Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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CONCENTRATED FABRIC SOFTENING COMPOST170N AND HIGHLY UNSATURATED FABRIC
SOFTENER COMPOUND THEREFOR
10
TECHNICAL FIELD
The present invention relates to highly-unsaturated, biodegradable fabric
softener
compounds for use in preparing softening compositions useful for softening
cloth. It
especially relates the preparation of concentrated textile softening
compositions with
good freeze/thaw recovery properties for use in the rinse cycle of a home
textile
laundering operation to provide excellent fabric-softening/static-control and
rewet
benefits.
BACKGROUND OF THE INVENTION
Fabric softening compositions containing high softener levels are known in the
art. However, there is a need for highly concentrated compositions that have
good
freeze/thaw recovery properties, especially compositions that can be prepared
by
processing at normal ambient temperatures.
The - present invention provides highly concentrated aqueous liquid textile
treatment compositions, that have improved stability (i.e., do not
precipitate, gel, thicken,
or solidify) at normal, i.e., room temperatures and sub-normal temperatures
under
prolonged storage conditions and that will recover after freezing to form
stable
compositions.
SUMMARY OF THE INVENTION
In one aspect, the liquid fabric softener compositions herein comprise:
A. from about 15% to about 50%, preferably from about 16% to about 35%, more
preferably from about I7% to about 30%, by weight of the composition, of
biodegradable fabric softener active selected from the group consisting of
1. softener having the formula:
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(R)4-m - NC+) - [(CH2)n - Y- R elm X(-)
(I)
wherein each R substituent is a short chain CI-C6, preferably CI-C3 alkyl or
hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl,
hydroxyethyl, and the
S like, benzyl, or mixtures thereof; each m is 2 or 3; each n is from 1 to
about 4; each Y is -
O-(O)C-, or -C(O)-O-; the sum of carbons in each R l , plus one when Y is -O-
(O)C-, is
C I 2-C22, preferably C I 4-C20, with each R 1 being a hydrocarbyl, or
substituted
hydrocarbyl, group, preferably, alkyl, monounsaturated alkylene, and
polyunsaturated
alkylene groups, with the softener active containing polyunsaturated alkylene
groups
being at least about 3%, preferably at least about 5%, more preferably at
least about 10%,
and even more preferably at least about I S%, by weight of the total softener
active
present (As used herein, the "percent of softener active" containing a given
RI group is
the same as the percentage of that same R I group is to the total R I groups
used to form
all of the softener actives.); (As used herein, the Iodine Value of a "parent"
fatty acid, or
IS "corresponding" fatty acid, is used to define a level of unsaturation for
an RI group that is
the same as the level of unsaturation that would be present in a fatty acid
containing the
same RI group.); and wherein the counterion, X-, can be any softener-
compatible anion,
preferably, chloride, bromide, methyl sulfate, or nitrate. more preferably
chloride;
2. softener having the formula:
~ YR~
R3 N~+) CH2CH X(-)
~ C H2 YR ~
(2)
wherein each Y, R, RI, and X(-) have the same meanings as before (Such
compounds
include those having the formula:
[CH3]3 N(+)[CH2CH(CH20(O)CRI)O(O)CRI] C1(-)
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especially where C(O)R1 is derived from mixtures of RI groups, containing some
saturated, some unsaturated, e.g., oleic, fatty acid, and some polyunsaturated
fatty acid,
and, preferably, each R is a methyl or ethyl group and preferably each RI is
in the range
of C 1 S to C 1 g with varying degrees of unsaturation being present in the
alkyl chains); and
3. mixtures thereof; said fabric softener active being in the form of a stable
dispersion;
B. optionally, from 0% to about I 0%, preferably from about 0. I % to about
5%, and
more preferably from about 0.2% to about 3%, of perfume;
C. optionally, from 0% to about 2%, preferably from about 0.01 % to about
0.2%, and
more preferably from about 0.035% to about 0.1%, of stabilizer; and
D. the balance being a liquid carrier comprising water and, optionally, from
about 5%
to about 30%, preferably from about 8% to about 25%, more preferably from
about 10%
to about 20%, by weight of the composition of water soluble organic solvent;
the
I S viscosity of the composition being less than about 500 cps, preferably
less than about 400
cps, more preferably less than about 200 cps, and recovering to less than
about 1000 cps,
preferably less than about 500 cps, more preferably less than about 200 cps
after freezing
and thawing.
In another aspect, the compositions can be clear and comprise:
A. from about 2% to about 80%, preferably from about 13% to about 75%, more
preferably from about 17% to about 70%, and even more preferably from about
19% to
about 65%, by weight of the composition, of biodegradable fabric softener
active selected
from the group consisting of:
1. -softener having the formula:
(R)4-m - N(+) - I(CH2)n - Y- R ~~m
(1)
wherein each R substituent is a short chain C1-C6, preferably CI-C3 alkyl or
hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl,
hydroxyethyl, and the
like, benzyl, or mixtures thereof; each m is 2 or 3; each n is from 1 to about
4; each Y is -
O-(O)C-, or -C(O)-O-; the sum of carbons in each R1, plus one when Y is -O-
(O)C-, is
C 12-C22~ preferably C 14-C20, with each R I being a hydrocarbyl, or
substituted
hydrocarbyl, group, preferably, alkyl, monounsaturated alkylene, and
polyunsaturated
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alkylene groups. with the softener active containing polyunsaturated alkylene
groups
being at least about 3%, 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 (As used herein, the "percent of softener active" containing a given
RI group is
S the same as the percentage of that same R I group is to the total R 1 groups
used to form
all of the softener actives.); (As used herein, the Iodine Value of a "parent"
fatty acid, or
"corresponding" fatty acid, is used to define a level of unsaturation for an
RI group that is
the same as the level of unsaturation that would be present in a fatty acid
containing the
same RI group.); and wherein the counterion, X-, can be any softener-
compatible anion,
preferably, chloride, bromide, methyl sulfate. or nitrate, more preferably
chloride;
2. softener having the formula:
~ YR~
R NC+) CH2CH X~-)
CH2 YR ~
(2)
I 5 wherein each Y, R, R I , and X(-) have the same meanings as before; and
3. mixtures thereof; and
B. less than about 40%, preferably from about 10% to about 38%, more
preferably
from about 12% to about 25%, and even more preferably from about 14% to about
20%,
by weight of the composition of principal solvent having a ClogP of from about
0.15 to
about 0.64,-preferably from about 0.25 to about 0.62. and more preferably from
about
0.40 to about 0.60, said principal solvent preferably comprising 1,2-
hexanediol, or,
alternatively, a mixture of 2,2,4-trimethyl-1,3-pentanediol and 1,4-
cyclohexanedimethanol the ratio range of TMPD to I ,4-cyclohexanedimethanol
for good
phase stability, especially low temperature phase stability preferably being
from about
80:20 to about 50:50, more preferably about 75:25.
The pH of the compositions should be from about 1 to about 5, preferably from
about 1.~ to about 4.5, more preferably from about 2 to about 3.5.
DETAILED DESCRIPTION OF THE INVENTION
A. FABRIC SOFTENING ACTIVE
The essential component herein is, from about i5% to about 50%, preferably
from
about 16% to about 35%, more preferably from about 17% to about 30%, by weight
of
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the composition. of a biodegradable fabric softener active selected from the
compounds
identified hereinafter, and mixtures thereof. These cnmnrnmrtc a,-P ".".P~
rnmr,rw,rv..l..
having unobvious properties when formulated into aqueous. concentrated fabric
softener
compositions of the traditional type that are dispersions/suspensions of
fabric softener
5 actives. The compounds should have at least about 3%, more preferably at
least about
5%, even more preferably at least about 10%, and still more preferably at
least about 15%
of softener active containing polyunsaturated groups. This polyunsaturation
provides
superior freeze/thaw recovery. Normally, one would not want polyunsaturated
groups in
actives, since they tend to be much more unstable than even monounsaturated
groups.
The presence of these highly unsaturated materials makes it highly desirable,
and for the
higher levels of polyunsaturation, essential, that the compounds and/or
compositions
herein contain antibacterial agents, antioxidants. and/or reducing materials.
to protect the
actives from degradation.
Diester Ouaternarv Ammonium Fabric Softening Active Compound (DEOA)
( 1 ) The first type of DEQA preferably comprises, as the principal active,
compounds of the formula
(R)4-m - N(+) - ~(CH2)n - Y- R ~)m X(-)
(1)
wherein each R substituent is a short chain C 1-C6, preferably C 1-C3 alkyl or
hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyi,
hydroxyethyl, and the
like, benzyl-or mixtures thereof; each m is 2 or 3; each n is from 1 to about
4; each Y is
-O-(O)C-, or -C(O)-O-; the sum of carbons in each Rl, plus one when Y is -O-
(O)C-, is
C 12-C22~ preferably C 14-C20, with each R 1 being a hydrocarbyl, or
substituted
hydrocarbyl group. Preferably, the softener active contains alkyl,
monounsaturated
alkylene, and polyunsaturated alkylene groups, with the softener active
containing
polyunsaturated alkylene groups being at least about 3%, 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. (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.)
The Iodine Value (hereinafter referred to as IV) of the parent fatty acids of
these R1
group is preferably from about 60 to about 140, more preferably from about 70
to about
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130; and even more preferably from about 75 to about I I ~, on the average. It
is believed
that the actives which comprise unsaturated R1 groups are preferably from
about SO% to
about 100%, more preferably from about 55% to about 95%, and even more
preferably
from about 60% to about 90%, by weight of the total active present. The
actives
containing polyunsaturated RI groups are at least about 3%, preferably at
least about 5%,
and more preferably at least about 10%, and yet more preferably at least about
I S%, by
weight, of the total actives present. These polyunsaturated groups are
necessary to
provide optimum viscosity stability, especially after freezing and thawing.
The higher the
level of polyunsaturated RI groups in the actives. the lower the level of
actives which
comprise unsaturated R1 groups can be.
The counterion, X(-) above, can be any softener-compatible anion, preferably
the
anion of a strong acid, for example, chloride, bromide, methylsulfate,
sulfate, nitrate and
the like, and more preferably chloride.
These biodegradable quaternary ammonium fabric softening compounds preferably
contain the group C(O)R1 which is derived, primarily from unsaturated fatty
acids, e.g.,
oleic acid, the essential polyunsaturated fatty acids. and/or saturated fatty
acids, and/or
partially hydrogenated fatty acids from natural sources, e.g., derived from
vegetable oils
and/or partially hydrogenated vegetable oils, such as, canola oil, safflower
oiI, peanut oil,
sunflower oil, corn oil, soybean oil, tall oil, rice bran oil. etc. In other
preferred
embodiments, the fatty acids have the following approximate distributions, the
comparative DEQAs being similar to those described in the art:
Fatty Acvl DEQA DE A2 DEOA3 DEQA'~ DEQAS
Group 1
C I 2 - trace trace 0 0 0
CI4 3 3 0 0 0
CI6 4 4 5 5 5
C18 0 0 S 6 6
C14:1 3 3 0 0 0
C16:1 11 7 0 0 3
C 18:1 74 73 7 I 68 67
C18:2 4 8 8 I1 Il
C18:3 0 1 1 2 2
C20:1 0 0 2 2 2
C20 and up 0 0 2 0 0
Unknowns 0 0 6 6 7
Total 99 99 100 100 102
IV 86-90 88-95 99 100 95
cis/trans 20-30 20-30 4 5
(C 18:1
)
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TPU 4 9 9 13 13
Nonlimiting examples of DEQA's are as follows:
Fattv Acvl DEOA1 0 DEQA11
Group
C14 0 1
C16 11 25
C 18 4 20
C14:1 0 0
C16:1 1 0
C 18:1 27 45
C 18:2 SO
6
C 18:3 7 0
Unknowns 0 3
Tonal 100 100
IV 125-138 56
cis/trans Not 7
(C 18:1 )
Available
TPU 57 6
DEQA10 is prepared from a soy bean fatty acid, and DEQAI l is prepared from a
slightly
hydrogenated tallow fatty acid.
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 95%, more
preferably
from about 60% to about 90%, and that the total level of active containing
polyunsaturated fatty acyl groups (TPU) be from about 3% to about 30%,
preferably from
about 5% to about 25%, more preferably from about 10% to about 18%. The
cis/trans
ratio for the unsaturated fatty acyl groups is important, with a cis/trans
ratio of from 1:1 to
about 50:1, the minimum being 1:1, preferably at least 3:1, and more
preferably from
about 4:1 to about 20:1.
The unsaturated, including the essential polyunsaturated, fatty acyl groups
surprisingly provide effective softening, but also provide better rewetting
characteristics,
good antistatic characteristics, and superior recovery after freezing and
thawing. These
unsaturated materials provide excellent softening and antistatic effects while
minimizing
loss of water absorbency and "greasy" feel. These two characteristics allow
one to use
higher levels of softener than would be ordinarily desirable, which provides
several
additional benefits, including less damage to the fabrics and improved color
maintenance
for colored items. The typical usage level in a rinse cycle is enough to
provide a ratio of
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grams of softener active to kilograms of fabric of at least about 3,
preferably from about
3.2 to about 10, more preferably from about 3.5 to about 7. The concentration
C
(in ppm - parts per million) of softener active of this invention in rinse
water, needed to
provide good fabric color maintenance, also depends on the relative amounts of
fabrics
and rinse water, as measured by the ratio R of fabric weight (in grams) to
rinse water
weight (in kilograms). The ratio a = C/R is at least about 3, preferably at
least about 3.3,
more preferably about 3.5, and even more preferably about 3.7.
The highly unsaturated materials are also easier to formulate into
concentrated
premixes that maintain their low viscosity and are therefore easier to
process, e.g., pump,
mixing, etc. These highly unsaturated materials with only a 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
dispersion 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 mimimizes degradation. Additional protection
against
degradation can be provided when the compounds and softener compositions
contain
effective antioxidants and/or reducing agents, as disclosed hereinafter.
It will be understood that substituents R and R1 can optionally be substituted
with
various groups such as alkoxyl or hydroxyl groups, so long as the R 1 groups
maintain
their basically hydrophobic character. The preferred compounds can be
considered to be
biodegradable diester variations of ditallow dimethyl ammonium chloride
(hereinafter
referred to as "DTDMAC"), which is a widely used fabric softener. 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-dimethyl ammonium chloride,
where
the acyl is derived from fatty acids containing sufficient polyunsaturation.
As used herein, when the diester is specified, it can include the monoester
that is
present. Preferably, at least about 80% of the DEQA is in the diester form,
and from 0%
to about 20% can be DEQA monoester (e.g., in formula ( 1 ), m is 2 and one YR
1 group is
either "H" or "-C-(O)-OH"). 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 S%. However, under high, anionic detergent surfactant or detergent
builder
carry-over conditions, some monoester can be preferred. The overall ratios of
diester to
monoester are from about 100:1 to about 2:1, preferably from about 50:1 to
about 5:1,
more preferably from about I3:1 to about 8:1. Under high detergent carry-over
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conditions. the di/monoester ratio is preferably about 11:1. The level of
monoester
present can be controlled in manufacturing the DEQA.
The above compounds, used as the biodegradable quaternized ester-amine
softening material in the practice of this invention, can be prepared using
standard
reaction chemistry. In one synthesis of a di-ester variation of DTDMAC, an
amine of the
formula RN(CH2CH20H)2 is esterified at both hydroxyl groups with an acid
chloride of
the formula R1C(O)CI, then quaternized with an alkyl halide, RX. to yield the
desired
reaction product (wherein R and R1 are as defined hereinbefore). However, it
will be
appreciated by those skilled in the chemical arts that this reaction sequence
allows a broad
selection of agents to be prepared.
Yet another DEQA softener active that is suitable for the formulation of the
concentrated, liquid fabric softener compositions of the present invention,
has the above
formula ( 1 ) wherein one R group is a C 1 _4 hydroxy alkyl group, preferably
one wherein
one R group is a hydroxyethyl group. An example of such a hydroxyethyl ester
active is
di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate, where the acyl
is
derived from the fatty acids described hereinbefore. Another example of this
type of
DEQA is derived from the same fatty acid as that of DEQA I , and is denoted
hereinafter
as DEQAB.
(2) A second type of DEQA active has the general formula:
~ YR ~
R3 N(+) CH2CH X~-)
C H2 YR ~
(2)
wherein each Y, R, R1, and ?~(') have the same meanings as before. Such
compounds
include those having the formula:
[CH3 j3 N(+)[CH2CH(CH20(O)CR I )O(O)CR l j C 1 (')
where 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, I 37,180, Naik et al., issued Jan. 30, 1979.
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An example of a preferred DEQA of formula ('_') 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 DEQA~,
and is
denoted hereinafter as DEQA9.
5 The DEQA actives described hereinabove can contain a low level of the fatty
acids
which can be unreacted starting material and/or by-product of any partial
degradation.
e.g., hydrolysis, of the softener actives in the finished compositions. It is
preferred that
the level of free fatty acid be low, preferably below about 10%, more
preferably below
about 5%, by weight of the softener active.
10 CONCENTRATED DISPERSION COMPOSITIONS
Stable "dispersion" compositions which can be prepared using the novel
compounds/compositions herein are those disclosed in
U.S. Patent No. 5,545,340. Vv'ahl et al., issued August 13, 1996.
1 ~ B. PERFUME
The premixes and/or finished compositions of the present invention can contain
any softener compatible perfume. Preferred perfumes are disclosed in U.S. Pat.
5,500,138. Bacon et al., issued March 19, 1996, said patent being incorporated
herein by
reference. Perfilme is optionally present at a level of from about 0% to about
10%,
:?0 preferably from about 0.1% to about 5%, more preferably from about 0.2% to
about 3%,
by weight of the finished composition. It is an advantage of the use of this
invention, that
the perfume preferably can be added in the premix to simplify the preparation
of the
finished dispersion compositions and to improve fabric deposition of said
perfume. The
premix can ~e added to water containing the requisite amount of acid,
preferably mineral
25 acid, more preferably HC1, to create the finished composition as discussed
hereinafter.
C. STABILIZERS
Stabilizers are highly desirable, and even essential, in the finished
dispersion
and/or clear compositions, and, optionally, the raw materials, of the present
invention.
The term "stabilizer," as used herein, includes antioxidants and reductive
agents. These
:30 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 0.03 S% to about 0.1 % for
antioxidants, and more
preferably from about 0.01 % to about 0.2% for reductive agents, in the final
composition.
For the premix, the levels are adjusted, depending on the concentrations of
the softener
active in the premix and the finished composition. These assure good odor
stability under
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long term storage conditions. Antioxidants and reductive agent stabilizers are
especially
critical for unscented or low scent products (no or low perfume).
Examples of antioxidants that can be added to the dispersion compositions 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 Tenox~-6; butylated hydroxytoluene, available from UOP Process
Division
under the trade name Sustane~ BHT; tertiary butylhydroquinone, Eastman
Chemical
Products, Inc., as Tenox~ TBHQ; natural tocopherols, Eastman Chemical
Products, Inc.,
as Tenox~ GT-1/GT-2; and butylated hydroxyanisole, Eastman Chemical Products,
Inc.,
as BHA; long chain esters (Cg-C22) of gallic acid, e.g., dodecyl gallate;
Irganox~ 1010;
Irganox~ 1035; Irganox~ B 1171; Irganox~ 1425; Irganox~ 3114; Irganox~ 3125;
and
mixtures thereof; preferably Irganox~ 3125, IrganoxO 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, I-diphosphonic acid (etidronic acid),
and
Tiron~, available from Kodak with a chemical name of 4,5-dihydroxy-m-benzene
sulfonic acid/sodium salt, and DTPA~, available from Aldrich with a chemical
name of
diethylenetriaminepentaacetic acid.
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D. WATER AND WATER SOLUBLE ORGANIC SOLVENT SYSTEM
The dispersion compositions of the present invention contain water and.
optionally, comprise from about 5% to about 30%, preferably from about 8% to
about
25%, more preferably from about 10% to about 20%, by weight of the composition
of
water soluble organic solvent. The solvent is preferably mixed with the fabric
softener
DEQA to help provide a low viscosity for ease of processing, e.g., pumping
and/or
mixing, even at ambient temperatures.
The organic solvent is preferably water soluble solvent, e.g., ethanol;
isopropanol;
1,2-propanediol; 1,3-propanediol; propylene carbonate; hexylene glycol,; etc.
The ability to create finished concentrated compositions with conventional
mixing
at ambient temperatures, e.g., from about 10°C to about 40°C,
preferably from about
20°C to about 35°C, with only low levels of water soluble
solvents, is possible with the
highly unsaturated fabric softener compounds disclosed hereinbefore. This
processing at
ambient temperatures is very important when the dispersion compositions
contain high
levels of polyunsaturated softener active materials.
CLEAR COMPOSITIONS
The compositions can be clear and comprise:
A. from about 2% to about 80%, preferably from about 13% to about 75%, more
preferably from about 17% to about 70%, and even more preferably from about
19% to
about 65%, by weight of the composition. of biodegradable fabric softener
active selected
from the group consisting of:
1. softener having the formula:
~R)4-m - NC+) - WH2)n - Y- R elm X~-)
(1)
wherein each R substituent is a short chain CI-C6, preferably C1-C3 alkyl or
hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl,
hydroxyethyl, and the
like, benzyl, or mixtures thereof; each m is 2 or 3; each n is from 1 to about
4; each Y is -
O-(O}C-, or -C(O)-O-; the sum of carbons in each RI, plus one when Y is -O-
(O)C-, is
C 12-C22, preferably C 14-C20, with each R 1 being a hydrocarbyl, or
substituted
hydrocarbyl, group, preferably, alkyl, monounsaturated alkylene, and
polyunsaturated
alkylene groups, with the softener active containing polyunsaturated alkylene
groups
being at least about 3%, preferably at least about 5%, more preferably at
least about 10%,
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and even more preferably at least about 15%, by weight of the total softener
active
present (As used herein, the "percent of softener active" containing a given
RI group is
the same as the percentage of that same R I group is to the total R 1 groups
used to form
all of the softener actives.); (As used herein, the Iodine Value of a "parent"
fatty acid, or
"corresponding" fatty acid, is used to define a level of unsaturation for an
R1 group that is
the same as the level of unsaturation that would be present in a fatty acid
containing the
same R1 group.); and wherein the counterion, X-, can be any softener-
compatible anion,
preferably, chloride, bromide, methyl sulfate, or nitrate, more preferably
chloride;
2. softener having the formula:
~ YR~
R NC+) CH2CH
C H2 YR ~
(2)
wherein each Y, R, R 1, and X(-) have the same meanings as before; and
_ 3. mixtures thereof;
1 S B. less than about 40%, preferably from about I 0% to about 38%, more
preferably
from about 12% to about 25%, and even more preferably from about 14% to about
20%,
by weight of the composition of principal solvent having a ClogP of from about
0.15 to
about 0.64, preferably from about 0.25 to about 0.62. and more preferably from
about
0.40 to about 0.60, and preferably having some degree of asymmetry, said
principal
solvent preferably comprising 1,2-hexanediol, or, alternatively. 2,2,4-
trimethyl-I,3-
pentanediol (TMPD) and 1,4-cyclohexanedimethanol the ratio range of TMPD to
1,4-
cyclohexanedimethanol for good phase stability, especially low temperature
phase
stability, preferably being from about 80:20 to about 50:50, more preferably
about 75:25;
C. optionally, but preferably, an effective amount, sufficient to improve
clarity, of
low molecular weight water soluble solvents like ethanol; isopropanol;
propylene glycol;
1,3-propanediol; propylene carbonate; hexylene glycol; etc., said water
soluble solvents
being at a level that will not form clear compositions by themselves;
D. optionally, but preferably, an effective amount to improve clarity, of
water soluble
calcium and/or magnesium salt, preferably chloride; and
E. the balance being water.
CA 02260920 2001-11-08
I~
The optional water soluble organic solvents have been described above. The
clear
compositions can also contain the perfume and stabilizer systems described
above and all
of the compositions can contain the following optional compositions.
B. Princiaal Solvent
The suitability of any principal solvent for the formulation of the liquid,
concentrated, preferably clear, fabric softener compositions herein with the
requisite
stability is surprisingly selective. Suitable solvents can be selected based
upon their
octanol/water partition coefficient (P). Octanoi/water partition coefficient
of a principal
solvent is the ratio between its equilibrium concentration in octanol and in
water. The
partition coefficients of the principal 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" (CIogP) is
determined by
the fragment approach of Hanseh 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.
ZO 29~, Pergamon Press, 1990). The fragment approach is
based on the chemical structure of each ingredient, and takes into account the
numbers
and types of atoms, the atom connectivity, and chemical bonding. The ClogP
values.
which are the most reliable and widely used estimates for this physicochemical
property.
are preferably used instead of the experimental IogP values in the selection
of the
:ZS principal solvent ingredients which are useful in the present invention.
CA 02260920 1999-O1-19
WO 98/03619 PCT/LTS97/05097
Solvents that have a low molecular weight and are biodegradable are also
desirable for some purposes. The more asymmetric solvents appear to be very
desirable,
whereas the highly symmetrical solvents, having a center of symmetry, such as
1,7-
heptanediol, or I ,4-bis(hydroxymethyl)cyclohexane, appear to be unable to
provide the
5 essentially clear compositions when used alone, even though their ClogP
values fall in the
preferred range. One can select the most suitable principal solvent by
determining
whether a composition containing about 27% di(oleyoyloxyethyl)dimethylammonium
chloride, about 16-20% of principal solvent, and about 4-6% ethanol remains
clear during
storage at about 40°F (about 4.4°C) and recovers from being
frozen at about 0°F (about
10 18°C).
Suitable solvents include: 2,2,4-trimethyl-1,3-pentanediol; the ethoxylate,
diethoxylate, or triethoxylate derivatives of 2,2,4-trimethyl-1,3-pentanediol;
and/or 2-
ethyl-1,3-hexanediol, and/or mixtures thereof;
I. mono-ols including: ,
15 a. n-propanol; and/or
b. 2-butanol and/or 2-methyl-2-propanol;
II. hexane diol isomers including: 2,3-butanediol, 2,3-dimethyl-; 1,2-
butanediol, 2,3-
dimethyl-; 1,2-butanediol, 3,3-dimethyl-; 2,3-pentanediol, 2-methyl-; 2,3-
pentanediol, 3
methyl-; 2,3-pentanediol, 4-methyl-; 2,3-hexanediol; 3,4-hexanediol; 1,2-
butanediol, 2
ethyl-; 1,2-pentanediol, 2-methyl-; 1,2-pentanediol, 3-methyl-; 1,2-
pentanediol, 4-methyl
and/or I,2-hexanediol;
CA 02260920 1999-O1-19
WO 98/03619 PCT/US97/05097
16
III. heptane diol isomers including: 1.3-propanediol, 2-butyl-; 1,3-
propanediol, 2,2-
diethyl-; 1,3-propanediol, 2-(1-methylpropyl)-; 1,3-propanediol, 2-(2-
methylpropyl)-; 1,3-
propanediol, 2-methyl-2-propyl-; 1,2-butanediol, 2,3,3-trimethyl-; 1,4-
butanediol, 2-
ethyl-2-methyl-; 1,4-butanediol, 2-ethyl-3-methyl-; 1,4-butanediol, 2-propyl-;
1,4-
butanedioi, 2-isopropyl-; 1,5-pentanedioI, 2.2-dimethyl-; I,5-pentanediol, 2,3-
dimethyl-;
1,5-pentanediol, 2,4-dimethyl-; 1,5-pentanediol, 3,3-dimethyl-; 2,3-
pentanediol, 2,3-
dimethyl-; 2,3-pentanediol, 2,4-dimethyl-; 2,3-pentanediol, 3,4-dimethyl-; 2,3-
pentanediol, 4,4-dimethyl-; 3,4-pentanediol, 2,3-dimethyl-; 1,5-pentanediol, 2-
ethyl-; 1,6-
hexanediol, 2-methyl-; 1,6-hexanediol, 3-methyl-; 2,3-hexanediol, 2-methyl-;
2,3-
hexanediol, 3-methyl-; 2,3-hexanediol, 4-methyl-; 2,3-hexanediol, 5-methyl-;
3,4-
hexanediol, 2-methyl-; 3,4-hexanediol, 3-methyl-; 1,3-heptanediol; 1,4-
heptanediol; I,S-
heptanediol; and/or 1,6-heptanediol;
IV. octane diol isomers , including: 1,3-propanediol, 2-(2-methylbutyl)-; 1,3
propanediol, 2-(1,1-dimethylpropyl)- 1,3-propanediol, 2-(1,2-dimethylpropyl)-;
1,3
propanediol, 2-(I-ethylpropyl)-; 1,3-propanediol, 2-(I-methylbutyl)-; 1,3-
propanediol, 2
(2,2-dimethylpropyl)-; 1,3-propanediol, 2-(3-methylbutyl)-; 1,3-propanediol, 2-
butyl-2-
methyl-; 1,3-propanediol, 2-ethyl-2-isopropyl-; 1,3-propanediol, 2-ethyl-2-
propyl-; 1,3-
propanediol, 2-methyl-2-(I-methylpropyl}-; 1,3-propanediol, 2-methyl-2-(2-
methyipropyl)-; 1,3-propanediol, 2-tertiary-butyl-2-methyl-; 1,3-butanediol,
2,2-diethyl-;
1,3-butanediol, 2-(1-methylpropyl)-; 1,3-butanediol, 2-butyl-; 1,3-butanediol,
2-ethyl-2.3-
dimethyl-; I,3-butanediol, 2-(I,l-dimethylethyl)-; 1,3-butanediol, 2-(2-
methylpropyl)-;
1,3-butanediol, 2-methyl-2-isopropyl-; 1,3-butanediol, 2-methyl-2-propyl-; 1.3-
butanediol, 3-methyl-2-isopropyl-; 1,3-butanediol, 3-methyl-2-propyl-; 1,4-
butanediol,
2,2-diethyl-; 1,4-butanediol, 2-methyl-2-propyl-; 1,4-butanediol, 2-(1-
methylpropyl)-;
1,4-butanediol, 2-ethyl-2,3-dimethyl-; 1,4-butanediol, 2-ethyl-3,3-dimethyl-;
1,4-
butanediol, 2-(I,1-dimethylethyl)-; 1,4-butanediol, 2-(2-methylpropyl}-; 1,4-
butanediol,
2-methyl-3-propyl-; 1,4-butanediol, 3-methyl-2-isopropyl-; 1,3-pentanediol,
2,2,3-
trimethyl-; 1,3-pentanediol, 2,2,4-trimethyl-; 1,3-pentanediol, 2,3,4-
trimethyl-; 1,3-
pentanediol, 2,4,4-trimethyl-; 1,3-pentanediol, 3,4,4-trimethyl-; 1,4-
pentanediol, 2,2,3-
trimethyl-; 1,4-pentanediol, 2,2,4-trimethyl-; 1,4-pentanediol, 2,3,3-
trimethyl-; 1,4-
pentanediol, 2,3,4-trimethyl-; 1,4-pentanediol, 3,3.4-trimethyl-; I,5-
pentanediol, ?.2,3-
trimethyl-; 1,5-pentanediol, 2,2,4-trimethyl-; I,5-pentanediol, 2,3,3-
trimethyl-; I,5-
pentanediol, 2,3,4-trimethyl-; 2,4-pentanediol, 2,3,3-trimethyl-; 2,4-
pentanediol, 2,3,4-
trimethyl-; 1,3-pentanediol, 2-ethyl-2-methyl-; 1,3-pentanediol, 2-ethyl-3-
methyl-; 1,3-
pentanediol, 2-ethyl-4-methyl-; 1,3-pentanediol, 3-ethyl-2-methyl-; 1,4-
pentanediol, 2-
CA 02260920 1999-O1-19
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17
ethyl-2-methyl-; 1.4-pentanediol. 2-ethyl-3-methyl-: 1,4-pentanediol, 2-ethyl-
4-methyl-;
1,4-pentanediol. 3-ethyl-2-methyl-; 1,4-pentanediol, 3-ethyl-3-methyl-; 1,5-
pentanediol,
2-ethyl-2-methyl-; 1,5-pentanediol, 2-ethyl-3-methyl-; 1,5-pentanediol, 2-
ethyl-4-methyl-
1,5-pentanediol, 3-ethyl-3-methyl-; .2,4-pentanediol, 3-ethyl-2-methyl-; 1,3-
pentanediol,
2-isopropyl-; I,3-pentanediol, 2-propyl-; 1,4-pentanediol, 2-isopropyl-; 1,4-
pentanediol,
2-propyl-; 1,4-pentanediol, 3-isopropyl-; I,5-pentanediol, 2-isopropyl-; 2,4-
pentanediol,
3-propyl-; 1,3-hexanediol, 2,2-dimethyl-; I,3-hexanediol, 2,3-dimethyl-; 1,3-
hexanediol.
2,4-dimethyl-; I ,3-hexanediol, 2,5-dimethyl-; 1,3-hexanediol, 3,4-dimethyl-;
1,3
hexanedioI, 3,5-dimethyl-; 1.3-hexanediol, 4,5-dimethyl-; 1,4-hexanediol, 2,2-
dimethyl-;
1,4-hexanediol, 2,3-dimethyl-; 1,4-hexanediol, 2,4-dimethyl-; l,4-hexanediol,
2,5-
dimethyl-; 1,4-hexanediol, 3,3-dimethyl-; 1,4-hexanediol, 3,4-dimethyl-; 1,4-
hexanediol,
3,5-dimethyl-; 1,3-hexanediol, 4,4-dimethyl-; l,4-hexanediol. 4,5-dimethyl-;
1,4-
hexanediol, 5.5-dimethyl-; 1,5-hexanediol, 2,2-dimethyl-; 1,5-hexanediol, 2,3-
dimethyl-;
1,5-hexanediol, 2,4-dimethyl-; 1,5-hexanediol, 2,5-dimethyl-; 1,5-hexanediol,
3,3-
dimethyl-; 1,5-hexanediol, 3,4-dimethyl-; 1,5-hexanediol, 3,5-dimethyl-; 1,5-
hexanediol,
4,5-dimethyl-; 1,6-hexanediol, 2,2-dimethyl-; 1,6-hexanediol, 2,3-dimethyl-;
1,6-
hexanedioi, 2,4-dimethyl-; 1,6-hexanediol, 2,5-dimethyl-; 1,6-hexanediol, 3,3-
dimethyl-;
1,6-hexanediol, 3,4-dimethyl-; 2,4-hexanediol, 2.3-dimethyl-; 2,4-hexanediol,
2,4-
dimethyl-; 2,4-hexanediol, 2,5-dimethyl-; 2,4-hexanediol, 3.3-dimethyl-; 2,4-
hexanediol,
3,4-dimethyl-; 2,4-hexanediol, 3,5-dimethyl-; '?,4-hexanediol, 4,5-dimethyl-;
2,4
hexanediol, 5,5-dimethyl-; 2.5-hexanediol, 2,3-dimethyl-; 2,5-hexanediol, 2,4-
dimethyl-;
2,5-hexanediol, 2,5-dimethyl-; 2,5-hexanediol, 3,3-dimethyl-: 2,5-hexanediol,
3,4
dimethyl-; 2,6-hexanediol, 3,3-dimethyl-; 1,3-hexanediol, 2-ethyl-; 1,3-
hexanediol, 4-
ethyl-; 1,4-hexanediol, 2-ethyl-; 1,4-hexanediol, 4-ethyl-; 1,5-hexanediol, 2-
ethyl-; 2,4-
hexanediol, 3-ethyl-; 2,4-hexanediol, 4-ethyl-; 2,5-hexanediol, 3-ethyl-; 1,3-
heptanediol,
2-methyl-; 1,3-heptanediol, 3-methyl-; 1,3-heptanediol, 4-methyl-; 1,3-
heptanediol, 5-
methyl-; I,3-heptanediol, 6-methyl-; 1,4-heptanediol, 2-methyl-; 1,4-
heptanediol, 3-
methyl-; 1,4-heptanediol, 4-methyl-; 1,4-heptanediol, 5-methyl-; 1,4-
heptanediol, 6-
methyl-; 1,5-heptanediol, 2-methyl-; 1,5-heptanediol, 3-methyl-; 1,5-
heptanediol, 4-
methyl-; 1,5-heptanediol, 5-methyl-; 1,5-heptanediol, 6-methyl-; 1,6-
heptanediol, 2-
methyl-; 1,6-heptanediol, 3-methyl-; 1,6-heptanediol, 4-methyl-; 1,6-
heptanediol, 5-
methyl-; 1,6-heptanediol, 6-methyl-; 2,4-heptanediol, 2-methyl-; 2,4-
heptanediol, 3-
methyl-; 2,4-heptanediol, 4-methyl-; 2,4-heptanediol, 5-methyl-; 2,4-
heptanediol, 6-
methyl-; 2,5-heptanediol, 2-methyl-; 2,5-heptanediol, 3-methyl-; 2,5-
heptanediol, 4-
methyl-; 2,5-heptanediol, 5-methyl-; 2,5-heptanediol, 6-methyl-; 2,6-
heptanediol, 2-
CA 02260920 1999-O1-19
WO 98/03619 PCT/US97105097
18
methyl-; 2.6-heptanediol, 3-methyl-; 2.6-heptanediol, 4-methyl-; 3,4-
heptanediol, 3-
methyl-; 3.5-heptanediol, 2-methyl-; 3,5-heptanediol, 3-methyl-; 3,5-
heptanediol, 4-
methyl-; 2,4-octanediol; 2,5-octanediol; 2,6-octanediol; 2,7-octanediol; 3,5-
octanediol;
and/or 3,6-octanediol;
V. nonane diol isomers including: 2,4-pentanediol, 2,3.3,4-tetramethyl-; 2,4-
pentanediol, 3-tertiarybutyl-; 2,4-hexanediol, 2,5,5-trimethyl-; 2,4-
hexanediol, 3.3.4-
trimethyl-; 2,4-hexanediol. 3,3,5-trimethyl-; 2,4-hexanediol, 3,5.5-trimethyl-
; 2,4-
hexanediol, 4,5.5-trimethyl-; 2,5-hexanediol, 3,3,4-trimethyl-; and/or 2,5-
hexanediol.
3,3,5-trimethyl-;
VI. glyceryl ethers and/or di(hydroxyalkyl)ethers including: 1,2-propanediol,
3-{n-
pentyloxy)-; 1,2-propanediol, 3-(2-pentyloxy)-; 1,2-propanediol, 3-(3-
pentyloxy)-; 1,2-
propanediol, 3-(2-methyl-1-butyloxy}-; 1.2-propanediol, 3-(iso-amyloxy)-; 1,2-
propanediol, 3-(3-methyl-2-butyioxy)-: I,2-propanediol, 3-(cyclohexyloxy)-;
I,2-
propanediol, 3-(1-cyclohex-I-enyloxy)-; 1,3-propanediol, 2-(pentyloxy)-; 1,3-
propanediol, 2-(2-pentyloxy)-; I,3-propanediol, 2-(3-pentyloxy)-; 1,3-
propanediol, 2-(2-
methyl-I-butyloxy)-; I,3-propanediol, 2-(iso-amyloxy)-; I,3-propanediol, 2-(3-
methyl-2-
butyloxy)-; I,3-propanediol, 2-(cyclohexyloxy)-; 1,3-propanediol, 2-(1-
cyclohex-1-
enyloxy}-; I,2-propanediol, 3-(butyloxy)-, triethoxylated; 1.2-propanediol, 3-
(butyloxy)-,
tetraethoxylated; 1,2-propanediol, 3-(butyloxy)-, pentaethoxylated; I,2-
propanediol, 3-
(butyloxy)-, hexaethoxylated; 1,2-propanediol, 3-(butyloxy)-,
heptaethoxylated; 1,2-
propanediol, 3-(butyloxy)-, octaethoxylated; 1.2-propanediol, 3-(butyloxy)-,
nonaethoxylated; 1,2-propanediol, 3-(butyloxy)-, monopropoxylated; 1,2-
propanediol, 3-
(butyioxy)-, dibutyleneoxylated; 1,2-propanediol, 3-(butyloxy)-,
tributyleneoxylated; 1,2-
propanedior 3-phenyloxy-; 1,2-propanediol, 3-benzyloxy-; I,2-propanediol, 3-(2-
phenylethyloxy)-; 1,2-propanediol, 3-(1-phenyl-2-propanyloxy)-; 1,3-
propanediol, 2-
phenyloxy-; 1,3-propanediol, 2-(m-cresyloxy)-; 1,3-propanedioI, 2-(p-
cresyloxy}-; 1,3-
propanediol, -benzyloxy-; 1,3-propanediol, 2-(2-phenylethyloxy)-; 1,3-
propanediol, 2-(I-
phenylethyloxy)-; bis(2-hydroxybutyl)ether; and/or bis(2-
hydroxycyclopentyl)ether;
VII. saturated and unsaturated alicyclic diols and their derivatives
including:
(a) the saturated diols and their derivatives, including:
1-isopropyl-1,2-cyclobutanediol; 3-ethyl-4-methyl-I,2-cyclobutanediol; 3-
propyl-1,2-
cyclobutanediol; 3-isopropyl-1,2-cyclobutanediol; 1-ethyl-I,2-
cyclopentanediol; 1,2-
dimethyl-1,2-cyclopentanediol; 1,4-dimethyl-1,2-cyclopentanediol; 2,4,5-
trimethyl-1,3-
cyclopentanediol; 3,3-dimethyl-1,2-cyclopentanediol; 3,4-dimethyl-1,2-
cyclopentanediol;
3,5-dimethyl-1,2-cyclopentanediol; 3-ethyl-I,2-cyclopentanediol; 4,4-dimethyl-
1,2-
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WO 98/03619 PCT/US97/05097
19
cyclopentanediol; 4-ethyl-1,2-cyclopentanediol; I,1-
bis(hydroxymethyl)cyclohexane; 1,2-
bis(hydroxymethyl)cyclohexane; 1,2-dimethyl-1.3-cyclohexanediol; 1,3-
bis(hydroxymethyl)cyclohexane; 1,3-dimethyl-1,3-cyclohexanediol; 1,6-dimethyl-
1.3-
cyclohexanediol; 1-hydroxy-cyclohexaneethanol; 1-hydroxy-cyclohexanemethanol:
I-
ethyl-1,3-cyclohexanediol; 1-methyl-1,2-cyclohexanediol; 2.2-dimethyl-1,3-
cyclohexanediol; 2,3-dimethyl-1,4-cyclohexanediol; 2,4-dimethyl-1,3-
cyclohexanediol;
2,5-dimethyl-1,3-cyclohexanediol; 2,6-dimethyl-1,4-cyclohexanediol; 2-ethyl-
I,3-
cyclohexanediol; 2-hydroxycyclohexaneethanol; 2-hydroxyethyl-1-cyclohexanol; 2-
hydroxymethylcyclohexanol; 3-hydroxyethyl-1-cyclohexanol; 3-
hydroxycyclohexaneethanol; 3-hydroxymethylcyclohexanol; 3-methyl-1,2-
cyclohexanediol; 4,4-dimethyl-1,3-cyclohexanediol; 4,S-dimethyl-1,3-
cyclohexanediol;
4,6-dimethyl-1,3-cyclohexanediol; 4-ethyl-1,3-cyclohexanediol; 4-hydroxyethyl-
1-
cyclohexanol; 4-hydroxymethylcyclohexanol; 4-methyl-1,2-cyclohexanediol; 5,5-
dimethyl-1,3-cyclohexanediol; 5-ethyl-1,3-cyclohexanediol; 1.2-
cycloheptanediol; 2-
methyl-1,3-cycloheptanediol; 2-methyl-1,4-cycloheptanediol; 4-methyl-1,3-
cycloheptanediol; 5-methyl-1,3-cycloheptanediol; S-methyl-1,4-
cycloheptanediol; 6-
methyl-1,4-cycloheptanediol; ; 1,3-cyclooctanediol; 1,4-cyclooctanediol; 1,5-
cyclooctanediol; 1,2-cyclohexanediol, diethoxyiate; 1,2-cyclohexanediol,
triethoxylate;
1,2-cyclohexanediol, tetraethoxylate; 1,2-cyclohexanediol, pentaethoxylate;
1,2-
cyclohexanediol, hexaethoxylate; 1,2-cyclohexanediol, heptaethoxylate; 1,2-
cyclohexanediol, octaethoxylate; 1,2-cyclohexanediol, nonaethoxylate; 1,2-
cyclohexanediol, monopropoxylate; 1,2-cyclohexanediol, monobutylenoxylate; I,2-
cyclohexanediol, dibutylenoxylate; and/or 1,2-cyclohexanediol,
tributylenoxylate; and
(b). the unsaturated alicyclic diols including: 1,2-cyclobutanediol, I-ethenyl-
2-ethyl-; 3-
cyclobutene-1,2-diol, 1,2,3,4-tetramethyl-; 3-cyclobutene-1,2-diol, 3,4-
diethyl-; 3-
cyclobutene-1,2-diol, 3-(1,1-dimethylethyl)-; 3-cyclobutene-1,2-diol, 3-butyl-
; 1,2-
cyclopentanediol, 1,2-dimethyl-4-methylene-; 1,2-cyclopentanediol, 1-ethyl-3-
methylene-
1,2-cyclopentanediol, 4-(1-propenyl); 3-cyclopentene-1,2-diol, I-ethyl-3-
methyl-; 1,2
cyclohexanediol, 1-ethenyl-; 1,2-cyclohexanediol, 1-methyl-3-methylene-; 1,2
cyclohexanediol, 1-methyl-4-methylene-; 1,2-cyclohexanediol, 3-ethenyl-; 1,2
cyclohexanediol, 4-ethenyl-; 3-cyclohexene-1,2-diol, 2,6-dimethyl-; 3-
cyclohexene-1,2-
diol, 6,6-dimethyl-; 4-cyclohexene-1,2-diol, 3,6-dimethyl-; 4-cyclohexene-1,2-
diol, 4,5-
dimethyl-; 3-cyclooctene-1,2-diol; 4-cyclooctene-I,2-diol; and/or 5-
cyclooctene-I,2-diol;
VIII. Alkoxylated derivatives of C3-g diols [In the following disclosure, "EO"
means
polyethoxylates, i.e., -(CH2CH20)nH; Me-En means methyl-capped polyethoxylates
-
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WO 98/03619 PCT/U597/05097
(CH2CH20)nCH3 ; "2(Me-En)" means 2 Me-En groups needed; "PO" means
polypropoxylates, -(CH(CH3)CH20)nH ; "BO" means polybutyleneoxy groups,
(CH(CH2CH3)CH20)nH ; and "n-BO" means poly(n-butyleneoxy) or
poly(tetramethylene)oxy groups -(CH2CH2CH2CH20)nH. The use of the term "{Cx)"
5 herein refers to the number of carbon atoms in the base material which is
alkoxylated.]
including:
1. 1,2-propanediol (C3) 2(Me-EI_4); 1,2-propanediol (C3) P04; 1,2-
propanediol, 2-methyl- (C4) (Me-Eq,_ 10); I,2-propanediol, 2-methyl- (C4) 2(Me-
E I ); I ,~
propanediol, 2-methyl- (C4) P03; 1,2-propanediol, 2-methyl- (C4) BOI; 1,3-
propanediol
10 (C3) 2(Me-E6_g); I,3-propanediol (C3) POS_6; I,3-propanediol, 2,2-diethyl-
(C7) EI_~;
1,3-propanediol, 2,2-diethyl- (C7) POI; 1,3-propanediol, 2,2-diethyl- (C7) n-
BOI_2; 1,3-
propanediol, 2,2-dimethyi- (C~) 2(Me EI_2); 1,3-propanediol, 2,2-dimethyl-
(CS) P03_4;
1,3-propanediol, 2-(I-methylpropyl)- (C7) EI_7; 1,3-propanediol, 2-(I-
methylpropyl)-
(C7) PO1; 1,3-propanediol, 2-(1-methylpropyl)- (C7) n-BOI_2; 1,3-propanediol,
2-(2-
15 methylpropyl)- (C7) EI_~; 1,3-propanediol, 2-(2-methylpropyl}- (C7) POI;
1,3-
propanediol, 2-(2-methylpropyl)- (C7) n-BOI_2; I,3-propanediol, 2-ethyl- (CS)
(Me E6_
_ 10)~ 1,3-propanediol, 2-ethyl- (CS) 2(Me EI); I,3-propanediol, 2-ethyl- (CS)
P03; i,3
propanediol, 2-ethyl-2-methyl- (C6) (Me EI_6); 1,3-propanediol, 2-ethyl-2-
methyl- (C6)
P02; 1,3-propanediol, 2-ethyl-2-methyl- (C6) BOI; 1,3-propanediol, 2-isopropyl-
(C6)
20 (Me EI_6); 1,3-propanediol, 2-isopropyl- (C6) P02; 1,3-propanediol, 2-
isopropyl- (C6)
BOI; 1,3-propanediol, 2-methyl- (C4) 2(Me E2_5); 1,3-propanediol, 2-methyl-
(C4) P04_
5; 1,3-propanediol, 2-methyl- (C4) B02; 1,3-propanediol, 2-methyl-2-isopropyl-
(C7)
E2_9; 1,3-propanediol, 2-methyl-2-isopropyl- (C7) POI; I,3-propanediol, 2-
methyl-2-
isopropyl- -(C7) n-BO1_3; 1,3-propanediol, 2-methyl-2-propyl- (C7) E1_7; 1,3-
propanediol, 2-methyl-2-propyl- (C7) POI; 1,3-propanediol, 2-methyl-2-propyl-
(C7) n-
BO1_2; 1,3-propanediol, 2-propyl- (C6) (Me EI_4); 1,3-propanediol, 2-propyl-
(C6) P02;
1,3-propanediol, 2-propyl- (C6) BOI;
2. 1,2-butanediol (C4) (Me E2_g); 1,2-butanediol (C4) P02_3; 1,2-butanediol
(C4) BO1; 1,2-butanediol, 2,3-dimethyl- (C6) EI_6; 1,2-butanediol, 2,3-
dimethyl- (C6) n
BO1 _2; I,2-butanediol, 2-ethyl- (C6) E I _3; 1,2-butanediol, 2-ethyl- (C6) n-
BO I ; 1,2
butanediol, 2-methyl- (CS) (Me E1_2); 1,2-butanediol, 2-methyl- (CS) POI; 1,2-
butanediol, 3,3-dimethyl- (C6) E1_6; 1,2-butanediol, 3,3-dimethyl- (C6) n-
BOI_2; 1,2-
butanediol, 3-methyl- (CS) (Me E1_2); 1,2-butanediol, 3-methyl- (CS) POI; 1,3-
butanediol (C4) 2(Me E3_6); I,3-butanediol (C4) POS; 1,3-butanediol (C4) B02;
1,3-
butanediol, 2,2,3-trimethyl- (C7) (Me E1_3); I,3-butanediol, 2,2,3-trimethyl-
(C7) POI-2~
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1,3-butanediol, 2,2-dimethyl- (C6) (Me E3_g); I.3-butanediol. 2,2-dimethyl-
(C6) P03;
1,3-butanediol, 2.3-dimethyl- (C6) (Me E3_g); 1,3-butanediol, 2,3-dimethyl-
(C6) P03;
1,3-butanediol, 2-ethyl- (C6) (Me EI_6); 1,3-butanediol, 2-ethyl- (C6) P02_3;
1,3-
butanediol, 2-ethyl- (C6) BO1; 1,3-butanediol, 2-ethyl-2-methyl- (C7) (Me EI);
I,3-
butanediol, 2-ethyl-2-methyl- (C7) POI; 1,3-butanediol, 2-ethyl-2-methyl- (C7)
n-B02_4;
1,3-butanediol, 2-ethyl-3-methyl- {C7) (Me EI); 1,3-butanediol. 2-ethyl-3-
methyl- (C7)
POI; I,3-butanediol, 2-ethyl-3-methyl- (C7) n-B02_4; I,3-butanediol, 2-
isopropyl- (C7)
(Me EI); 1,3-butanediol, 2-isopropyl- (C7) PO1; I,3-butanediol, 2-isopropyl-
(C7) n
B02_4; 1.3-butanediol, 2-methyl- (CS) 2(Me EI_3); 1,3-butanediol, 2-methyl-
(CS) P04;
1,3-butanediol, 2-propyl- (C7) E2_9; 1,3-butanediol, 2-propyl- (C7) POI; 1,3-
butanediol,
2-propyl- (C7) n-BOI _3; I ,3-butanediol, 3-methyl- (C5) 2(Me E I _3 ); 1,3-
butanediol, 3-
methyl- (CS) P04; 1,4-butanediol (C4) 2(Me E~_4); I,4-butanediol (C4) P04_~;
1,4-
butanediol (C4) B02; 1,4-butanediol, 2,2,3-trimethyl- (C7) E2_9; 1.4-
butanediol, 2,2,3-
trimethyl- (C7) POI ; 1,4-butanediol, 2,2,3-trimethyl- (C7) n-BO I _3; 1,4-
butanediol, 2,2-
15. dimethyl- (C6) (Me EI_6); 1,4-butanediol, 2,2-dimethyl- (C6) P02; 1,4-
butanediol, 2,2-
dimethyl- (C6) BOI; 1,4-butanediol, 2,3-dimethyl- (C6) (Me EI_6); 1,4-
butanediol, 2,3-
dimethyl- (C6) P02; 1,4-butanediol, 2,3-dimethyl- (C6) BO I ; 1,4-butanediol,
2-ethyl-
(C6) (Me E I _4); 1,4-butanediol, 2-ethyl- (C6) P02; 1,4-butanediol, 2-ethyl-
(C6) BO I ;
1,4-butanediol, 2-ethyl-2-methyl- (C7) E I _~: 1,4-butanediol, 2-ethyl-2-
methyl- (C7) POI ;
1,4-butanediol, 2-ethyl-2-methyl- (C7) n-BOI _2; I ,4-butanediol. 2-ethyl-3-
methyl- (C7)
EI_~; 1,4-butanediol, 2-ethyl-3-methyl- (C7) POI; 1,4-butanediol, 2-ethyl-3-
methyl- (C7)
n-BOI_2; 1,4-butanediol, 2-isopropyl- (C7) EI_~; 1,4-butanediol. 2-isopropyl-
(C7) POI;
1,4-butanediol, 2-isopropyl- (C7) n-BOI_2; 1,4-butanediol, 2-methyl- (CS) {Me
E6_10);
1,4-butanediol, 2-methyl- (CS) 2(Me EI); 1,4-butanediol, 2-methyl- (CS) P03;
1,4-
butanediol, 2-methyl- (CS) BOI; 1,4-butanediol, 2-propyl- (C7) EI_S; 1,4-
butanediol, 2-
propyl- (C7) n-BOI_2; 1,4-butanediol, 3-ethyl-I-methyl- (C7) E2_9; I,4-
butanediol, 3-
ethyl-1-methyl- (C7) POI; 1,4-butanediol, 3-ethyl-I-methyl- (C7) n-BOI_3; 2,3-
butanediol (C4) (Me E6_10); 2,3-butanediol (C4) 2(Me EI); 2,3-butanediol (C4)
P03_4
2,3-butanediol (C4) BOI; 2,3-butanediol, 2,3-dimethyl- (C6) E3_9; 2,3-
butanediol, 2,3-
dimethyl- (C6) POI; 2,3-butanediol, 2,3-dimethyl- (C6) n-BOI_3; 2,3-
butanediol, 2-
methyl- (CS) (Me EI_5); 2,3-butanediol, 2-methyl- (CS) P02; 2,3-butanediol, 2-
methyl-
(CS) BOI;
3. 1,2-pentanediol (CS) E3_10: 1,2-pentanediol, (C~) POI; 1,2-pentanediol,
(CS) n-B02_3; 1,2-pentanediol, 2-methyl (C6) E1_3; 1,2-pentanedioI, 2-methyl
(C6) n
BO I ; 1,2-pentanediol, 2-methyl (C6) BO 1; 1,2-pentanediol, 3-methyl (C6) E 1
_3; 1,2
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pentanediol, 3-methyl (C6) n-BOI; 1,2-pentanediol, 4-methyl (C6) EI_3; 1,2-
pentanediol,
4-methyl (C6) n-BOI ; 1,3-pentanediol (CS) 2(Me-E I _~); I ,3-pentanediol (CS)
P03_4;
1,3-pentanediol, 2,2-dimethyl- (C7) (Me-EI); 1,3-pentanediol, 2.2-dimethyl-
(C7) POI;
1,3-pentanediol, 2,2-dimethyl- (C7) n-B02_4; I,3-pentanediol, 2,3-dimethyl-
(C7) (Me-
E1); I,3-pentanediol, 2,3-dimethyl- (C7) POI; 1,3-pentanediol, 2.3-dimethyl-
(C7) n-
BO2_4; 1,3-pentanediol, 2,4-dimethyl- (C7) (Me-EI); 1,3-pentanediol, 2.4-
dimethyl- (C7)
PO I ; I ,3-pentanediol, 2,4-dimethyl- (C7) n-B02_4; 1,3-pentanediol, 2-ethyl-
(C7) E2_9;
1,3-pentanediol, 2-ethyl- (C7) POI; I,3-pentanediol, 2-ethyl- (C7) n-BOI_3;
1,3-
pentanediol, 2-methyl- (C6) 2(Me-EI_6); 1,3-pentanediol, 2-methyl- (C6) PO~_3;
1,3-
pentanediol, 2-methyl- (C6) BOI; 1,3-pentanediol, 3,4-dimethyl- (C7) (Me-EI);
1,3-
pentanediol, 3,4-dimethyl- (C7) POI; 1,3-pentanediol, 3,4-dimethyl- (C7) n-
B02_4; 1,3-
pentanediol, 3-methyl- (C6) (Me-EI_6); 1,3-pentanediol, 3-methyl- (C6) P02_3;
1,3-
pentanediol, 3-methyl- (C6) BOI; 1,3-pentanediol, 4,4-dimethyl- (C7) {Me-EI);
1,3-
pentanediol, 4,4-dimethyl- (C7) POI; 1,3-pentanediol, 4,4-dimethyl- (C7) n-
B02_4; 1,3-
pentanediol, 4-methyl- (C6) (Me-EI_6); 1,3-pentanediol, 4-methyl- (C6) P02_3;
1,3-
pentanediol, 4-methyl- (C6) BOI; 1,4-pentanediol, (C5) 2(Me-EI_2); 1,4-
pentanediol
(CS) P03_4; 1,4-pentanediol, 2,2-dimethyl- (C7) (Me-EI ); 1,4-pentanediol, 2,2-
dimethyl-
(C7) POI; 1,4-pentanediol, 2,2-dimethyl- (C7) n-B02_4; 1.4-pentanediol, 2,3-
dimethyl-
(C7) (Me-EI); 1,4-pentanediol, 2,3-dimethyl- (C7) POI; 1.4-pentanediol, 2,3-
dimethyl-
(C7) n-B02_4; 1,4-pentanediol, 2,4-dimethyl- (C7) (Me-EI ); 1,4-pentanediol,
2,4-
dimethyl- (C7) POI; 1,4-pentanediol, 2,4-dimethyl- (C7) n-B02_4; 1,4-
pentanediol, 2-
methyl- (C6) (Me-EI_6); 1,4-pentanediol, 2-methyl- (C6) P02_3; 1,4-
pentanediol, 2-
methyl- (C6) BOI; 1,4-pentanediol, 3,3-dimethyl- (C7) (Me-EI); 1,4-
pentanediol, 3,3-
dimethyl- (e7) POI; 1,4-pentanediol, 3,3-dimethyl- (C7) n-B02_4; 1,4-
pentanediol, 3,4-
dimethyl- (C7) (Me-EI); 1,4-pentanediol, 3,4-dimethyl- (C7) POI; 1,4-
pentanediol, 3,4-
dimethyl- (C7) n-B02_4; I,4-pentanediol, 3-methyl- (C6) 2{Me-EI_6); 1,4-
pentanediol,
3-methyl- (C6) P02_3; 1,4-pentanediol, 3-methyl- (C6) BOI; 1,4-pentanediol, 4-
methyl-
(C6) 2(Me-EI_6); 1,4-pentanediol, 4-methyl- (C6) P02_3; 1,4-pentanediol, 4-
methyl-
(C6) BOI; 1,5-pentanediol, (CS) (Me-E4_10); I,5-pentanediol (CS) 2(Me-EI); 1,5-
pentanediol (CS) P03; 1,5-pentanediol, 2,2-dimethyl- (C7) EI_~; 1,5-
pentanediol, 2,2-
dimethyl- (C7) PO1; 1,5-pentanediol, 2,2-dimethyl- (C7) n-BOI_2; I,5-
pentanediol, 2,3-
dimethyl- (C7) E1_~; 1,5-pentanediol, 2,3-dimethyl- (C7) POI; I,5-pentanediol,
2,3-
dimethyl- (C7) n-BOI_2; 1,5-pentanediol, 2,4-dimethyl- (C7) EI_7; 1,5-
pentanediol, 2,4-
dimethyl- (C7) POI; 1,5-pentanediol, 2,4-dimethyl- (C7) n-BOI_2; 1,5-
pentanediol, 2-
ethyl- (C7) E I _5; 1,5-pentanediol, 2-ethyl- (C7) n-BO I _2; I ,5-
pentanediol, 2-methyl-
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(C6) (Me-E I _,~); I ,5-pentanediol, 2-methyl- (C6) P02; I ,5-pentanediol, 3.3-
dimethyl-
(C7) EI_~: 1,5-pentanediol, 3,3-dimethyl- (C7) POI; 1,5-pentanediol, 3,3-
dimethyl- (C7)
n-BOI _~; 1,5-pentanediol, 3-methyl- (C6) (Me-E I _4); 1,5-pentanediol, 3-
methyl- (C6)
P02; 2.3-pentanediol, (C5) (Me-E1_3); 2,3-pentanediol, (CS) P02; 2,3-
pentanediol, 2-
methyl- (C6) EI_7; 2,3-pentanediol, 2-methyl- (C6) POI; 2,3-pentanediol, 2-
methyl- (C6)
n-BOI _2; 2,3-pentanediol, 3-methyl- (C6) E I _7; 2,3-pentanediol, 3-methyl-
(C6) PO I ;
2,3-pentanediol, 3-methyl- (C6) n-BOI _2; 2,3-pentanediol, 4-methyl- (C6) E I
_7; 2,3-
pentanediol, 4-methyl- (C6) POI ; 2,3-pentanediol, 4-methyl- (C6) n-BOI _z;
2,4-
pentanediol, (CS) 2(Me-E~_4); 2,4-pentanediol (C5) P04; 2,4-pentanediol, 2,3-
dimethyl-
I0 (C7) {Me-E I _4); 2,4-pentanediol, 2,3-dimethyl- (C7) P02; 2,4-pentanediol,
2,4-dimethyl-
(C7) (Me-E I _4); 2,4-pentanediol, 2,4-dimethyl- (C7) P02; 2,4-pentanediol, 2-
methyl-
{C7) (Me-ES_10); 2,4-pentanediol, 2-methyl- (C7) P03; 2,4-pentanediol, 3.3-
dimethyl-
(C7) (Me-E1_4); 2,4-pentanedioI, 3,3-dimethyl- (C7) P02; 2,4-pentanediol, 3-
methyl-
(C6) (Me-E5_10); 2,4-pentanediol, 3-methyl- (C6) P03;
4. 1,3-hexanediol (C6) (Me-E1_5); 1,3-hexanediol (C6) P02; 1,3-hexanediol
(C6) BOI; 1,3-hexanediol, 2-methyl- (C7) E2_9; 1,3-hexanediol,. 2-methyl- (C7)
POI;
1,3-hexanediol, 2-methyl- (C7) n-B01_3; I,3-hexanediol, 2-methyl- (C7) BOI;
1,3-
hexanediol, 3-methyl- (C7) E2_9; 1,3-hexanediol, 3-methyl- (C7) POI; 1,3-
hexanediol, 3-
methyl- (C7) n-BO1_3; 1,3-hexanediol, 4-methyl- (C7) E2_9; 1,3-hexanediol, 4-
methyl-
(C7) POI; 1,3-hexanediol, 4-methyl- (C7) n-BO1_3; 1,3-hexanediol, 5-methyl-
(C7) E2_
g; 1,3-hexanediol, 5-methyl- (C7) POI; 1,3-hexanediol, 5-methyl- (C7) n-BO1_3;
1,4-
hexanediol (C6) (Me-EI_5); 1,4-hexanediol (C6) P02; 1,4-hexanediol (C6) BOI;
1,4-
hexanediol, 2-methyl- (C7) E2_9; 1,4-hexanediol, 2-methyl- (C7) POI; 1,4-
hexanediol, 2-
methyl- (C7) n-BOI_3; 1,4-hexanediol, 3-methyl- (C7) E2_9; 1,4-hexanediol, 3-
methyl-
(C7) POI; 1,4-hexanediol, 3-methyl- (C7) n-BOI_3; 1,4-hexanediol, 4-methyl-
(C7) E~_
9; 1,4-hexanediol, 4-methyl- (C7) POI; 1,4-hexanediol, 4-methyl- {C7) n-BOI_3;
1,4-
hexanediol, 5-methyl- (C7) E2_9; 1,4-hexanediol, 5-methyl- (C7) POI; 1,4-
hexanediol, 5-
methyl- (C7) n-BOI_3; 1,5-hexanediol (C6) (Me-EI_5); 1,5-hexanediol (C6) P02;
1,5-
hexanediol (C6) BOI; 1,5-hexanediol, 2-methyl- (C7) E2_9; 1,5-hexanediol, 2-
methyl-
(C7) POI; 1,5-hexanediol, 2-methyl- (C7) n-BOI_3; 1,5-hexanediol, 3-methyl-
(C7) E~_
g; 1,5-hexanediol, 3-methyl- (C7) POI; 1,5-hexanediol, 3-methyl- (C7) n-BOI_3;
1,5-
hexanediol, 4-methyl- (C7) E2_9; 1,5-hexanediol, 4-methyl- (C7) POI; 1,5-
hexanediol, 4-
methyl- (C7) n-BO1_3; 1,5-hexanediol, 5-methyl- (C7) E2_9; 1,5-hexanediol, 5-
methyl-
(C7) PO I ; 1,5-hexanediol, 5-methyl- (C7) n-BOI _3; 1,6-hexanediol (C6) (Me-E
I _2); 1,6-
hexanediol (C6) POI_2; 1,6-hexanediol (C6) n-B04; 1,6-hexanediol, 2-methyl-
(C7) EI_
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24
5; I ,6-hexanediol, 2-methyl- (C7) n-BO I _~; 1,6-hexanediol. 3-methyl- (C7) E
1 _5; I .6-
hexanediol, 3-methyl- (C7) n-BO 1 _2: 2.3-hexanediol (C6) E I _5; 2,3-
hexanediol (C6) n-
BO 1; 2,3-hexanediol (C6) BOI ; 2,4-hexanediol (C6) (Me-E3_g); 2,4-hexanediol
(C6)
P03; 2,4-hexanediol, 2-methyl- (C7) (Me-EI_2); 2,4-hexanediol 2-methyl- (C7)
POI-~;
2,4-hexanediol, 3-methyl- (C7) (Me-EI_2); 2,4-hexanediol 3-methyl- (C7) POI_2;
2,4-
hexanediol, 4-methyl- (C7) (Me-E I _2}; 2,4-hexanediol 4-methyl- (C7) PO I _2;
2,4-
hexanediol, 5-methyl- (C7) (Me-E1_2); 2,4-hexanediol 5-methyl- (C7) POI_2; 2,5-
hexanediol (C6) (Me-E3_g); 2,5-hexanediol (C6) P03; 2,5-hexanediol, 2-methyl-
(C7)
(Me-EI_2}; 2,5-hexanediol 2-methyl- (C7) POI_2; 2,5-hexanediol, 3-methyl- (C7)
(Me-
E I _2); 2,5-hexanediol 3-methyl- (C7) PO I _2; 3,4-hexanediol (C6) EO I _5;
3,4-hexanediol
(C6) n-BOI; 3,4-hexanediol (C6) BOI;
5. 1,3-heptanediol (C7) EI_7; 1,3-heptanediol (C7) PO1; 1,3-heptanediol
(C7) n-BO1_2; 1,4-heptanediol (C7) E1_7; 1,4-heptanediol (C7) PO1; I,4-
heptanediol
(C7) n-BOI_2; 1,5-heptanediol (C7) EI_7; 1,5-heptanediol (C7) POI; I,5-
heptanediol
(C7) n-BOI _2; 1,6-heptanediol (C7) E I _7; I ,6-heptanediol (C7) POI ; 1,6-
heptanediol
(C7) n-BOI_2; 1,7-heptanedioi (C7) EI_2; I,7-heptanediol (C7) n-BO1; 2,4-
heptanediol
(C7) E3_10; 2,4-heptanediol (C7) (Me-EI); 2,4-heptanediol (C7) POI; 2,4-
heptanediol
(C7) n-B03; 2,5-heptanediol (C7) E3_ 10; 2,5-heptanediol (C7) {Me-EI ); 2,5-
heptanediol
(C7) POI; 2,5-heptanediol (C7) n-B03; 2,6-heptanediol (C7} E3_10; 2,6-
heptanediol
(C7.) (Me-EI); 2,6-heptanediol (C7) PO1; 2,6-heptanediol (C7) n-B03; 3,5-
heptanediol
(C7) E3_10; 3,5-heptanediol (C7) (Me-EI); 3,5-heptanediol (C7) POI; 3,5-
heptanediol
(C7) n-B03;
6. 1,3-butanediol, 3-methyl-2-isopropyl- (C8) PO1; 2,4-pentanediol, 2,3.3
trimethyl- (C8) PO1; 1,3-butanediol, 2,2-diethyl- (C8) E2_5; 2,4-hexanediol,
2,3
dimethyl- (C8) E2_5; 2,4-hexanediol, 2,4-dimethyl- (C8) E2_~; 2,4-hexanediol,
2,5
dimethyl- (C8) E2_5; 2,4-hexanediol, 3,3-dimethyl- (C8) E2_5; 2,4-hexanediol,
3,4-
dimethyl- {C8) E2_5; 2,4-hexanediol, 3,5-dimethyl- (C8) E2_5; 2,4-hexanediol,
4,5-
dimethyl- (C8) E2_5; 2,4-hexanediol, 5,5-dimethyl- (C8) E2_5; 2,5-hexanediol,
2,3-
dimethyl- (C8) E2_5; 2,5-hexanediol, 2,4-dimethyl- (C8) E2_5; 2,5-hexanediol,
2,5-
dimethyl- (C8) E2_5; 2,5-hexanediol, 3,3-dimethyl- (C8) E2_5; 2,5-hexanediol,
3,4-
dimethyl- (C8) E2_5; 3,5-heptanediol, 3-methyl- (C8) E2_5; I,3-butanediol, 2,2-
diethyl-
(C8) n-BOI_2; 2,4-hexanediol, 2,3-dimethyl- (C8) n-BOI_2; 2,4-hexanediol, 2,4-
dimethyl- (C8) n-BOI _2; 2,4-hexanediol, 2,5-dimethyl- (C8) n-BOI _2; 2,4-
hexanediol,
3,3-dimethyl- (C8) n-BO1_2; 2,4-hexanediol, 3,4-dimethyl- (C8) n-BOI_2; 2,4-
hexanediol, 3,5-dimethyl- (C8) n-BOl_2; 2,4-hexanediol, 4,5-dimethyl- {C8) n-
BOI_2;
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2,4-hexanediol. ~,~-dimethyl-, n-BOI _2; 2,5-hexanediol, 2,3-dimethyl- (C8) n-
BOI _2;
2.~-hexanediol. 2.4-dimethyl- (C8) n-BOI _2; 2,5-hexanediol, 2,~-dimethyl-
(C8) n-BOI _
2; 2.~-hexanediol, 3,3-dimethyl- (C8) n-BOI_2; 2,~-hexanediol, 3,4-dimethyl-
(C8) n-
BOI _2; 3,5-heptanediol, 3-methyl- (C8) n-BOI _2; 1,3-propanediol, 2-( 1.2-
5 dimethylpropyl)- (C8) n-BOI; I,3-butanediol, 2-ethyl-2,3-dimethyl- (C8) n-
BOI; 1,3-
butanediol, 2-methyl-2-isopropyl- (C8) n-BOI; I,4-butanediol, 3-methyl-2-
isopropyl-
(C8) n-BOI; I,3-pentanediol, 2,2,3-trimethyl- (C8) n-BOI; I,3-pentanediol,
~,2,4-
trimethyl- (C8) n-BOI; I,3-pentanediol, 2,4,4-trimethyl- (C8) n-BOI; 1,3-
pentanediol.
3,4,4-trimethyl- (C8) n-BOI; 1,4-pentanediol, 2,2,3-trimethyl- (C8) n-BOI; 1,4-
10 pentanediol, 2.2.4-trimethyl- (C8) n-BOI; 1,4-pentanediol, 2.3,3-trimethyl-
(C8) n-BOI;
1,4-pentanediol, 2,3,4-trimethyl- (C8) n-BOI; I,4-pentanediol, 3,3,4-trimethyl-
(C8) n-
BOI; 2,4-pentanediol, 2,3,4-trimethyl- (C8) n-BOI; 2,4-hexanediol, 4-ethyl-
(C8) n-BOI;
2,4-heptanediol, 2-methyl- (C8) n-BO 1; 2,4-heptanediol, 3-methyl- (C8) n-BO l
; 2,4-
heptanediol, 4-methyl- (C8) n-BOI; 2,4-heptanediol, 5-methyl- (C8) n-BOI; 2,4
15 heptanediol, 6-methyl- (C8) n-BOI ; 2,5-heptanediol, 2-methyl- (C8) n-BO I
; 2,~
heptanediol, 3-methyl- (C8) n-BOI; 2,5-heptanediol, 4-methyl- (C8) n-BOI; 2,5
heptanediol, 5-methyl- (C8) n-BOI; 2,5-heptanediol, 6-methyl- (C8) n-BOI; 2,6
heptanediol, 2-methyl- (C8) n-BOI; 2,6-heptanediol, 3-methyl- (C8) n-BOI; 2,6
heptanediol, 4-methyl- (C8) n-BOI; 3,5-heptanediol, 2-methyl- (C8) n-BOI; 1,3
20 propanediol, 2-(1,2-dimethylpropyl)- (C8) EI_3; 1,3-butanediol, 2-ethyl-2,3-
dimethyl-
(C8) E 1 _3; 1,3-butanediol, 2-methyl-2-isopropyl- (C8) E I _3; I ,4-
butanediol, 3-methyl-2-
isopropyl- (C8) El_3; 1,3-pentanediol, 2,2,3-trimethyl- (C8) EI_3; 1,3-
pentanediol, 2,2,4-
trimethyl- (C8) EI_3; 1,3-pentanediol, 2,4,4-trimethyl- (C8) EI_3; 1,3-
pentanediol, 3,4,4-
trimethyl- (C8) EI_3; 1,4-pentanediol, 2,2,3-trimethyl- (C8) EI_3; 1,4-
pentanediol, 2,2,4-
25 trimethyl- (C8) EI_3; 1,4-pentanediol, 2,3,3-trimethyl- (C8) EI_3; 1,4-
pentanediol, 2,3,4-
trimethyl- (C8) EI_3; I,4-pentanediol, 3,3,4-trimethyl- (C8) EI_3; 2,4-
pentanediol, 2,3,4-
trimethyl- (C8) E I _3; 2,4-hexanediol, 4-ethyl- (C8) E I _3; 2,4-heptanediol,
2-methyl- (C8)
E I _3; 2,4-heptanediol, 3-methyl- (C8) E I _3; 2,4-heptanediol, 4-methyl-
(C8) E I _3; 2,4-
heptanediol, 5-methyl- (C8) EI_3; 2,4-heptanediol, 6-methyl- (C8) EI_3; 2,5-
heptanediol,
2-methyl- (C8) E 1 _3; 2,5-heptanediol, 3-methyl- (C8) E I _3; 2,5-
heptanediol, 4-methyl-
(C8) E I _3; 2,5-heptanediol, 5-methyl- (C8) E I _3; 2,5-heptanediol, 6-methyl-
(C8) E I -3
2,6-heptanediol, 2-methyl- (C8) EI_3; 2,6-heptanediol, 3-methyl- (C8) EI_3;
2,6-
heptanediol, 4-methyl- (C8) E I _3; and/or 3,5-heptanediol, 2-methyl- (C8) E I
_3; and
7. mixtures thereof;
CA 02260920 1999-O1-19
WO 98/03619 PCT/US97105097
26
IX. aromatic diols including: I-phenyl-1,2-ethanediol; I-phenyl-1,2-
propanediol; 2-
phenyl-1.2-propanediol; 3-phenyl-1,2-propanediol; 1-(3-methylphenyl)-I,3-
propanediol;
I-(4-methylphenyl)-1,3-propanediol; 2-methyl-I-phenyl-1,3-propanediol; 1-
phenyl-1,3-
butanediol; 3-phenyl-1,3-butanediol; I-phenyl-1,4-butanediol; 2-phenyl-1.4-
butanediol;
and/or 1-phenyl-2,3-butanediol;
X. principal solvents which are homologs, or analogs, of the above structures
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, including the following:
1,3-Propanediol, 2,2-di-2-propenyl-; 1,3-Propanediol, 2-(I-pentenyl)-; 1,3-
Propanediol,
2-(2-methyl-2-propenyl)-2-(2-propenyl)-; 1,3-Propanediol. 2-(3-methyl-1-
butenyl)-; 1.3-
Propanediol, 2-(4-pentenyl)-; 1,3-Propanediol, 2-ethyl-2-(2-methyl-2-propenyl)-
; 1,3-
Propanediol, 2-ethyl-2-(2-propenyl)-; 1,3-Propanediol, 2-methyl-2-(3-methyl-3-
butenyl)-;
1,3-Butanediol, 2.2-diallyl-; 1,3-Butanediol, 2-(1-ethyl-I-propenyl)-; 1,3-
Butanediol, 2-
(2-butenyl)-2-methyl-; 1,3-Butanediol, 2-(3-methyl-2-butenyl)-; i,3-
Butanediol, 2-ethyl-
2-(2-propenyl)-; 1,3-Butanediol, 2-methyl-2-(I-methyl-2-propenyl)-; 1,4-
Butanediol, 2,3-
bis(1-methylethylidene)-; 1,4-Butanediol, 2-(3-methyl-2-butenyl)-3-methylene-;
2-
Butene-1,4-diol, 2-(1,1-dimethylpropyl}-; 2-Butene-1.4-diol, 2-(1-
methylpropyl)-; 2-
Butene-1,4-diol, 2-butyl-; 1,3-Pentanediol, 2-ethenyl-3-ethyl-; 1,3-
Pentanediol, 2-ethenyl-
4,4-dimethyl-; 1,4-Pentanediol, 3-methyl-2-(2-propenyl}-; 1,5-Pentanediol, 2-(
I
propenyl)-; 1,5-Pentanediol, 2-(2-propenyl)-; i.5-Pentanediol, 2-ethylidene-3-
methyl-;
1,5-Pentanediol, 2-propylidene-; 2,4-Pentanediol, 3-ethylidene-2,4-dimethyl-;
4-Pentene-
1,3-diol, 2-(I,I-dimethylethyl}-; 4-Pentene-1,3-diol, 2-ethyl-2,3-dimethyl-;
1,4-
Hexanediol, 4-ethyl-2-methylene-; 1,5-Hexadiene-3,4-diol, 2,3,5-trimethyl-;
I,5-
Hexadiene-3,4-diol, 5-ethyl-3-methyl-; 1,5-Hexanediol, 2-(I-methylethenyl)-;
1,6-
Hexanediol, 2-ethenyl-; 1-Hexene-3,4-diol, 5,5-dimethyl-; 1-Hexene-3,4-diol,
5,5-
dimethyl-; 2-Hexene-1,5-diol, 4-ethenyl-2,5-dimethyl-; 3-Hexene-1,6-diol, 2-
ethenyl-2,5-
dimethyl-; 3-Hexene-1,6-diol, 2-ethyl-; 3-Hexene-1,6-diol, 3,4-dimethyl-; 4-
Hexene-2,3-
diol, 2,5-dimethyl-; 4-Hexene-2,3-diol, 3,4-dimethyl-; 5-Hexene-1,3-diol, 3-(2-
propenyl)
5-Hexene-2,3-diol, 2,3-dimethyl-; 5-Hexene-2,3-diol, 3,4-dimethyl-; 5-Hexene-
2,3-diol,
3,5-dimethyl-; 5-Hexene-2,4-dioI, 3-ethenyl-2,5-dimethyl-; 1,4-Heptanediol, 6-
methyl-5
methylene-; 1,5-Heptadiene-3,4-diol, 2,3-dimethyl-; 1,5-Heptadiene-3,4-diol,
2,5
dimethyl-; 1,5-Heptadiene-3,4-diol, 3,5-dimethyl-; 1,7-Heptanediol, 2,6-
bis(methylene)-;
1,7-Heptanedioh 4-methylene-; 1-Heptene-3,5-diol, 2,4-dimethyl-; I-Heptene-3,5-
diol.
CA 02260920 1999-O1-19
WO 98/03619 PCT/US97/05097
27
2,6-dimethyl-; 1-Heptene-3,5-diol, 3-ethenyl-~-methyl: 1-Heptene-3,~-diol, 6,6-
dimethyl-
2,4-Heptadiene-2,6-diol, 4.6-dimethyl-; 2,5-Heptadiene-1,7-diol, 4,4-dimethyl-
; 2.6-
Heptadiene-1,4-diol, 2.~,~-trimethyl-; 2-Heptene-1,4-diol, 5,6-dimethyl-; 2-
Heptene-I,S
diol, 5-ethyl-; 2-Heptene-1,7-diol, 2-methyl-; 3-Heptene-1,5-diol, 4,6-
dimethyl-; 3
Heptene-1,7-diol, 3-methyl-6-methylene-; 3-Heptene-2,5-diol, 2,4-dimethyl-; 3-
Heptene
2,5-diol, 2,5-dimethyl-; 3-Heptene-2,6-diol, 2,6-dimethyl-: 3-Heptene-2.6-
diol, 4.6-
dimethyl-; 5-Heptene-1,3-diol, 2,4-dimethyl-; 5-Heptene-1,3-diol, 3,6-dimethyl-
; S-
Heptene-1,4-diol, 2,6-dimethyl-; 5-Heptene-I,4-diol, 3,6-dimethyl-; 5-Heptene-
2,4-diol,
2,3-dimethyl-; 6-Heptene-1,3-diol, 2,2-dimethyl-; 6-Heptene-1,4-diol, 4-(2-
propenyl)-; 6-
Heptene-1,4-diol, 5,6-dimethyl-; 6-Heptene-I,5-diol, 2.4-dimethyl-; 6-Heptene-
I,5-diol,
2-ethylidene-6-methyl-; 6-Heptene-2,4-diol, 4-(2-propenyl)-; 6-Heptene-2,4-
diol, 5,~-
dimethyl-; 6-Heptene-2.5-diol, 4,6-dimethyl-; 6-Heptene-2,5-diol, S-ethenyl-4-
methyl-;
1,3-Octanediol, 2-methylene-; 1,6-Octadiene-3,5-diol, 2.6-dimethyl-; 1,6-
Octadiene-3,~-
diol, 3,7-dimethyl-; 1,7-Octadiene-3,6-diol, 2,6-dimethyl-; 1,7-Octadiene-3,6-
diol, 2,7-
dimethyl-; 1,7-Octadiene-3,6-diol, 3,6-dimethyl-; 1-Octene-3,6-diol, 3-ethenyl-
; 2,4,6-
Octatriene-1,8-diol, 2,7-dimethyl-; 2,4-Octadiene-1,7-diol, 3,7-dimethyl-; 2,5-
Octadiene-
1,7-diol, 2,6-dimethyl-; 2,5-Octadiene-1,7-diol, 3,7-dimethyl-; 2,6-Octadiene-
1,4-diol,
3,7-dimethyl- (Rosiridol); 2,6-Octadiene-1,8-diol, 2-methyl-; 2,7-Octadiene-
1,4-diol, 3,7-
dimethyl-; 2,7-Octadiene-1,5-diol, 2,6-dimethyl-; 2,7-Octadiene-1,6-diol, 2,6-
dimethyl-
(8-Hydroxylinalool); 2,7-Octadiene-1,6-diol, 2,7-dimethyl-; 2-Octene-1,4-diol;
2-Octene-
1,7-diol; 2-Octene-1,7-diol, 2-methyl-6-methylene-; 3,5-Octadiene-I,7-diol,
3,7-
dimethyl-; 3,5-Octadiene-2,7-diol, 2,7-dimethyl-; 3,5-Octanediol, 4-methylene-
; 3,7-
Octadiene-1,6-diol, 2,6-dimethyl-; 3,7-Octadiene-2,5-diol, 2,7-dimethyl-; 3,7-
Octadiene-
2,6-diol, 2,6-dimethyl-; 3-Octene-1,5-diol, 4-methyl-; 3-Octene-1,5-diol, ~-
methyl-; 4,6-
Octadiene-1,3-diol, 2,2-dimethyl-; 4,7-Octadiene-2,3-diol, 2,6-dimethyl-; 4,7-
Octadiene-
2,6-diol, 2,6-dimethyl-; 4-Octene-1,6-diol, 7-methyl-; 2,7-bis(methylene}-; 2-
methylene-;
5,7-Octadiene-1,4-diol, 2,7-dimethyl-; 5,7-Octadiene-1,4-diol, 7-methyl-; 5-
Octene-1,3-
diol; 6-Octene-1,3-diol, 7-methyl-; 6-Octene-1,4-diol, 7-methyl-; 6-Octene-1,5-
diol; 6-
Octene-1,5-diol, 7-methyl-; 6-Octene-3,5-diol, 2-methyl-; 6-Octene-3,5-diol, 4-
methyl-;
7-Octene-1,3-diol, 2-methyl-; 7-Octene-1,3-diol, 4-methyl-; 7-Octene-I,3-diol,
7-methyl-;
7-Octene-1,5-diol; 7-Octene-I,6-diol; 7-Octene-1,6-diol, 5-methyl-; 7-Octene-
2,4-diol, 2-
methyl-6-methylene-; 7-Octene-2,5-diol, 7-methyl-; 7-Octene-3,5-diol, 2-methyl-
; 1-
Nonene-3,5-diol; I-Nonene-3,7-diol; 3-Nonene-2,5-diol; 4,6-Nonadiene-1,3-diol,
8-
methyl-; 4-Nonene-2,8-diol; 6,8-Nonadiene-1,~-diol; ?-Nonene-2,4-diol; 8-
Nonene-2.4-
diol; 8-Nonene-2,5-diol; 1,9-Decadiene-3,8-diol; and/or 1,9-Decadiene-4,6-
diol; and
CA 02260920 1999-O1-19
WO 98/03619 PCT/US97/05097
28
XI. mixtures thereof.
The principal solvents are desirably kept to the lowest levels that are
feasible in
the present compositions for obtaining translucency or clarity. The presence
of water
exerts an important effect on the need for the principal solvents to achieve
clarity of these
compositions. The higher the water content, the higher the principal solvent
level
(relative to the softener Ievel) is needed to attain product clarity.
Inversely, the less the
water content, the less principal solvent (relative to the softener) is
needed. Thus, at low
water levels of from about 5% to about 15%, the softener active-to-principal
solvent
weight ratio is preferably from about 55:45 to about 85:15, more preferably
from about
60:40 to about 80:20. At water levels of from about 15% to about 70%, the
softener
active-to-principal solvent weight ratio is preferably from about 45:55 to
about 70:30,
more preferably from about 55:45 to about 70:30. But at high water levels of
from about
70% to about 80%, the softener, active-to-principal solvent weight ratio is
preferably from
about 30:70 to about 55:45, more preferably from about 35:65 to about 45:55.
At even
, higher water levels, the softener to principal solvent ratios should also be
even higher.
Mixtures of the above principal solvents are particularly preferred, since one
of
the problems associated with large amounts of solvents is safety. Mixtures
decrease the
amount of any one material that is present. Odor and flammability can also be
mimimized by use of mixtures, especially when one of the principal solvents is
volatile
and/or has an odor, which is more likely for low molecular weight materials.
Preferred
mixtures are those where the majority of the solvent is one, or more, that are
within the
ClogP range identified hereinbefore as most preferred. The use of mixtures of
solvents is
also preferred, especially when one, or more, of the preferred principal
solvents are solid
at room temperature. In this case, the mixtures are fluid, or have lower
melting points,
thus improving processability of the softener compositions.
It is also discovered that it is possible, and desirable, to substitute for
part of a
principal solvent or a mixture of principal solvents of this invention with 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 5%, preferably more than about 7%, more preferably
more than
about 10% of the composition, when at least about 15% of the softener active
is also
present. The substitute solvents) can be used at any level, but preferably
about equal to,
CA 02260920 1999-O1-19
WO 98103619 PCT/US97/05097
29
or less than, the amount of operable principal solvent. as defined
hereinbefore, that is
present in the fabric softener composition.
For example, even though 1,4-cyclohexanedimethanol, 1,2-pentanediol, 1.3-
octanediol, and hydroxy pivalyl hydroxy pivalate (HPHP) having the following
formula:
HO-CH2-C(CH3)2-CH2-O-CO-C(CH3)~_CH~-OH (CAS # I I I S-20-4)
are inoperable solvents according to this invention, mixtures of these
solvents with the
principal solvent, e.g., with 2,2,4-trimethyl-i,3-pentanediol, also provide
liquid
concentrated, clear fabric softener compositions. 1,4-Cyclohexanedimethanol is
desirable
since it has a low odor. The principal advantage of the principal solvent is
that it provides
the maximum advantage for a given weight of solvent. It is understood that
"solvent", as
used herein, refers to the effect of the principal solvent and not to its
physical form at a
given temperature, since some of the principal solvents are solids at ambient
temperature.
F. OPTIONAL INGREDIENTS
(A) Brishteners
The premix, and especially the finished dispersion compositions herein can
also
optionally contain from about 0.005% to 5% by weight of certain types of
hydrophilic
optical brighteners which also provide a dye transfer inhibition action. If
used, the
dispersion compositions herein will preferably comprise from about 0.001% to
1% by
weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having the structural formula:
Ri~ R
~N H H N~-
N~OON O C-C O NOO N
ON H H NO
R2 S03M S03M Ri
wherein RI is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is
selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino,
chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, RI is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-
triazine-2-yl)amino)-2,2'-stilbenedisulfonic acid and disodium salt. This
particular
brightener species is commercially marketed under the tradename Tinopal-LJNPA-
GX~
CA 02260920 1999-O1-19
WO 98/03619 PCT/US97/05097
by Ciba-Geigy Corporation. Tinopal-L1NPA-GX is the preferred hydrophilic
optical
brightener useful in the rinse added dispersion compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2
methylamino and M is a cation such as sodium, the brightener is 4.4'-bis[(4-
anilino-6-(N
S 2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic
acid
disodium salt. This particular brightener species is commercially marketed
under the
tradename Tinopal SBM-GX~ by Ciba-Geigy Corporation.
When in the above formula. RI is anilino, R2 is morphilino and M is a cation
such
as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-
yl)amino]2,2'
10 stilbenedisulfonic acid, sodium salt. This particular brightener species is
commercially
marketed under the tradename Tinopal AMS-GX~' by Ciba Geigy Corporation.
(B) Dispersibilitv Aids
The dispersion compositions of the present invention can optionally contain
dispersibility aids. e.g., those selected from the group consisting of mono-
long chain alkyl
I S cationic quaternary ammonium compounds, mono-long chain alkyl amine
oxides, and
mixtures thereof, to assist in the formation of the finished dispersion
compositions. When
said dispersibility aid is present , it is typically present at a total 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 5% to about 13% by weight of the
20 composition. These materials can either be added as part of the active
softener raw
material, (I), or added as a separate component. The total level of
dispersibility aid
includes any amount that may be present as part of component (I).
( 1 ) Mono-Alkyl Cationic Quaternary Ammonium Compound
When the mono-alkyl cationic quaternary ammonium compound is present, it is
25 typically present at a level of from about 2% to about 25%, preferably from
about 3% to
about I 7%, more preferably from about 4% to about I S%, and even more
preferably from
5% to about I3% by weight of the composition, the total mono-alkyl cationic
quaternary
ammonium compound being at least at an effective level.
Such mono-alkyl cationic quaternary ammonium compounds useful in the present
30 invention are, preferably, quaternary ammonium salts of the general
formula:
[R4N+(RS)3~ X_
wherein
R4 is Cg-C22 alkyl or alkenyl group, preferably C l 0-C I g alkyl or alkenyl
group; more
preferably C I 0-C 14 or C I 6-C I g alkyl or alkenyl group;
CA 02260920 2001-11-08
31
each R~ is a Cl-C6 alkyl or substituted alkyl group (e.g., hydroxy alkyl),
preferably C1-
C3 alkyl group, e.g.. methyl (most preferred), ethyl, propyl, and the like, a
benzyl group.
hydrogen. a polyethoxylated chain with from about ? to about ?0 oxyethyiene
units.
preferably from about 2.~ to about 13 oxyethylene units, more preferably from
about 3 to
about 10 oxyethylene units, and mixtures thereof; and
X' is as defined hereinbefore for (Formula (I)).
Especially preferred dispersibility aids are monolauryl trimethyl ammonium
chloride and monotallow trimethyl ammonium chloride available from Witco under
the
trade name Vatisoft~ 471 and monooleyl trimethyl ammonium chloride available
from
Witco under the tradename Varisoft~ 417.
The R4 group can also be attached to the cationic nitrogen atom through a
group
containing one. or more, ester, amide. ether, amine, etc., linking groups
which can be
desirable for increased concentratabiiity of component (I), etc. Such linking
groups are
preferably within from about one to about three carbon atoms of the nitrogen
atom.
Mono-alkyl cationic quaternary ammonium compounds also include Cg-C22 alkyl
choline esters. The preferred dispersibility aids of this type have the
formula:
R1C(O)-C>-CH~CH~N+(R)3 X-
wherein R 1, R and X- are as defined previously.
Highly preferred dispersibility aids include C 12-C 14 coco choline ester and
C l 6'
~0 C 1 g tallow choline ester.
Suitable biodegradable single-long-chain alkyl dispersibili:y aids 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.
When the dispersibility aid comprises alkyl choline esters, preferably the
~5 dispersion compositions also contain a small amount, preferably from about
2% to about
5% by weight of the composition, of organic acid. Organic acids are described
in
European Patent Application No. 404,471, Machin et al., published on Dec. 27,
1990,
Preferably the organic acid is selected
from the group consisting of glycolic acid. acetic acid, citric acid, and
mixtures thereof.
:30 Ethoxylated quaternary ammonium compounds which can serve as the
dispersibility aid include ethylbis(polyethoxy ethanol)alkylammonium ethyl-
sulfate with
17 moles of ethylene oxide, available under the trade name Variquat~ 66 from
Sherex
Chemical Company; polyethylene glycol ( 15) oleammonium chloride, available
under the
trade name Ethoquad~ 0/25 from Akzo: and polyethylene glycol ( 15) cocomonium
a5 chloride, available under the trade name Ethoquad~ C/25 from Akzo.
CA 02260920 1999-O1-19
WO 98/03619 PCT/US97/05097
32
Although the main function of the dispersibility aid is to increase the
dispersibility
of the ester softener, preferably the dispersibility aids of the present
invention also have
some softening properties to boost softening performance of the composition.
Therefore,
preferably the dispersion compositions of the present invention are
essentially free of
non-nitrogenous ethoxylated nonionic dispersibility aids which will decrease
the overall
softening performance of the dispersion compositions.
Also, 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.
(2) Amine Oxides
Suitable amine oxides include those with one alkyl or hydroxyalkyl moiety of
about 8 to about 22 carbon atoms, preferably from about 10 to about 18 carbon
atoms,
more preferably from about 8 to about 14 carbon atoms, and two alkyl moieties
selected
from the group consisting of alkyl groups and hydroxyalkyl groups with about 1
to about
3 carbon atoms.
Examples include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-
hydroxyethyl)dodecyl-amine oxide, dimethyldodecylamine oxide, dipropyl-
tetradecylamine oxide, methylethylhexadecylamine oxide, dimethyl-2-
hydroxyoctadecylamine oxide, and coconut fatty alkyl dimethylamine oxide.
(C) Soil Release Agent
In the present invention, an optional soil release agent can be added,
especially to
the finished dispersion compositions. 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 finished
softening
composition prepared by the process of the present invention herein can
contain from 0%
to about 10%, preferably from 0.2% to about 5%, of a soil release agent. The
concentration in the premix is adjusted to provide the desired end
concentration.
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
CA 02260920 1999-O1-19
WO 98/03619 PCT/US97/05097
33
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
5,000.
Another preferred polymeric soil release agent is a crystallizable polyester
with
repeat units of ethylene terephthalate units containing from about 10% to
about 1 S% by
weight of ethylene terephthalate units together with from about 10% to about
SO% by
weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene
glycol of
average molecular weight of from about 300 to about 6.000, and the molar ratio
of
ethylene terephthalate units to polyoxyethylene terephthalate units in the
crystallizable
polymeric compound is between 2:1 and 6:1. Examples of this polymer include
the
commercially available materials Zelcon 4780~ (from Dupont) and Milease T~
(from
ICI).
Highly preferred soil release agents are polymers of the generic formula:
O
14 II 15 O
X-(OCH2CH2)p(O-C-R - C -OR )~{O-~-R14_OC-O)(CH2CH20-)n-X
in which each X can be a suitable capping group, with each X typically being
selected
from the group consisting of H, and alkyl or acyl groups containing from about
1 to about
4 carbon atoms. p is selected for water solubility and generally is from about
6 to about
113, preferably from about 20 to about 50. 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 R14 moieties are essentially 1,4-phenylene moieties. As used herein, the
term "the R 14 moieties are essentially 1,4-phenylene moieties" refers to
compounds
where the R 14 moieties consist entirely of 1,4-phenylene moieties, or are
partially
substituted with other arylene or alkarylene moieties, alkylene moieties,
alkenylene
moieties, or mixtures thereof. Arylene and alkarylene moieties which can be
partially
substituted for 1,4-phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-
naphthylene, 1,4-
naphthylene, 2,2-biphenylene, 4,4-biphenylene, and mixtures thereof. Alkylene
and
alkenylene moieties which can be partially substituted include 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 R 14 moieties, the degree of partial substitution with moieties other
than
1,4-phenylene should be such that the soil release properties of the compound
are not
CA 02260920 2001-11-08
34
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 R 14 comprise from about ~0% to about 100% 1,=t-phenylene
moieties (from 0% to about ~0% moieties other than 1,4-phenylene) have
adequate soil
release activity. For example. polyesters made according to the present
invention with a
40:60 mole ratio of isophthalic (I,3-phenylenej to terephthalic (1,4-
phenylene) acid have
adequate soil release activity. However, because most polyesters used in fiber
making
comprise ethylene terephthalate units, it is usually desirable to minimize the
degree of
partial substitution with moieties other than 1,4-phenylene for best soil
release activity.
Preferably, the RI4 moieties consist entirely of (i.e., comprise 100%) 1,4-
phenylene
moieties, i.e., each R14 moiety is 1,4-phenylene.
For the R I ~ moieties, suitable ethylene or substituted ethylene moieties
include
ethylene, 1,2-propylene, 1,2-butylene, I,2-hexylene, 3-methoxy-1,2-propylene,
and
mixtures thereof. Preferably, the R15 moieties are essentially ethylene
moieties, 1,2
propylene moieties, or mixtures thereof. Inclusion of a greater percentage of
ethylene
moieties tends to improve the soil release activity of compounds.
Surprisingly, inclusion
of a greater percentage of 1.2-propylene moieties tends to improve the water
solubility of
compounds.
Therefore, the use of 1,2-propylene moieties or a similar branched equivalent
is
desirable for incorporation of any substantial part of the soil release
component in the
liquid fabric softener dispersion compositions. Preferably, from about 75% to
about
100%, are 1.2-propylene moieties.
The value for each p is at least about 6, and preferably is at least about I
0. The
value for each n usually ranges from about 12 to about 113. Typically the
value for each
,p is in the range of from about 12 to about 43.
A more complete disclosure of soil release agents is contained in U.S. Pat.
Nos.:
4,661,267, Decker, Konig, Straathof, and Gosselink, issued Apr. 28, 1987;
4,711,730,
Gosselink and Diehl, issued Dec. 8, 1987; 4,749,596, Evans, Huntington,
Stewart, Wolf,
and Zimmerer, issued .tune 7, 1988; 4,818,569, Trinh, Gosselink, and
Rattinger, issued
April 4, 1989; 4,877,896, :N,aldonado. Trinh, and Gosselink, issued Oct. 31,
1989;
4,956,447, Gosselink et al., issues Sept. I I , 1990; and 4,976,879,
Maldonado, Trinh, and
Gosselink, issued Dec. I1, 1990.
These soil release agents can also act as scum dispersants.
CA 02260920 1999-O1-19
WO 98/03619 PCT/US97/05097
(D) Scum Dispersant
In the present invention, the premix can be combined with an optional scum
dispersant, other than the soil release agent, and heated to a temperature at
or above the
melting points} of the components. Scum dispersants are desirable components
of the
5 finished dispersion compositions herein.
The preferred scum dispersants herein are formed by highly ethoxylating
hydrophobic materials. The hydrophobic material can be a fatty alcohol, fatty
acid, fatty
amine, fatty acid amide, amine oxide, quaternary ammonium compound, or the
hydrophobic moieties used to form soil release polymers. The preferred scum
dispersants
10 are highly ethoxylated, e.g., more than about 17, preferably more than
about 25, more
preferably more than about 40, moles of ethylene oxide per molecule on the
average, with
the polyethylene oxide portion being from about 76% to about 97%, preferably
from
about 81 % to about 94%, of the, total molecular weight.
The level of scum dispersant is sufficient to keep the scum at an acceptable,
15 preferably unnoticeable to the consumer, level under the conditions of use,
but not
enough to adversely affect softening. For some purposes it is desirable that
the scum is
nonexistent. Depending on the amount of anionic or nonionic detergent, etc.,
used in the
wash cycle of a typical laundering process, the efficiency of the rinsing
steps prior to the
introduction of the dispersion compositions herein, and the water hardness,
the amount of
20 anionic or nonionic detergent surfactant and detergency builder (especially
phosphates
and zeolites) entrapped in the fabric (laundry) will vary. Normally, the
minimum amount
of scum dispersant should be used to avoid adversely affecting softening
properties.
Typically scum dispersion requires at least about 2%, preferably at least
about 4% (at
least 6% and preferably at least 10% for maximum scum avoidance) based upon
the level
25 of softener active. However, at levels of about 10% (relative to the
softener material) or
more, one risks loss of softening efficacy of the product especially when the
fabrics
contain high proportions of nonionic surfactant which has been absorbed during
the
washing operation.
Preferred scum dispersants are: Brij 700~; Varonic U-250~; Genapol T-500~,
30 Genapol T-800~; Plurafac A-79~; and Neodol 25-50~.
(E) Bactericides
Examples of bactericides used in the premixes and/or finished dispersion
compositions of this invention include glutaraldehyde, formaldehyde, 2-bromo-2-
nitro-
propane-1,3-diol sold by Inolex Chemicals, located in Philadelphia,
Pennsylvania, under
35 the trade name Bronopol~, and a mixture of 5-chloro-2-methyl-4-
isothiazoline-3-one and
CA 02260920 1999-O1-19
WO 98103619 PCT/US97/05097
36
2-methyl-4-isothiazoline-3-one sold by Rohm and Haas Company under the trade
name
Kathon CG/ICP~. Typical levels of bactericides used in the present dispersion
compositions are from about 1 to about 1,000 ppm by weight of the agent.
(F) Chelatine A~,ents
The finished dispersion compositions and processes herein can optionally
employ
one or more copper and/or nickel chelating agents ("chelators"). Such water-
soluble
chelating agents can be selected from the group consisting of amino
carboxylates, amino
phosphonates, polyfunctionaily-substituted aromatic chelating agents and
mixtures
thereof, all as hereinafter defined. The whiteness and/or brightness of
fabrics are
substantially improved or restored by such chelating agents and the stability
of the
materials in the dispersion and clear compositions are improved, especially
when the
chelating agents are present with the fabric softening active during
processing.
Amino carboxylates useful as chelating agents herein include
ethylenediaminetetraacetates , (EDTA), N-
hydroxyethylethylenediaminetriacetates,
nitrilotriacetates (NTA), ethylenediamine tetraproprionates, ethylenediamine-
N,N'
diglutamates, 2-hyroxypropylenediamine-N,N'-disuccinates,
triethylenetetraaminehexacetates, diethylenetriaminepentaacetates (DETPA), and
ethanoldiglycines, including their water-soluble salts such as the alkali
metal, ammonium,
and substituted ammonium salts thereof and mixtures thereof.
Amino phosphonates are also suitable for use as chelating agents in the
dispersion
compositions of the invention when at least low levels of total phosphorus are
permitted
in detergent dispersion compositions, and include ethylenediaminetetrakis
(methylenephosphonates), diethylenetriamine-N,N,N',N",N"-pentakis(methane
phosphonate) (DETMP) and 1-hydroxyethane-l,l-diphosphonate (HEDP). Preferably,
these amino phosphonates to not contain alkyl or alkenyl groups with more than
about 6
carbon atoms.
The chelating agents are typically used in the present rinse process at levels
from
about 2 ppm to about 25 ppm, for periods from 1 minute up to several hours'
soaking.
The preferred EDDS chelator 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):
H-N-CH2-CHI-N-H
CH2 CH CH CHI
COOH COOH COOH COOH
CA 02260920 2001-11-08
37
As disclosed in the patent. EDDS can be prepared using malefic anhydride and
ethylenediamine. The preferred biodegradable [S,SJ isomer of EDDS can be
prepared by
reacting L-aspartic acid with 1,:?-dibromoethane. The EDDS has advantages over
other
chelators in that it is effective for chelating both copper and nickel canons,
is available in
a biodegradable form, and does not contain phosphorus. The EDDS employed
herein as a
chelator is typically in its salt form, i.e., wherein one or more of the four
acidic hydrogens
are replaced by a water-soluble cation M, such as sodium, potassium, ammonium.
triethanolammonium, and the like. As noted before, the EDDS chelator is also
typically
used in the present rinse process at levels from about 2 ppm to about 25 ppm
for periods
from 1 minute up to several hours' soaking. At certain pH's the EDDS is
preferably used
in combination with zinc canons;.
As can be seen from the foregoing, 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
l5 phosphonates, on a weight basis. Accordingly, usage levels may be adjusted
to take into
account differing degrees of cheiating effectiveness. The chelators herein
will preferably
have a stability constant (of the fully ionized chelator) for copper ions of
at least about 5.
preferably at least about 7. Typically, the chelators will comprise from about
0.5% to
about 10%, more preferably from about 0.75% to about 5%, by weight of the
dispersion
0 compositions herein. Preferred chelators include DETMP. DETPA, NTA, EDDS and
mixtures thereof. The polycarboxylate chelating agents like
ethylenediaminetetraacetic
acid and diethylenetriaminepentaacetic acid are more preferred.
(G) Optional ViscositvlDispersibility Modifiers
Relatively concentrated finished dispersion compositions containing the
:~S unsaturated diester quaternary ammonium compounds herein can be prepared
that are
stable without the addition of concentration aids. However, the dispersion
compositions
of the present invention may require organic and/or inorganic concentration
aids to go to
even higher concentrations and,'or to meet higher stability standards
depending on the
other ingredients. These concentration aids which typically can be viscosity
modifiers
_l0 may be needed, or preferred, for ensuring stability under extreme
conditions when
particular softener active levels pare used. The surfactant concentration aids
are typically
selected from the group consisting of ( 1 ) single tong chain alkyl cationic
surfactants; (2)
nonionic surfactants; (3) amine oxides; (4) fatty acids; and (5) mixtures
thereof. These
aids are described in U.S. Patent No. ~.~45.340, Wahl. et al., issued August
13. 1996.
CA 02260920 2001-11-08
38
(H) Other Optional Ingredients
The finished dispersion compositions of the present invention can include
optional
components conventionally used in textile treatment dispersion compositions,
for
example: colorants; preservatives; surfactants: anti-shrinkage agents; fabric
crisping
agents: spotting agents; germicides; fungicides; anti-oxidants such as
butylated hydroxy
toluene, anti-corrosion agents. and the like.
Particularly preferred ingredients include water soluble calcium and/or
magnesium compounds, as described above for the clear compositions, which
provide
additional stability. The chloride salts are preferred, but acetate, nitrate,
etc. salts can be
used. The level of said calcium and/or magnesium salts is from 0% to about 2%,
preferably from about 0.05% to about 0.5%, more preferably from about 0.1 % to
about
0.25%. These materials are desirably added to the water and/or acid (water
seat) used to
prepare the finished dispersion compositions to help adjust the finished
viscosity.
The present invention ~~an also include other compatible ingredients,
including
those as disclosed in the following published PCT applications, WO 96/21714 on
July
18, 1996; WO 96/21715 on .luly 18, 1996 and WO 96/02625 on February 1, 1996.
The invention is examplified by the following non-limiting examples in which
all
numerical values are approximations consistent with normal experience. The
compositions can be made with preheated softener active by adding it to the
"water seat"
comprising water and minors, but more preferably are made at ambient
temperature.
especially after premixing the active and perfume.
Preparatioa of Biodegradable Fabric Softening Actives
One preferred triglyceride source which can be used to prepare the fabric
softening compositions herein is canola oil. Canola oil is a mixture of
triglycerides
having an appropriate chain length distribution and degree of unsaturation of
the
respective acyl groups. Canola oil is a particularly desirable starting
product in
:30 accordance with the process of the present invention, for several reasons.
In particular. its
natural distribution of the chain lengths of the respective acyl groups has a
notably high
proportion of acyl groups containing 18 carbon atoms, thus avoiding the
additional
expense incurred when using other commercial sources of C 1 g fatty acids as
starting
materials.
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WO 98/03619 PCT/US97/05097
39
The triglyceride starting product can be partially hydrogenated, if desired,
to
convert diunsaturated and triunsaturated acyl groups, particularly those
containing 18
carbon atoms, to their monounsaturated counterparts. It is normally desirable
that
hydrogenation of mono-unsaturated acyl groups is minimized and even completely
avoided. Saturated acyl groups can be obtained from normally saturated sources
and
mixed with unsaturated acyl groups. In some useful mixtures of acyl groups, no
more
than about 10% of unsaturated C 1 g acyl groups are hydrogenated to their
saturated
counterparts. For some products, hydrogenation of diunsaturated and
triunsaturated C 1 g
acyl groups is preferably maximized, consistent with minimal formation of
saturated C 1 g
groups. For instance, triunsaturated acyl groups can be completely
hydrogenated without
achieving complete hydrogenation of diunsaturated acyI groups.
Hydrogenation of the triglyceride starting product which maximizes
monounsaturated acyl groups can be readily achieved by maintaining an
appropriate
balance of the conditions of the hydrogenation reaction. The process variables
in the
hydrogenation of triglycerides and the effects of altering such variables, are
generally
quite familiar to those of ordinary skill in this art. In general,
hydrogenation of the
triglyceride starting product can be carried out at a temperature ranging
(broadly stated)
between about 170°C and about 205°C and more preferably within a
somewhat narrower
range of about 185°C to about 195°C. The other significant
process variable is the
pressure of hydrogen within the hydrogenation reactor. In general, this
pressure should
be maintained within a range (broadly stated) of about 2 psig to about 20
psig, and more
preferably between about 5 psig and about 15 psig.
Within these ranges of parameters, hydrogenation can be carried out with a
particular view to the effects of these parameters. Lower hydrogen pressures
in the
reactor permit a greater degree of control of the reaction, particularly as to
its selectivity.
By "selectivity" is meant the hydrogenation of diunsaturated and
triunsaturated acyl
groups without excessive hydrogenation of mono unsaturated acyl groups. On the
other
hand, higher hydrogen pressures afford less selectivity. Selectivity can be
desirable in
certain instances.
Higher hydrogenation temperatures are associated with faster rates of
hydrogenation and with greater selectivity of the hydrogenation. Conversely,
lower
hydrogenation temperatures are associated with less selectivity (i.e.
increased
hydrogenation of the mono unsaturated groups), and particularly with slower
hydrogenation rates in general.
CA 02260920 1999-O1-19
WO 98/03619 PCT/U597/05097
These considerations are also balanced with considerations of stereochemistry.
More specifically, the presence of unsaturation in the acyl groups can lead to
the
formation of different stereoisomers in the acyl groups upon hydrogenation.
The two
possible stereoisomeric configurations for unsaturated fatty acyl groups are
known as the
S "cis" and the "trans" forms. The presence of the cis form is preferred, as
it is associated
with a lower melting point of the eventual product and thus with greater
fluidity. Thus,
another reason that canola oil is a particularly preferred triglyceride
starting product is
that, as a naturally occurring material, the acyl groups present in this
triglyceride exhibit
only the cis form. In the hydrogenation. higher hydrogen pressures are
associated also
10 with a decreased tendency of the acyl group to undergo configuration change
from the cis
form to the trans form. Also, higher hydrogenation temperatures while
favorable for
some reasons are also associated with higher conversion of cis unsaturation to
the trans
form. Products exhibiting satisfactory properties can be obtained by
appropriate control
of the hydrogenation conditions so as to afford both selectivity and control
of the
15 , stereochemical configurations of the product.
The hydrogenation is carried out in the presence of a suitable hydrogenation
catalyst. Such catalysis are well known and commercially available. They
generally
comprise nickel, palladium, ruthenium or platinum, typically on a suitable
catalyst
support. A suitable catalyst is a nickel based catalyst such as sold by
Engelhard under the
20 trade designation "N-545".
In one variation, the hydrogenation is carried out to an end point at which
hydrogenation of the diunsaturation and triunsaturation in the triglyceride
product is
maximized, while formation of saturated acyl groups is minimized. The progress
of the
hydrogenation reaction toward the end point can readily be monitored by
periodic
25 measurement of the Iodine Value of the reaction mass. As the hydrogenation
proceeds,
the Iodine Value decreases. For example, the hydrogenation reaction can be
discontinued
when the Iodine Value reaches about 95.
Other requirements for hydrogenation reactions are well known, such as the
types
of reactor, cooling means to maintain the desired temperature, the provision
of means for
30 agitation effective to provide adequate contact between the triglyceride
and the hydrogen
and catalyst, etc.
The triglyceride containing the desired acyl groups is typically hydrolyzed to
obtain the desired fatty aryl groups as, e.g., the corresponding fatty acids.
That is, the
three ester bonds in the triglyceride are broken so that the hydrogenated
combination of
35 acyl groups is converted to a mixtures of fatty acids having the same chain
length
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WO 98/03619 PCT/US97/05097
41
distribution as in the acyl groups, and having the distribution of saturation
and
unsaturation provided by the hydrogenation reaction. However, other approaches
include
using transesterification to create, e.g., methyl esters, which then can be
used to esterify
the alkanolamine, as described hereinafter.
Hydrolysis can be carried out under any of the suitable conditions known in
this
art for hydrolysis of triglycerides into their fatty acid constituents. In
general, the
triglyceride is reacted with high temperature steam in a reactor, wherein the
fatty acids are
split off from glycerine, following which the steam is condensed to form an
aqueous
solution of glycerine and this solution is removed.
The mixture of fatty acids which is obtained in the hydrolysis step is then
used to
esterify, e.g., one or more amines of the formula R-N(CH2CH~OH)2 wherein R is
defined above, and is preferably methyl. Alternatively, the desired
esterification can be
obtained by transesterification with the corresponding fatty acyl ester like
methyl ester.
Esterification can be carried out under conventional esterification
conditions,
providing an acidic catalyst and providing for withdrawal of by-product water
of
condensation. Preferably, a small amount, generally up to about 1.0 wt.% of
the reactant
(i.e. acids and amine), of hypophosphorous acid (HPPA) can be added to the
esterification
reaction mixture. HPPA is believed to catalyze the reaction and preserve, or
even
improve the color of the product obtained in this reaction.
In one embodiment of this invention, esterification is allowed to proceed
completely such that all amine present is diesterified with fatty acids
produced in the
previous hydrolysis step. It is, however, sometimes desirable to produce a
minor amount
of the corresponding monoester as discussed hereinbefore.
The-mixture of diesters, or mixture of diester and monoester components, as
the
case may be, is quaternized. Quaternization is carried out under conditions
and with
reactants generally familiar to those experienced in this field. The
quaternizing agent has
the formula RX, wherein R is preferably methyl, benzyl, or ethyl, and X is the
anion as
defined hereinabove. Preferably RX is methyl chloride, benzyl chloride,
dimethyl sulfate.
or diethyl sulfate. This quaternization step produces a mixture of
biodegradable fabric
softening actives as described hereinabove.
It is highly desirable that the compounds used herein are relatively free from
unwanted impurities. Therefore, it is desirable to process the fatty acid
sources in ways
that are known to eliminate such impurities, e.g., processing under
atmospheres that are
low in oxygen, separating unwanted materials by filtration, adsorption, etc.,
either before
and/or after chemical modification by controlled hydrogenation and/or
oxygenation. etc.
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WO 98/03619 PCT/US97/05097
42
However, the purity of the materials is not part of the invention herein,
which is equally
applicable to less pure materials, the trade-off between purity and cost
always being
adjusted in light of the consumer's desires and needs.
The synthesis of the mixtures of biodegradable fabric softening actives of the
present invention is further illustrated in the following Synthesis Examples.
These
Synthesis Examples are provided for purposes of illustration only.
Compound Synthesis Example A
Approximately 1,300 grams of 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. Stirring at 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 I 1 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 78.0
and a cisarans ratio of about 1.098. After another about 20 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.
The product that forms in the reactor is removed and filtered. It has a cloud
poim
of about 22.2°C. The chain length distributions of the acyl
substituents on the sample
taken at about 127 minutes, and of the final product. are determined to be as
shown in
Table 1 in which "sat." means saturated, and "mono" and "di" means
monounsaturated
and diunsaturated, respectively.
TABLE 1
Approximate Percent (mol.)
Chain length Sample @ 127 min. Product
C 14-sat. 0.1 0.1
C 16-sat. 4.7 4.6
C 16-mono. 0.4 0.4
C 18-sat. 8.9 13.25
C 18-mono. 77.0 73 .8
C 18-di. 4.5 3. I
C20-sat. 0.7 0.75
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WO 98/03619 PCT/US97/05097
43
C-20-mono. 2.1 2.0
Other 1.6 2.0
Compound Synthesis Example B
About 1,300 grams of canola oil and about 5.2 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
175°C and
hydrogen is fed into the reactor. Stirring is maintained at about 450 rpm
throughout the
course of reaction. After about S minutes the temperature in 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 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 80Ø The product that forms in
the reactor
is removed and filtered. It has a cloud point of about 18.6°C.
Compound Synthesis Example C
About 1,300 grams of 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 85.5. After another about 20 minutes at about 19O°('._
the hvrtrnQPn
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.
Compound Synthesis Example D
About 1,300 grams of 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 5 minutes the temperature in the
reactor is about
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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.
Compound Synthesis Example.E
About 1.300 grams of 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. After
about 3
hours from the start of the hydrogen feed, a sample of the reaction mass is
drawn and
1 S 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 anotherabout 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 16.0°C.
Compound Synthesis Example F
About 1,300 grams of 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.
Compound Synthesis Example 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
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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
5 and the head temperature rose gradually from about 17~°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.
10 Compound Synthesis Example H
About 800 grams of mixture of fatty acids obtained from canola oil by the
foregoing procedures, about 194.4 grams of MDEA (methyl diethanolamine) about
2
grams of BHT (butylated hydroxytoluene), and about 1 gram of an approximately
50
wt.% aqueous solution of HPPA are placed in a pot at the bottom of a
distillation column.
15 Nitrogen flow through the column is established. The pot is heated, and
distillation began
at a pot temperature of about 150°C, and a head temperature of about
102°C. The
mixture temperature rose to about 193°C in the first hour and then
gradually rose to about
202°C through the next about 4 hours. The head temperature rose to
about 107°C in the
first hour and then declined gradually to about 62°C over the next
about 4 hours. The
20 product in the pot is then cooled, recovered and analyzed. The distillate
contained about
3 wt.% MDEA, about 51 grams of water, and exhibited a total amine value (TAV)
of
about 0.5. The product remaining in the pot has a total amine value (TAV) of
about 93.3.
Compound Synthesis Example I
About 900 grams of the product of Synthesis Example H, about 158 grams of
25 ethanol, about 0.3 grams of ADPA, 1-hydroxyethane-I,I-diphosphonic acid (a
chelant,
for color stability), about O. I S grams of antifoam, and sufficient methyl
chloride to
establish an initial pressure of about 43 psig are combined in a sealed
reactor. After about
7 minutes the temperature is about 106°C and the pressure is about 84
psig. The contents
are then maintained at about 105~1 °C for about 3-5 hours while the
pressure is
30 maintained at about 57~2 psig by additions of methyl chloride. Then the
reactor is
vented, and the contents cooled to about 95°C. A total of about I 10
grams of methyl
chloride is used. The product is then removed and stripped at about
65°C on a rotary
evaporator. The product has a diester content of about 75.9% and a monoester
content of
about 11.4%.
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EXAMPLES I TO 4
Ex.l Ex.2 Ex.3 Ex.4
Ingredients Wt.% Wt.% Wt.% Wt.%
DEQA 1 (85% active in 17.7 23.5 30.6 30.6
ethanol)
Perfume 0.8 I 1.35 --
Tenox 6 0.02 0.03 0.04 0.04
CaCl2 (25% solution) 1.2 I .5 2 2
HC11N O.i7 0.23 0.30 0.30
Distilled Water Balance Balance Balance Balance
Examples I to 3 - Process
The compositions of Examples 1-3 are made at ambient temperature by the
following process:
I. Prepare the water seat containing HC1.
2. Separately, mix perfume and Tenox 6~ antioxidant to the diester softener
active.
3. Add the diester active blend into the water seat with mixing.
4. Add about 10-20% of the CaCl2 solution at approximately halfway through the
diester
addition.
5. Add the remainder of the CaCl2 solution after the diester addition is
complete with
mixing.
EXAMPLES
5 TO
8
Ex.l Ex.2 Ex.3 Ex.4
I~redients Wt.% Wt.% Wt.% Wt.%
DEQAS (85% active in ethanol)17.7 23.5 30.6 30.6
Perfume _ 0.8 1 1.3 S --
Tenox 6 0.02 0.03 0.04 0.04
CaCl2 (25% solution) 1.2 1.5 2 2
HC11N O.I7 0.23 0.30 0.30
Distilled Water Balance Balance Balance Balance
Examples 4 to 6 - Process
The compositions of Examples 5 to 8 are made similar to those of Examples 1 to
4,
except that DEQAS is used instead of DEQA I .
The compositions of Examples 1 to 8 have good viscosity. They are frozen when
placed in a constant temperature room for about 3 days at a temperature of
about 0°F
(about -18°C}. After thawing at ambient temperature, these compositions
recover as fluid
and have good viscosity.
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Comparative Examples 9 to 12
. The compositions of Comparative Examples 9 to 12 are made similar to those
of
Examples 1 to 4, with the exception that (a) DEQA 11 (prepared from a slightly
hydrogenated tallow fatty acid) is used instead of DEQA1, (b) softener active
needs to be
heated to melt at about 75°C before it is added to the water seat, also
preheated to about
75°C, (c) about 50% more CaCl2 is needed to provide good product
viscosity, and (d)
perfume is added last, to the cooled finished composition to avoid perfume
degradation.
The compositions of Examples 9 to 12 have good viscosity when they are cooled
after
preparation to room temperature. However, after being frozen when placed in a
constant
temperature room for about 3 days at a temperature of about 0°F (about -
18°C) and then
thawed at ambient temperature, these compositions do not recover and still
remain
thickened or have lumpy consistency.
EXAMPLES 13 AND 14
Example Example
13 14
Ingredients Wt.% Wt.%
DEQAB (85% active in 30.6 --
ethanol)
DEQA9 (85% active in -- 30.6
ethanol)
Perfume 1.35 I .35
Tenox 6 0.04 0.04
CaCl2 (25% solution) 2 2
HC11N 0.30 0.30
Distilled Water Balance Balance
Examples I3 and 14
The compositions of Examples 13 and 14 are made similar to that of Example 3,
except that DEQAB and DEQA9 are used instead of DEQA 1.
EXAMPLES 15 TO 19
Ex. Ex.
15 16
Ingredients Wt.% Wt.%
DEQA 10 (85% active in ethanol)20.8 --
DEQA11 (85% active in ethanol) 20.8
Perfume 1.3 1.3
5 5
Tenox 6 0.04 0.04
CaCl2 (25% solution) 2 2
HC11N 0.30 0.30
Distilled Water Bal. Bal.
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EXAMPLES 20 TO 22
Ex.20 Ex.21 Ex.22
Ingredients Wt.% Wt.% Wt.%
Canola DEQA ( 100%) 26.0 42.5 52.0
Ethanol 2.3 3.8 4.6
Hexylene Glycol 2.3 3.8 4.6
TMPD* 15.0 22.0 22.0
1,4-Cyclohexanedimethanol5.0 8.0 8.0
HC1 (1N) 0.25 0.40 0.50
Perfume 1.25 1.25 2.50
DTPA* * 0.01 0.01 0.01
Kathon ( 1.5%) 0.02 0.02 0.02
DI Water 47.82 18.17 5.77
* 2,2.4-trimethyl-1,3-pentanediol
** Diethylenetriaminepentaacetic acid
The weight ratio range of TMPD to 1,4-cyclohexanedimethanol for good phase
stability, especially low temperature phase stability, is preferably from
about 80:20 to
about 50:50, more preferably about 75:25.
