PCT/US00/30232
that are stabilizers. Preferred chelators include DETMP, DETPA, NTA, EDDS, and
EDTA.
Mixtures of metal chelating agents are acceptable for use herein.
C. OPTIONAL PRINCIPAL SOLVENT SYSTEM
The principal solvent, when present, 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 in Serial No. Case
7258 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 disclosed therein 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. Okamoto, and D. L. Duval, 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 1 S% 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
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. 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.
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CA 02387385 2002-04-11
WO 01/34743 PCT/US00/30232
Principal solvents are efficient in that they provide 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
coefficient (P). Octanol/water partition coefficient of a solvent is the ratio
between its
equilibrium concentration in octanol and in water. The partition coefficients
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, 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,
27
CA 02387385 2002-04-11
WO 01/34743 PCT/US00/30232
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. Inf. Comput. Sci., 29, 163 (1989); and Broto's
method as
disclosed in Eur. J. Med. Chem. - Chim. Theor., 19, 71 (1984).
The principal solvents are typically selected from those having a ClogP 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; mono-ols;
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
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
28
CA 02387385 2002-04-11
WO 01/34743 PCT/US00/30232
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 sufficient 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 ClogP 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
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CA 02387385 2002-04-11
WO 01/34743 PCT/US00/30232
long as the ClogP value of the new solvent remains within the effective range.
The
following are some illustrative examples:
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.
D OPTIONAL, BUT HIGHLY PREFERRED, ELECTROLYTE
The compositions of this invention can contain a low or a relatively high
level of
electrolyte, e.g., from 0% up, normally 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 in a clear/translucent
formulation
provides benefits such as (a) it lowers the amount of principal solvent having
a ClogP of
from about 0.15 to about 0.64 or l, which is required to provide clarity (It
can even
eliminate the need for such a principal solvent completely.); (b) it modifies
the
viscosity/elasticity profile on dilution, to provide lower viscosity and/or
elasticity; and (c)
it 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 in clear formulations 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 of from
about -2.0 to about 2.6, preferably from about -1.7 to about 1.6, and more
preferably from
about -1.0 to about 1Ø The principal solvents are also more effective with
the high
electrolyte level, thus allowing one to use less of such principal solvents.
CA 02387385 2002-04-11
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Electrolytes significantly modify the microstructures and/or alter the phases
that
the products dilute through compared to products with no or lowered 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
rheological ,
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 (i.e. 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" 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 rheological parameters as well as well as
guidance for
choosing instrumentation and making rheological measurements is available in
the article
on Rheology Measurements in the Kirk Othmer Encyclopedia of Chemical
Technolo~y
3rd 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.
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There is a problem that appears when some clear formulas are diluted.
Principal
solvents, in general, promote 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 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' <_ about 3 Pa
and G" <_
about 2 Pa sec; even more preferred G' <_ about 1 Pa G" _< about 1 Pa.
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 solvent/softener 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
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WO 01/34743 PCT/US00/30232
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
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 cation 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 73.8°C; and magnesium
chloride - about 69.8°C.
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Potassium acetate provides a cloud point of about 69.8°C, thus placing
the acetate anion
somewhere between the chloride and sulfate anions.
Inorganic salts suitable for reducing dilution viscosity include MgIz, MgBrz,
MgClz, Mg(N03)z, Mg3(P04)z, MgzP20~, MgS04, magnesium silicate, NaI, NaBr,
NaCI,
NaF, Na3(P04), NaS03, NazS04, NazS03, NaN03, NaI03, Na3(P04), Na4P207, sodium
silicate, sodium metasilicate, sodium tetrachloroaluminate, sodium
tripolyphosphate
(STPP), NazSi307, sodium zirconate, CaFz, CaClz, CaBrz, CaIz, CaS04, Ca(N03)z,
Ca,
KI, KBr, KCI, KF, KN03, KI03, KzS04, KZS03, K3(P04), K4(PzO~), potassium
pyrosulfate, potassium pyrosulfite, LiI, Liar, LiCI, LiF, LiN03, A1F3, A1C13,
AlBr3, AlI3,
Alz(S04)3, Al(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)z 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
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 cations 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
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WO 01/34743 PCT/US00/30232
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.
E. OPTIONAL 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 perfumes, 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
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.
CA 02387385 2002-04-11
WO 01/34743 PCT/US00/30232
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 5 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)]rn CH20(RZO)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 <_ 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)n and/or -[CH(CH3)CHZ]-; 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:
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WO 01/34743 PCT/US00/30232
R5 . ... R5
Rs Y" R5
R' R5
R5 \R5
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
(ORZ)Z~-C(O) Rl, x and R~ are as defined above and 5 <_ z, z', and z" <_ 20,
more
preferably S <_ z + z' + z" <_ 20, and most preferably, the heterocyclic ring
is a five
member ring with Y" = O, one RS is -H, two RS are -O-(RZO)z-H, and at least
one R5 is
the following structure -CH(CHZ-(OR2)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(R1 ) - Z
wherein: each R1 is H, Cl-C4 hydrocarbyl, Cl-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)
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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 S 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-111 and N-150 from Union Carbide, Dowfax~ 9N5 from Dow and
Lutensol~
AP9 and AP 14, from BASF.
(2)- Alkyl or alkyl-aryl amine or amine oxide nonionic alkoxylated 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, amide 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 1 S
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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.
Preferably, the compounds of the alkyl or alkyl-aryl alkoxylated surfactants
and
alkyl or alkyl-aryl amine, amide, and amine-oxide alkoxylated have the
following general
formula:
R~"' - Y - [(RZ-O)Z - HJP
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 RZ is selected
from the
following groups or combinations of the following groups: -(CHZ)"- and/or -
[CH(CH3)CHZJ-; wherein about 1 < n <_ about 3; Y is selected from the
following groups:
-O-; -N(A)q-; -C(O)O-; - (O~)N(A)q-; -B-R3-O-; -B-R3-N(A)q-; -B-R3-C(O)O-; -B-
R3-
N(-~O)(A)-; and mixtures thereof; wherein A is selected from the following
groups: H;
R~; -(RZ-O)Z H; -(CHZ)XCH3; phenyl, or substituted aryl, wherein 0 5 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: RZ;
phenyl; or substituted aryl. The terminal hydrogen in each alkoxy chain can be
replaced
by a short chain C,_4 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.
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Preferred structures are those in which m = 1, p = 1 or 2, and 5 <_ 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 =
1, p = 1 or 2,
and 9 <_ z <_ 12. The preferred y is 0.
(3)- AIkoxKlated and non-alkox~ated nonionic surfactants with bulky head
~rouns
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
S0,
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(~)-Y'-U(RS)~m-CH2~(Rz~)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: -
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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(RZO)Z H ; and m is from about 2 to about 4;
Another useful general formula for this class of surfactants is
R5 . ... R5
R5 Y" R5
R' R5
R5 \R5
R°
wherein Y" = N or O; and each RS is selected independently from the following:
-H, -OH, -(CHZ)xCH3, -(OR2)Z H, -ORS, - OC(O)R~, and -CHZ(CHZ-(ORZ)Z~~-H)-CH2-
(ORZ)Z~-C(O) R'. With x R~, and RZas 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-(R20)Z
H, and at least one RS has the following structure -CH(CHZ-(ORz)Z»-H)-CHz-
(ORZ)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~) - W
wherein: each R~ is H, C1-C4 hydrocarbyl, CI-C4 alkoxyalkyl, or hydroxyalkyl,
e.g., 2-
hydroxyethyl, 2-hydroxypropyl, etc., preferably C I-C4 alkyl, more preferably
C I or C2
alkyl, most preferably C1 alkyl (i.e., methyl) or methoxyalkyl; and R6 is a CS-
C31
hydrocarbyl moiety, preferably straight chain C~-C 1 g alkyl or alkenyl, more
preferably
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straight chain Cg-C 1 ~ alkyl or alkenyl, most preferably straight chain C 11-
C 1 ~ alkyl or
alkenyl, or mixture thereof; and W 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. W
preferably
will be derived from a reducing sugar in a reductive amination reaction; more
preferably
W is a glycityl moiety. W 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)4-CH20.
Mixtures of
the above W moieties are desirable.
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.
W can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl,
1-
deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
(4)- Alkoxylated cationic~uaternary 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 5 about 50 alkylene oxide
moieties. The
amine hydrocarbons for use herein have from about 6 to about 22 carbon atoms,
and are
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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:
fR~n' - Y - ~(RZ-O)Z - H~p~+ X
wherein R~ and RZ are as defined previously in section D above;
Y is selected from the following groups: = N+-(A)q; -(CH2)"-N+-(A)q; -B-(CHz)"-
N+-(A)2; -(phenyl)-N+-(A)q; -(B-phenyl)-N+-(A)q; with n being from about 1 to
about 4.
Each A is independently selected from the following groups: H; R'; -(R20)Z H; -
(CHZ)xCH3; phenyl, and substituted aryl; where 0 <_ x <_ about 3; and B is
selected from
the following groups: -O-; -NA-; -NAZ; -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 = f or 2, and about 7 <_ z
<_ about 20,
and most preferred are structures in which m = 1, p = 1 or 2, and about 9 <_ 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
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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
Armeeri APA-10 and calcium xylene sulfonate, Armeen APA-10 and magnesium
chloride, lauryl carboxylate and triethanol 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~-Yz
wherein R' is as hereinbefore from section D above and Yz can be chosen from
the following structures: -N(A)z; -C(O)N(A)z; -(Of-)N(A)z; -B-R3-N(A)z; -B-R3-
C(O)N(A)z; -B-R3-N(~O)(A)z; -COZ ; -S03-z; -OS03-z; -O(RZO)XCOz-; -O(R20)XS03-
z;
and -O(RZO)XOS03-z; 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 Yzare as hereinbefore and R4 can be chosen from the
following: -(CHz)yCH3; -(CHz)y-phenyl or -(CHz)y substituted phenyl with 0 <_
y _< 6
(6)- Block copolymers obtained by copolymerization of ethylene oxide and
nropylene
oxide
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Suitable polymers include a copolymer having blocks of terephthalate and
polyethylene oxide. More specifically, these polymers are comprised_of
repeating units
of ethylene and/or 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-L~-C(~)-R1-C(~)-~-R2)a-U-C(~)-R1-C(~)-~)-(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 S0, 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.
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
R1 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
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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 R1 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 R1 moieties consist entirely of (i.e., comprise 100%) 1,4-
phenylene
moieties, i.e., each R1 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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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 30°C to about 100°C, 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.
(7)- Alkyl amide alkoxvlated nonionic surfactants
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Suitable surfactants have the formula:
R - C(O) - N(R4)n - [(R~O)X(R20)YR3]rn
wherein R is C~_z, linear alkyl, C~_Z, branched alkyl, C~_2~ linear alkenyl,
C7_2~
branched alkenyl, and mixtures thereof. Preferably R is Cg_,g linear alkyl or
alkenyl.
R' is -CH2-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 -CHz-CHZ- 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-CHZ- units.
R3 is hydrogen, C,-Cg 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 1, provided that m + n equals 2;
preferably m is equal to 1 and n is equal to 1, resulting in one -
[(R~O)X(R20)yR3] unit and
R4 being present on the nitrogen. The index x is from 0 to about 50,
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 surfactants 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
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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
thereof. The various stabilizers have different advantages. For example,
alkoxylated
cationic materials or cationic surfactant complexes improve softness and
provide
enhanced wrinkle release benefits.
Fabric softener compositions with highly preferred dilution and dispensing
behaviors can be identified as disclosed hereinbefore.
F. OPTIONAL AUXILIARY WHITENESS PRESERVATIVES
Auxiliary whiteness preservatives are optionally, but preferably
incorporated..
Using auxiliary whiteness preservatives together with the metal chelant gives
an extra
boost to whiteness maintenance when the metal chelants are used at their most
preferred
levels below 1%. Better formula stability is achieved while maintaining
desired levels of
softness when an auxiliary whiteness preservative is used together with a
metal chelant.
1. Bri~hteners
Optical brighteners also known as fluorescent whitening agents (FWAs) or
fluorescent brighteners preserve whiteness by compensating for the yellow
appearance by
adding a complementary color to the fabric and thus the undesired yellowing is
rendered
invisible. Not to be bound by theory, but auto-oxidation of the
polyunsaturated softener
compounds generates compounds that appear yellow on white fabrics because
these
compounds absorb short-wavelength light, light in the range of violet to blue
or
wavelengths between about 370 nm to 550 nm. Optical brighteners replace this
missing
part of the spectrum and so a white appearance is retained. Optical
brighteners absorb
light shorter wavelength ultraviolet light and emit light via fluorescence in
the blue to
blue violet range of the spectrum.
The product contains from at least about 0.005%, preferably at least about
0.01%,
more preferably at least about 0.05%, even more preferably at least about
0.1%, still more
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preferably at least about 0.17% and less than about 5%, preferably less than
about 3%,
more preferably less than about 2% and most preferably less than about 1 % of
an agent
know as an optical brightening agent (brightener). Lower levels of brightener
are used in
the presence of the metal chelating compound. In the absence of the metal
chelating
compound, higher levels of brightener are preferred.
Preferred optical brighteners are colorless on the substrate and do not absorb
in
the visible part of the spectrum. Preferred optical brighteners are also
lightfast, meaning
that these do not degrade substantially in sunlight. Optical brighteners
suitable for use in
this invention absorb light in the ultraviolet portion of the spectrum between
275 nm and
about 400 nm and emit light in the violet to violet-blue range of the spectrum
from about
400 nm to about 550 nm. Preferably, the optical brightener will contain an
uninterrupted
chain of conjugated double bounds. Optical brighteners are typically, but not
limited to,
derivatives of stilbene or 4,4'-diaminostilbene, biphenyl, five-membered
heterocycles
such as triazoles, oxazoles, imidiazoles, etc., or six-membered heterocycles
(coumarins,
naphthalamide, s-triazine, etc.). Many specific brightener structures are
described in The
Kirk-Othmer Encyclopedia of Chemistry 3rd Ed., pp 214-226 and in references
therein U.
S. Pat. No. 5,759,990 at column 21, lines 15-60; said references being
incorporated herein
by reference as suitable for use in this invention. Ionic brighteners with a
positive or
negative charge are preferred as this improves solubility in the compositions
disclosed
herein and thus are easier to formulate and are more stable. Cationic
brighteners are also
preferred since these can compete effectively with cationic fabric softeners
to partition to
the surface of the fabric.
Some preferred, but nonlimiting brighteners are Optiblanc GL and Optiblanc~
LSN
from 3V Inc., Weehawken, New Jersey, Tinopals CBS SP Slurry 33, PLC, UNPA-GX,
4BM, 4BMS, SBM, SBMS, SBM-GX, AMS-GX, DMS-X, DCS Liquid, K, ERN, LCS,
LFW, and TAS, UniveX , SK, ERN, and AT, from Ciba, High Point, North Carolina,
Blankophor~ FBW, FB, LPG , and HRS, from Mobay. In addition to preventing auto-
oxidation, some brighteners also prevent dye transfer.
2. Bluing Agents
Bluing agents also act to preserve whiteness by compensating for the yellow
appearance by again adding a complementary color to the fabric and thus the
undesired
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yellowing is no longer noticeable. Like optical brighteners, bluing agents
replace this
missing part of the spectrum and so a white appearance is retained. Typically,
the water
soluble blue dyes that are used as bluing agents are anionic and associate
with cationic
softener actives and thereby deposit on fabric along with the softener
active(s). Typically
the bluing agents are included at levels of at least about 0.0005%, more
preferably at
0.001% even more preferably at 0.005% and most preferably at least about 0.01%
and
less than about 10%, preferably less than about 5%, and more preferably less
than about
1% by weight of the composition. Examples are Polar Brilliant Blue (Acid Blue
127:1),
Liquitint Patent Blue, and Liquitint Blue 65, all from Milliken & Company and
Acid Blue
80 from the Hilton-Davis Co., Cincinnati, Ohio. Oil soluble blue dyes and
pigments can
also be used.
3. UV Absorbers.
Not to be bound by theory, but UV absorbers can operate by protecting the
fabric and any
fabric softener compound deposited on the fabric from UV exposure. UV light is
know to
initiate auto-oxidation processes and suprisingly, UV absorbers can be
deposited on
fabric in such a way that UV light is blocked from the fabric and fabric plus
composition
thus preventing the initiation of auto-oxidation.
Preferably the UV absorber compound absorbs light at a wavelength of from
about
315nm to about 400nm and is a preferably solid having a melting point of from
about
25 C to about 75 C, more preferably from about 25 C to about 50 C. UV
absorbers
are included at levels of at least about 0.005% preferably at least about
0.05% and less
than about 10%, preferably less than about 5% by weight of the composition.
Preferably these UV absorber compounds contain at least one chromophore
selected from the group consisting o~
I)
Phenylbenzotriazole
(II)
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H
\ ~
2-Hydroxybenzophenone
(III)
0
c,cHz
i U
Dibenzoylmethane
(IV)
Phenylbenzimidazole
(V)
~N / \ ~-OH
R
Esters of P-Aminobenzoic Acid (PABA)
(VI)
g
OOH
Esters of Cinnamic Acid
(VII)
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/ ~~~~OH
\ ~ ICN
Esters of 2-Cyano-3, 3-diphenyl-2-Propenoic Acid
(VIII)
OH
O
I I
C-OH
Esters of Salicylic Acid
and
(IX)
mixtures thereof;
wherein each R is a hydrogen, methyl, ethyl, C I to C22 branched or straight
chain alkyl
group and mixtures thereof, preferably a methyl group; and wherein the
compound
containing the chromophore is a non-fabric staining, light stable compound
containing
preferably at least one Cg-C22 hydrocarbon fatty organic moiety; wherein the
chromophore absorbs light at a wavelength of from about 290nm to about 450nm;
wherein the compound is a solid having a melting point of from about 25 C to
about
90 C or, optionally, a viscous liquid at a temperature of less than about 40
C.
Preferably the UV absorber compound is a compound containing at least one
chromophore selected from the group consisting of (I), (II), (III), (IV), (V),
(VII), (VIII),
and mixtures thereof; more preferably the UV absorber compound is a compound
containing at least one chromophore selected from the group consisting of (I),
(II), (III),
(IV), and mixtures thereof; and even more preferably (I), (II), and mixtures
thereof.
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Furthermore, compounds containing at least one formula (I) chromophore are
especially
preferred.
More preferably these UV absorber compounds are selected from the group
consisting of:
1 O
R %N ~ ~ C-O-R3 O)
R2
R \N ~ ~ ~-C~ ~-NvR4 (II)
R2 ~ R4
R5 HO
R5 ~ ~ ~ ~ R6 (III)
R7 Ra
/ N\ -
(IV)
N
R9
(V)
mixtures thereof;
wherein R1 is a hydrogen or a C1 to C22 alkyl group; preferably a hydrogen or
a
methyl group;
R2 is a hydrogen or a C 1 to C22 alkyl group; preferably a hydrogen or methyl
group;
R3 . is a C 1 to C22 alkyl group; preferably a Cg to C 1 g alkyl group; more
preferably
a C 12 to C 1 g alkyl group;
each R4 is a hydrogen, a C 1 to C22 alkyl group, and mixtures thereof;
preferably a
methyl group, a Cg to C22 alkyl group, and mixtures thereof, more preferably
one
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R4 is a C 1 p to C20 alkyl group, preferably a C 12 to C 1 g alkyl group, and
the other
R4 group is a methyl group;
each RS is a hydrogen, hydroxy group, a C 1 to C22 alkyl group, (which can be
an
ester, amide, or ether interrupted group), and mixtures thereof, preferably a
hydrogen, hydroxy group, and mixtures thereof, more preferably hydrogen;
R6 is a hydrogen, hydroxy group, methoxy group, a C 1 to C22 alkyl group,
(which
can be an ester, amide, or ether interrupted group), and mixtures thereof,
preferably
a C 1 to C22 alkyl group with an ether or ester interrupted group, and
mixtures
thereof, more preferably a methoxy group, a Cg to C22 alkyl group with an
ester
interrupted group, and mixtures thereof;
R~ is a hydrogen, hydroxy group, or a C 1 to C20 alkyl group, preferably a
hydrogen
or a hydroxy group, more preferably a hydroxy group;
Rg is a hydrogen, hydroxy group, or a C 1 to C22 alkyl group, (which can be an
ester, amide, or ether interrupted group); preferably a C 1 to C22 alkyl
group; more
preferably a C 1 to Cg alkyl group, and even more preferably a methyl group,
'a
"tert"-amyl group, or a dodecyl group;
R9 is a hydrogen, hydroxy group, or a C 1 to C22 alkyl group, (which can be an
ester, amide, or ether interrupted group); preferably a "tent"-amyl, methyl
phenyl
group, or a coco dimethyl butanoate group.
These UV absorber compounds absorb light at a wavelength of from about 290nm
to about 450nm, preferably from about 315nm to about 400nm.
R5~ R6~ R~, Rg, and R9 can be interrupted by the corresponding ester linkage
interrupted group with a short alkylene (C 1-C4) group.
Preferred UV absorber agents of the present invention are selected from the
group
consisting of fatty derivatives of PABA, benzophenones, cinnamic acid, and
phenyl
benzotriazoles, specifically, octyl dimethyl PABA, dimethyl PABA lauryl ester,
dimethyl
PABA oleoyl ester, benzophenone-3 coco acetate ether, benzophenone-3 available
under
the tradename Spectra-Sorb~ UV-9 from Cyanamid, 2-(2'-Hydroxy-3',5'-di-tert
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amylphenyl benzotriazole which is available under the tradename Tinuvin~ 328
from
Ciba-Geigy, Tinuvin~ coco ester 2-(2'-Hydroxy,3'-(coco dimethyl butanoate)-5'-
methylphenyl) benzotriazole, and mixtures thereof. Preferred UV absorbers
agents of the
present invention are benzotriazole derivatives since these materials absorb
broadly
throughout the UV region. Preferred benzotriazole derivatives are selected
from the
group consisting of 2-(2'-Hydroxy, 3'-dodecyl, 5'-methylphenyl) benzotriazole
available
under the tradename Tinuvin~571 (Ciba) available from Ciba-Geigy, and Coco 3-
[3'-
(2H-benzotriazol-2'-yl)-5-tert-butyl-4'-hydroxyphenyl] propionate.
Other conventional UV absorbers can be used but are generally less suitable
because they less effectively deposit on surfaces, they sometimes discolor
fabrics, they
are not always stable or compatible with other components in the composition,
and they
are often expensive.
4. Oxidative Stabilizers
Oxidative stabilizers can be present in the compositions of the present
invention
and these prevent yellowing by acting as a scavenger for oxidative processes,
thus
preventing and/or terminating auto-oxidation or by reversing oxidation and
thus reversing
yellowing. The term " oxidative 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.
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 gallate, and citric acid, available from Eastman
Chemical
Products, Inc., under the trade name Tenor -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 Tenor GT-1/GT-2; and butylated 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;
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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-1, 1-diphosphonic acid
(etidronic acid), and Tiron~, available from Kodak with a chemical name of 4,5-
di-
hydroxy-m-benzene-sulfonic acid/sodium salt, and DTPA~, available from Aldrich
with a
chemical name of diethylenetriaminepentaacetic acid.
Oxidative stabilizers can also be added at any point during the process of
making
fabric softener raw materials where polyunsaturated compounds would be
present. E.g.,
these could be added into oils used to make fatty acids, during fatty acid
making and/or
storage during fabric softener making and/or storage. These assure good odor
stability
under long term storage conditions. It is especially critical to add these to
the process
steps used to make unscented or low scent products (no or low perfume).
5. Combinations of auxiliary whiteness preservatives.
G. 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.
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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
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
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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.
(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) Quaternary 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:
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R2
RI-N+ R3 X _
R4
wherein RI, R2, R3, and R4 are each independently CI-C22 alkyl, C3-C22
alkenyl, R5-
Q-(CH2)m-, wherein RS is CI-C22 alkyl, and mixtures thereof, m is from I to
about 6; X
is an anion.
Preferably RI is C6-C22 alkyl, C6-C22 alkenyl, and mixtures thereof, more
preferably C I I -C I g alkyl, C I I -C I g alkenyl, and mixtures thereof; R2,
R3, and R4 are
each preferably CI-C4 alkyl, more preferably each R2, R3, and R4 are methyl.
The formulator may similarly choose RI to be a RS-Q-(CH2)m- moiety wherein
RS is an alkyl or alkenyl moiety having from I 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:
O ~ H3
~N-CH3
O CHI
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) Polyvin~ Amines
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A preferred composition according to the present invention contains at least
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 -NH2 unit hydrogens
can be substituted by an alkyleneoxy unit having the formula:
-~1 O)xR2
wherein R1 is C2-C4 alkylene, R2 is hydrogen, C 1-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:
~ H3
-(CH2CH0)-(CH2CH20)xH
wherein x has the value of from 1 to about 50. 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 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.
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(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-Ran+1-~-R~rri ~-R~ri 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
primary:secondaryaertary 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:
-(R1 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:
--[CHZC(CH3)HO]---(CHZCH20)xH
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wherein x has the value of from 1 to about 50. 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 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
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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
peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing
PEI's are
disclosed in U.S. 2,182,306, Ulrich et al., issued December S, 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-Quaternary 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:
[RZ-N(R~)Z-R-- N(R~)2-RZ] 2X-
wherein R is substituted or unsubstituted C2-C12 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 RS 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.
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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, C11-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:
C1 CH3
/~NHj~N-CH3
C1 ~ __ CH3
wherein 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 1,000 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.,
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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 copol,~s 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
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.
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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
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
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about 50% of the available amino nitrogens.; These cationic polymers can be
prepared in a
known manner by quaternizing 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-),
bromine (Br-), iodine (I-) or any other negatively charged radical such as
sulfate (5042-)
and methosulfate (CH3S03-).
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 polyoxyalkyleneoxy 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). Mono-Alkyl Cationic Quaternary Ammonium Compound
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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_
[R1C(O)-O-CH2CH2N+(R)3 ~ A_
wherein R1, 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 R1 group is present in the
molecule.
The R1 group or YR1 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 wrinkle 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
10 ppm to about 25 ppm in the rinse.
(fj. Soil Release Agent
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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 S%, 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 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).
These soil release agents can also act as a scum dispersant.
(g). Bactericides
Examples of bactericides used in the compositions of this invention include
glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-diol sold by Inolex
Chemicals, located in Philadelphia, Pennsylvania, under the trade name
Bronopol~, and
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a mixture of S-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). Silicones
The silicone herein can be either a polydirriethyl 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
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-Cl 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.
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The amount of PDMS needed to provide a noticeable improvement in water
absorbency is dependent on the initial rewettability 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.
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 July 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 non-limiting Examples show clear, or translucent, products with
acceptable viscosities.
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Fatty Acid Compound A
About 1,300 grams of food grade (refined, bleached, degummed) canola oil and
approximately 6.5 grams of a commercial nickel hydrogenation catalyst
(Engelhard, "N-
545"~) corresponding to approximately 0.13 wt.% Ni, are placed in a
hydrogenation
reactor which is equipped with stirrer. The reactor is sealed and evacuated.
The contents
are heated to about 170 C and hydrogen is fed into the reactor. Stirnng at
about 450
rpm is maintained throughout the reaction. After about 10 minutes the
temperature in the
reactor is about 191 C and the hydrogen pressure is about 11 psig. The
temperature is
held at about 190 C. After about 127 minutes from when the hydrogen feed
began, the
hydrogen pressure is about 10 psig. A sample of the reaction mass is drawn and
found to
have an Iodine Value of about 78 and a cisarans ratio of about 1.098. After
another about
minutes at about 190 C, the hydrogen pressure is about 9.8 psig. The hydrogen
feed
is discontinued and the reactor contents cooled with stirring. The final
reaction product
has an Iodine Value of about 74.5 and a cisarans ratio of about 1.35.
15 The product that forms in the reactor is removed and filtered. It has a
cloud point
of about 22.2 C.
Fatty Acid Compound B
About 1,300 grams of food grade canola oil and about 5.2 grams of Engelhard "N-
545"~ nickel hydrogenation catalyst are placed in a hydrogenation reactor
which is
20 equipped with a stirrer. The reactor is sealed and evacuated. The contents
are heated to
about 175 C and hydrogen is fed into the reactor. Stirring is maintained at
about 450
rpm throughout the course of reaction. After about 5 minutes the temperature W
the
reactor is about 190 C and the hydrogen pressure is about 7 psig. The
temperature is
held at about 190 C. After about 125 minutes from the start of the hydrogen
feed, the
hydrogen pressure is about 7 psig. A sample of the reaction mass is drawn and
found to
have an Iodine Value of about 85.4. After another about 20 minutes at about
190 C, the
hydrogen pressure is about 6 psig. The hydrogen feed is discontinued and the
reactor
contents cooled with stirring. The final reaction product has an Iodine Value
of about 80.
The product that forms in the reactor is removed and filtered. It has a cloud
point of
about 18.6 C.
Fatty Acid Compound C
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About 1,300 grams of food grade canola oil and about 2.9 grams of Engelhard "N-
545"~ nickel hydrogenation catalyst are placed in a hydrogenation reactor
which is
equipped with a stirrer. The reactor is sealed and evacuated. The contents are
heated to
about 180 C and hydrogen is fed into the reactor. Stirring is maintained at
about 450
rpm throughout the course of the reaction. After about 5 minutes the
temperature in the
reactor is about 192 C and the hydrogen pressure is about 10 psig. The
temperature is
held at about 190 +3 C. After about 105 minutes from the start of the hydrogen
feed, the
hydrogen pressure is about 10 psig. A sample of the reaction mass is drawn and
found to
have an Iodine Value of about 85.5. After another about 20 minutes at about
190 C, the
hydrogen pressure is about 10 psig. The hydrogen feed is discontinued and the
reactor
contents cooled with stirring. The final reaction product has an Iodine Value
of about
82.4. The product that forms in the reactor is removed and filtered. It has a
cloud point
of about 17.2 C.
Fatty Acid Compound D
About 1,300 grams of food grade canola oil and about 1.4 grams of Engelhard "N-
545"~ nickel hydrogenation catalyst are placed in a hydrogenation reactor
which is
equipped with a stirrer. The reactor is sealed and evacuated. The contents are
heated to
about 180 C and hydrogen is fed into the reactor. After about 5 minutes the
temperature
in the reactor is about 191 C and the hydrogen pressure is about 10 psig. The
temperature is held at about 190 ~3 C. After about 100 minutes from the start
of the
hydrogen feed, the hydrogen pressure is about 10 psig. A sample of the
reaction mass is
drawn and found to have an Iodine Value of about 95.4. After another about 20
minutes
at about 190 C, the hydrogen pressure is about 10 psig. The hydrogen feed is
discontinued and the reactor contents cooled with stirring. The final reaction
product had
an Iodine Value of about 2.3. The product that forms in the reactor is removed
and
filtered. It has a cloud point of about 34 C.
Fatty Acid Compound E
About 1,300 grams of food grade canola oil and about 1.3 grams of Engelhard "N
545"~ nickel hydrogenation catalyst are placed in a hydrogenation reactor
which is
equipped with a stirrer. The reactor is sealed and evacuated. The contents are
heated to
about 190 C and hydrogen is fed into the reactor to a hydrogen pressure of
about 5 psig.
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After about 3 hours from the start of the hydrogen feed, a sample of the
reaction mass is
drawn and found to have an iodine value of about 98. The hydrogenation is
interrupted,
another about 0.7 grams of the same catalyst is added, and the reaction
conditions are
reestablished at about 190 C for another about 1 hour. The hydrogen feed is
then
discontinued and the reactor contents cooled with stirring. The final reaction
product had
an Iodine Value of about 89.9. The product that forms in the reactor is
removed and
filtered. It has a cloud point of about 16 C.
Fatty Acid Compound F
About 1,300 grams of food grade canola oil and about 2.0 grams of Engelhard "N
545"~ nickel hydrogenation catalyst are placed in a hydrogenation reactor
which is
equipped with a stirrer. The reactor is sealed and evacuated. The contents are
heated to
about 190 C and hydrogen is fed into the reactor to a hydrogen pressure of
about 5 psig.
Stirring is maintained at about 420 rpm throughout the course of reaction of
the hydrogen
feed. After about 130 minutes from the start of the hydrogen feed, the
hydrogen feed is
discontinued and the reactor contents cooled with stirring. The final reaction
product had
an Iodine Value of about 96.4. The product that forms in the reactor is
removed and
filtered. It has a cloud point of about 11.2 C.
Fatty acid Compound G
A mixture of about 1,200 grams of the hydrogenated oil from Synthesis Example
F and about 200 grams of the hydrogenated oil from Synthesis Example A is
hydrolyzed
three times with about 250 C steam at about 600 psig for about 2.5 hours at a
ratio of
steam:oil of about 1.2 (by weight). An aqueous solution containing the
glycerine which
had split off is removed.
The resulting mixture of fatty acids is vacuum distilled for a total of about
150
minutes, in which the pot temperature rose gradually from about 200 C to about
238 C
and the head temperature rose gradually from about 175 C to about 197 C.
Vacuum of
about 0.3-0.6 mm is maintained.
The fatty acids product of the vacuum distillation has an Iodine Value of
about
99.1, an amine value (AV) of about 197.6 and a saponification value (SAP) of
about
198.6.
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The following are examples of softener compounds useful in the present
invention:
Softener compound 1 (DEA Di-ester Quat )
1 )-Esterification:
About 489 grams of partly hydrogenated tallow fatty acid with an IV of about
45
and an Acid Value of about 206, commercially available under the tradename
Distal 51
and sold by 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 1.8:1. 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 5 is reached.
2)-Quaternization:
To about 627 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. 749
grams of softener compound of the invention is obtained.
The quaternized material is optionally diluted with e.g. about 7.5% of ethanol
and
about 7.5% of hexylene glycol which lowers the melting point of the material
thereby
providing a better handling of the material.
The above synthesized softener compound is also exemplified below in the non-
limiting fabric softening composition examples.
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 2 to about S 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
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added to the softener premix and said premix is mixed for about S 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).
Component Wt. % 1 2 3 4 5 6
TEA Di-ester Quat~ 35 35 35 35 35 35
Ethanol (from softener 2.9 2.9 2.9 2.9 2.9 2.9
active)
Hexylene Glycol (from 3.1 3.1 3.1 3.1 3.1 3.1
softener
active)
TMPDZ 5 5 5 5 5 5
NEODOL~ 91-83 6 6 6.5 6 6 6
PLURONIC~ L-354 1 1 1 1 1 1
Amine Chelators 0.75 0.75 0.75 2.5 5 10
MgCl2 1.75 1.75 1.75 1.75 1.75 1.75
DTPA6 0.01 0.01 0.01 0.01 0.01 0.01
Perfume 2.5 1.7 3 2.5 2.5 2.5
Blue dye 0.0006 0.00060.0006 0.00060.0006 0.0006
Deionized water qs 100% qs qs 100%qs qs 100%qs
100% 100% 100%
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Component Wt. % 7 8 9 10 11 12
TEA Di-ester Quat~ 35 35 35 35 35 35
Ethanol (from softener2.9 2.9 2.9 2.9 2.9 2.9
active)
Hexylene Glycol (from 3.1 3.1 3.1 3.1 3.1 3.1
softener
active)
TMPDZ 5 S 5 5 5 5
NEODOL~ 91-83 6.5 6.5 6.5 6.5 6.5 6.5
PLURONIC~ L-354 1 1 1 1 1 1
Amine Chelators 0.75 0.75 0.75 0.75 0.75 0.75
MgClz 1 1 1 1 1 1.00
DTPA6 0.01 0.01 0.01 0.01 0.01 0.01
Tinopal~ CBS' 0.17 0.17 0.17 0.5 2 5
Perfume 2.5 1.7 3 2.5 1.7 3
Blue dye 0.00060.0006 0.00060.0006 0.0006 0.0006
Deionized water qs qs 100%qs qs 100%qs 100%qs
100% 100% 100%
Component Wt. % 13 14 15 16 17 18
TEA Di-ester Quat~ 35 35 35 35 35 35
Ethanol (from softener2.9 2.9 2.9 2.9 2.9 2.9
active)
Hexylene Glycol (from 3.1 3.1 3.1 3.1 3.1 3.1
softener
active)
TMPDZ 5 5 5 S 5 5
NEODOL~ 91-83 6.5 6.5 6.5 6.5 6.5 6.5
PLURONIC~ L-354 1 1 1 1 1 1
Amine Chelator5 10 5 2 0.01 0.05 0.1
MgClz 1 1 1 1 1 1.00
DTPA6 0.01 0.01 0.01 0.01 0.01 0.01
Tinopal~ CBS' 0.17 0.17 0.17 0.5 2 5
Perfume 2.5 1.7 3 2.5 1.7 3
Blue dye 0.00060.0006 0.00060.0006 0.0006 0.0006
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Deionized water qs 100% qs 100% qs 100% qs 100% qs 100% qs 100%
Component Wt. % 19 20 21 22 23 24
TEA Di-ester Quat~ 35 35 35 35 35 35
Ethanol (from softener2.9 2.9 2.9 2.9 2.9 2.9
active)
Hexylene Glycol (from 3.1 3.1 3.1 3.1 3.1 3.1
softener
active)
TMPDZ 5 5 5 5 5 5
NEODOL~ 91-83 6.5 6.5 6.5 6.5 6.5 6.5
PLURONIC~ L-354 1 1 1 1 1 1
Amine Chelator5 1 3.5 9 1 4 7
MgCl2 1 1 1.00 1 1 1.00
DTPA6 0.01 0.01 0.01 0.01 0.01 0.01
Tinopal~ CBS' 0.17 0.17 0.17 0.5 2 5
Perfume 2.5 1.7 3 2.5 1.7 3
Blue dye 0.00060.0006 0.0006 0.00060.0006 0.0006
Deionized water qs qs 100%qs 100%qs qs 100%qs
100% 100% 100%
Component Wt. % 25 26 27 28 29 30
TEA Di-ester Quat~ 35 35 35 35 35 35
Ethanol (from softener 2.9 2.9 2.9 2.9 2.9 2.9
active)
Hexylene Glycol (from 3.1 3.1 3.1 3.1 3.1 3.1
softener
active)
TMPDZ 5 5 S 5 5 5
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NEODOL~ 91-83 6 6 6.5 6 6 6.5
PLURONIC~ L-354 1 1 1 1 1 1
MgCl2 1 1 1 1 1 1
DTPAS 1 1 1 5 7 2
Perfume 2.5 1.7 3 2.5 1.7 3
Blue dye 0.0006 0.0006 0.0006 0.00060.00060.0006
Deionized water qs 100% qs 100%qs 100% qs qs qs 100%
100% 100%
Component Wt. % 31 32 33 34 35 36
TEA Di-ester Quat~ 35 35 35 35 35 35
Ethanol (from softener2.9 2.9 2.9 2.9 2.9 2.9
active)
Hexylene Glycol (from 3.1 3.1 3.1 3.1 3.1 3.1
softener
active)
TMPDZ 5 5 5 5 5 5
NEODOL~ 91-83 6 6 6.5 6 6 6.5
PLURONIC~ L-354 1 1 1 1 1 1
MgCl2 1 1 1 1 1 1
DTPAS 10 6.25 0.5 0.1 2 0.75
Perfume 2.5 1.7 3 2.5 1.7 3
Blue dye 0.0006 0.0006 0.00060.0006 0.00060.0006
Deionized water qs 100%qs 100%qs qs 100%qs qs 100%
100% 100%
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Component Wt. % 37 38 39 40 41 42
TEA Di-ester Quat~ 35 35 35 35 35 35
Ethanol (from softener2.9 2.9 2.9 2.9 2.9 2.9
active)
Hexylene Glycol (from 3.1 3.1 3.1 3.1 3.1 3.1
softener
active)
TMPDZ 5 5 5 5 5 5
NEODOL~ 91-83 6.5 6.5 6.5 6.5 6.5 6.5
PLURONIC~ L-354 1.5 1.5 1.5 1.5 1.5 1.5
Amine Chelator5 0.75 0.75 0.75 2 0.5 2
MgCl2 1 1 1 1 1 1
DTPA6 0.01 0.01 0.01 0.01 0.01 0.01
Liquitint~ Blue 658 0.01 0.01 0.02 0.005 2 1
Perfume 2.5 1.7 3 2.5 1.7 3
Blue dye 0.00060.0006 0.00060.0006 0.0006 0.0006
Deionized water qs qs 100%qs qs 100%qs 100%qs
100% 100% 100%
% 43 44 45 46 47 48
Component Wt .
TEA Di-ester Quat~ 35 35 35 35 35 35
Ethanol (from softener2.9 2.9 2.9 2.9 2.9 2.9
active)
Hexylene Glycol (from 3.1 3.1 3.1 3.1 3.1 3.1
softener
active)
TMPDZ 5 5 5 5 S 5
NEODOL~ 91-83 6.5 6.5 6.5 6.5 6.5 6.5
PLURONIC~ L-354 1.5 1.5 1.5 1.5 1.5 1.5
Amine Chelator5 8 8 0.2 0.5 0.01 1
MgCl2 1 1 1 1 1 1
DTPA6 0.01 0.01 0.01 0.01 0.01 0.01
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Liquitint~ Blue 1 0.001 5 1 10 0.3
658
Perfume 2.5 1.7 3 2.5 1.7 3
Blue dye 0.0006 0.0006 0.00060.0006 0.00060.0006
Deionized water qs 100% qs 100% qs qs 100% qs qs 100%
100% 100%
Component Wt. % 49 50 51 52 53 54
TEA Di-ester Quat' 32 32 32 32 32 32
Ethanol (from softener2.63 2.63 2.63 2.63 2.63 2.63
active)
Hexylene Glycol (from 2.8 2.8 2.8 2.8 2.8 2.8
softener
active)
Canola fatty acid 1 1 1 1 1 1
TMPD2 4.4 4.9 4.4 4.9 4.4 4.9
NEODOL~ 91-83 5.9 5.8 5.9 5.8 5.9 5.8
PLURONIC~ L-354 1 1 1 1 1. 1
Amine Chelators 0.75 0.75 3 0.01 0.5 2
MgCl2 1.75-2.01.75-2.01.75-2.01.75-2.01.75-2.01.75-2.0
DTPA6 0.01 0.01 0.01 0.01 0.01 0.01
Optiblanc~GL9 0.25 0.25 0.25 3 2 0.5
Perfume ~ 2 1.7 2 1.7 2 1.7
Blue dye 0.00060.0006 0.00060.0006 0.0006 0.0006
Deionized water qs qs 100%qs qs 100%qs 100%qs
100% 100% 100%
Component Wt. % 55 56 57 58 59 60
TEA Di-ester Quat' 35 35 35 35 35 35
Ethanol (from softener2.9 2.9 2.9 2.9 2.9 2.9
active)
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Hexylene Glycol (from 3.1 3.1 3.1 3.1 3.1 3.1
softener
active)
TMPDZ 5 5 5 5 5 5
NEODOL~ 91-83 6 6 6 6 6 6
PLURONIC~ L-354 1 1 1 1 1 1
Amine Chelators 0.75 0.75 0.75 0.1 6 0.5
MgCl2 1 1 1 1 1 1
DTPA6 0.01 0.01 0.01 0.01 0.01 0.01
Optiblanc~ GL9 0.5 0.5 0.5 2 0.05 5
Perfume 2.5 1.7 3 2.5 1.7 3
Blue dye 0.00060.0006 0.00060.0006 0.0006 0.0006
Deionized water qs qs 100%qs qs 100%qs 100%qs
100% 100% 100%
Component Wt% 70 71 72 73 74 75
TEA Di-ester Quat' 35 35 35 35 35 35
Ethanol (from softener2.9 2.9 2.9 2.9 2.9 2.9
active)
Hexylene Glycol (from 3.1 3.1 3.1 3.1 3.1 3.1
softener
active)
TMPDZ 5 5 5 5 5 5
NEODOL~ 91-83 6 6 6.5 6 6 6.5
PLURONIC~ L-354 1 1 1 1 1 1
Amine Chelator5 1 1 1 0.1 0.05 0.5
MgClz 1.25-1.51.25-1.51.25-1.5-1.25-1.51.25-1.51.25-1.5-
DTPA6 0.01 0.01 0.01 0.01 0.01 0.01
Optiblanc~GL9 0.1 0.1 0.1 1.75 0.1 0.1
Perfume 2.5 1.7 3 2.5 1.7 3
Blue dye 0.0006 0.0006 0.00060.0006 0.0006 0.0006
Deionized water qs 100%qs 100%qs qs 100%qs 100%qs
100% 100%
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Comuonent Wt% 76 77 78 79 80 81
TEA Di-ester Quat~ 35 35 35 35 35 35
Ethanol (from softener2.9 2.9 2.9 2.9 2.9 2.9
active)
Hexylene Glycol (from 3.1 3.1 3.1 3.1 3.1 3.1
softener
active)
TMPDZ 5 5 5 5 5 5
NEODOL~ 91-83 6 6 6.5 6 6 6.5
PLURONIC~ L-354 1 1 1 1 1 1
Amine Chelator5 8 4.5 1.75 2 3 1.75
MgClz 1-1.5 1-1.5 1-1.5 1-1.5 1-1.5 1-1.5-
DTPA6 0.01 0.01 0.01 0.01 0.01 0.01
OptiblancGL9 0.1 0.1 0.1 1.5 1 2.8
Perfume 2.5 1.7 3 0.5 0.001 3
Blue dye 0.00060.0006 0.00060.0006 0.0006 0.0006
Deionized water qs qs 100%qs qs 100%qs 100%qs
100% 100% 100%
Component Wt. % 82 83 84 85 86 87
TEA Di-ester Quat~ 35 35 35 35 35 35
Ethanol (from softener 2.9 2.9 2.9 2.9 2.9 2.9
active)
Hexylene Glycol (from 3.1 3.1 3.1 3.1 3.1 3.1
softener
active)
TMPDZ 5 5 5 5 5 5
NEODOL~ 91-83 6.5 6.5 6.5 6.5 6.5 6.5
PLURONIC~ L-354 1 1 1 1 1 1
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MgCl2 1 1 1 1 1 1
DTPA6 0.6 0.6 0.6 2 0.6 0.6
Tinopal~ CBS' 0.17 0.17 0.17 0.17 1 S
Perfume 2.5 1.7 3 2.5 1.7 3
Blue dye 0.0006 0.0006 0.00060.0006 0.0006 0.0006
Deionized water qs 100% qs 100%qs qs 100%qs 100%qs
100% 100%
Component Wt. % 88 89 90 91 92 93
TEA Di-ester Quat~ 35 35 35 35 35 35
Ethanol (from softener2.9 2.9 2.9 2.9 2.9 2.9
active)
Hexylene Glycol (from 3.1 3.1 3.1 3.1 3.1 3.1
softener
active)
TMPDZ S 5 5 5 5 5
NEODOL~ 91-83 6.5 6.5 6.5 6.5 6.5 6.5
PLURONIC~ L-354 1 1 1 1 1 1
MgClz 1 1 1 1 1 1
DTPA6 2.75 5.45 3.4 2 0.6 0.2
Tinopal~ CBS' 0.2 0.02 0.15 0.17 2.5 4.45
Perfume 2.5 1.7 3 2.5 1.7 3
Blue dye 0.0006 0.0006 0.00060.0006 0.0006 0.0006
Deionized water qs 100%qs 100%qs qs 100%qs 100%qs
100% 100%
Component Wt 94 95 96 97 98 99
%
TEA Di-ester Quat~ 35 35 35 35 35 35
Ethanol (from softener 2.9 2.9 2.9 2.9 2.9 2.9
active)
Hexylene Glycol (from 3.1 3.1 3.1 3.1 3.1 3.1
softener
active)
TMPDZ 5 5 S 5 S 5
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NEODOL 91-83 6 6 6 6 6 6
PLURONIC L-354 1 1 1 1 1 1
MgClz 1 1 1 1 1 1
DTPA6 1 1 1 6.85 0.52 2.3
Optiblanc GL9 0.5 0.5 0.5 0.05 3.45 0.17
Perfume 2.5 1.7 3 2.5 1.7 3
Blue dye 0.0006 0.0006 0.0006 0.00060.00060.0006
Deionized water qs 100% qs 100%qs 100% qs qs qs 100%
100% 100%
Component Wt% 100 101 102 103 104 105
TEA Di-ester Quat~ 35 35 35 35 35 35
Ethanol (from softener 2.9 2.9 2.9 2.9 2.9 2.9
active)
Hexylene Glycol (from 3.1 3.1 3.1 3.1 3.1 3.1
softener
active)
TMPDz 5 5 5 5 5 5
NEODOL~ 91-83 6.5 6.5 6.5 6.5 6.5 6.5
PLURONIC~ L-354 1 1 1 1 1 1
Amine Chelators 0.25 0.25 0.25 3.82 0.10 0.89
MgCl2 1 1 1 1 1 1
DTPA6 0.5 0.5 0.5 2.1 1.5 0.75
Liquitint~ Patent Blue 0.01 0.02 0.03 0.005 0.2 0.003
$
Perfume 2.5 1.7 3 2.5 1.7 3
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Blue dye 0.0006 0.0006 0.0006 0.0006 0.0006 0.0006
Deionized water qs 100% qs 100% qs 100% qs 100% qs 100% qs 100%
Component Wt% 106 107 108 109 110 111
TEA Di-ester Quat' 35 35 35 35 35 35
Ethanol (from softener2.9 2.9 2.9 2.9 2.9 2.9
active)
Hexylene Glycol (from 3.1 3.1 3.1 3.1 3.1 3.1
softener
active)
TMPDZ 5 5 5 5 5 5
NEODOL~ 91-83 6.5 6.5 6.5 6.5 6.5 6.5
PLURONIC~ L-354 1 1 1 1 1 1
Amine Chelator5 0.25 4.25 0.25 3.82 0.10 0.89
MgCl2 1 0.25 1 1 1 I
DTPA6 0.5 0.5 0.5 2.1 1.5 0.75
OptiblancGL9 3.12 0.02 0.13 0.005 0.5 0.01
Perfume 2.5 1.7 3 2.5 1.7 3
Blue dye 0.0006 0.0006 0.0006O.OU06 0.00060.0006
Deionized water qs 100%qs 100%qs qs 100%qs qs
100% 100% 100%
' Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate where the
acyl group is derived from partially hydrogenated canola fatty acid.
2 2,2,4-trimethyl-1,3-pentanediol
Alkyl alkoxylated surfactants trademarked by Shell
Block copolymer of ethylene oxide and propylene oxide trademarked by BASF,
Mount Olive, NJ.
Tetrakis-(2-hydroxylpropyl) ethylenediamine (TPED).
6 Sodium diethylenetriaminepentaacetate
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Disodium-4,4-bis-(2-sulfostyryl)biphenyl, 33% active slurry , trademarked by
Ciba Geigy, High Point, NC. Levels listed in the formula tables represent the
amount of active brightener.
Liquitints~ are proprietary mixtures useful as bluing agents and trademarked
by
Milliken & Co.
Benzimidazol derivative trademarked by 3V Inc., Weehauken, NJ, 10-20% active
dispersion. Levels used in the formula tables represent amount of dispersion
added.
88
