Note: Descriptions are shown in the official language in which they were submitted.
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CLEAR OR TRANSLUCENT AQUEOUS POLYOUATERNARY AMMONIUM FABRIC
SOFTENER COMPOSITIONS CONTAINING LOW SOLVENT
TECHNICAL FIELD
The present invention relates to specific clear or translucent fabric softener
compositions.
It has been demonstrated extensively in the patent literature that clear
formulations of mono-
quaternary or polyquaternary ammonium fabric softener actives can be achieved
using high levels
of organic solvents. However, formulations with high levels of organic
solvents are costly, so it
is desirable to formulate quaternary ammonium or polyquaternary ammonium
fabric softener
actives with lower levels of organic solvent.
BACKGROUND OF THE INVENTION
Much of the previous art related to concentrated clear compositions containing
ester
and/or amide linked fabric softening actives and specific principal solvents
relates to the
formulation of mono-quaternary ammonium fabric softener actives and these are
disclosed in U.
S. Pat. No. 5,759,990, issued Jun. 2, 1998 in the names of E. H. Wahl, H. B.
Tordil, T. Trinh, E.
R. Carr, R. O. Keys, and L. M. Meyer, for Concentrated Fabric Softening
Composition With
Good Freeze/'Thaw Recovery and Highly Unsaturated Fabric Softener Compound
Therefor, and
in U. S. Pat. No. 5,747,443, issued May 5, 1998 in the names of Wahl, Trinh,
Gosselink, Letton,
and Sivik for Fabric Softening Compound/Composition, said patents being
incorporated herein
by reference. The fabric softener actives in said patents are preferably
biodegradable ester-linked
materials, containing, long hydrophobic groups with unsaturated chains.
Similar clear liquid
fabric softening compositions are described in WO 97/03169, incorporated
herein by reference,
which describes the formulation of liquid fabric softening compositions using
said specific
principal solvents.
European Patent Application EP 0,803,498, A1, Robert O. Keys and Floyd E.
Friedli,
filed April 25, 1997 teaches that polyquaternary ammonium actives can be
formulated into clear
compositions. This application exemplifies clear compositions of
polyquaternary actives at high
principal solvent levels, typically 15% or more. It is economically desirable
to formulate
compositions with lower solvent levels, but formulating stable, isotropic,
single-phase products at
solvent levels at or below about 10%, particularly when using less preferred
principal solvent
systems is difficult.
SUMMARY OF THE INVENTION
This application discloses surprising approaches used to create
clear/translucent aqueous
formulations comprising polyquaternary ammonium active in continuous bilayer
with lower
solvent levels and very surprisingly, even some formulations with no solvent
added except the
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solvent which is normally present in the polyquaternary ammonium active raw
material stocks.
Approaches to lowering solvent levels including choosing highly efficient
principal solvents
within a specific Clog P range, employing higher levels of polyquaternary,
and/or augmenting the
bilayer with surfactants and/or polar oils.
Compositions with lowered solvent levels often contain a certain percentage of
phases)
other than the desired isotropic phase. Often, but not necessarily, these
secondary phases are
liquid crystalline, because, often, but not necessarily, the desirable
isotropic phase shares a phase
boundary with the liquid crystalline phase. The % volume of the secondary
phases) present is an
indicator of the degree of product stability. The smaller the % volume of
secondary phases) the
more likely it is that these secondary phases will remain dispersed within the
desirable isotropic
phase. When the % volume of the dispersed phase becomes too large,
compositions tend to
separate into layers, and thus stability and homogeneous product performance
are lost. When the
secondary phase separates, the line of demarcation between the two phases is
usually apparent,
because the specific density of the phases is often different. Also, the
secondary phase is often
composed of liquid crystal which can be identified by its birefringent optical
properties as shown
in The Aqueous Phase Chemistry of, Robert Laughlin Preferred compositions have
at or below
about 5% by volume of secondary dispersed phases, more preferred compositions
have below
about 3% by volume of secondary dispersed phases, even more preferred
compositions have
below about 1% by volume of secondary dispersed phases, and the most preferred
compositions
are essentially free of secondary dispersed phases. High-speed ultra-
centrifugation is used to
determine the % volume of secondary phase(s).
The clear, or translucent aqueous liquid fabric softener compositions herein
comprise:
A. typically, a lower limit of at least about 1%, preferably at least about
5%, more
preferably at least about 15%, and most preferably at least about 19% and
typically an upper limit
of equal to or below about 80%, preferably below about 75%, more preferably
below about
70%, and most preferably below about 65%, by weight of the composition, of
polyquaternary
ammonium fabric softener active, relatively biodegradable fabric softener
actives being preferred,
as disclosed hereinafter. The phase transition temperature of the softener
active or mixture of
actives, containing less than 5% organic solvent or water, is preferably less
than 50°C, more
preferably less than about 35°C, even more preferably less than about
20°C, and yet even more
preferably less than about 10°C, or has no significant endothermic
phase transition in the region -
50°C to 100°C, as measured by differential scanning calorimetry
as disclosed hereinafter.
B. The composition also comprises stabilizer for the composition selected from
the
group of organic solvents, bilayer modifiers, and mixtures thereof:
( 1 ) an effective level of organic solvent with the organic solvent being
preferably chosen from the group of principal solvents or mixtures of
principal solvents
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especially when solvent is employed in the absence of a bilayer modifier and
with the principal
solvent preferably having a ClogP of from about -2.0 to about 2.6 , more
preferably from about -
1.7 to about 1.6, and even more preferably from about -1.0 to about 1Ø as
defined hereinafter.
typically used at levels where the lower limit is set at or above about 0.25%,
preferably at or
above 0.5%, more preferably at or above about 1% and even more preferably at
or above 1.5% by
weight of the composition and the upper limit is set at or below about 13.5%,
preferably at or
below about 10%, more preferably at or below about 7.5%, and even more
preferably at or below
about 5% by weight of the composition.
(2) an effective level of bilayer modifier having lower limits typically set
at
levels of at or above about 0.25%, preferably at or above about 0.5%, more
preferably at or above
about 1%, even more preferably at or above about 2.5% by weight of the
composition and with
higher limits typically set at levels at or below about 20%, preferably at or
below about 15%,
more preferably at or below about 12%, even more preferably, at or below about
10% and still
more preferably at or below about 8% and most preferably at or below about
7.5% by weight of
the composition.
(3) mixtures of organic solvent and bilayer modifier; and
C. the balance water.
The clear, or translucent liquid fabric softener compositions can optionally
also contain:
(a) optionally, but preferably, from 0% to about 15%, more preferably from
about
0.1 % to about 8%, and even more preferably from about 0.2% to about 5%, of
perfume;
(b) optionally, additional fabric softener actives and/or cationic charge
boosters;
(c) other optional ingredients such as brighteners, chemical stabilizers, soil
release
agents, bactericides, chelating agents, silicones, color care agents; fabric
abrasion reducing
polymer; malodor control agents and/or;
(d) mixtures thereof.
Preferably, the compositions herein are aqueous, translucent or clear,
preferably clear,
compositions containing from about 10%, preferably from about 20%, more
preferably from
about 30%, and even more preferably from about 40%, up to about 95%,
preferably up to about
80%, more preferably up to about 70%, and most preferably up to about 60%, by
weight of the
composition, of water. As discussed before, clear, or translucent liquid
compositions comprising
polyquaternary ammonium fabric softener actives are preferably prepared such
that the
compositions have good stability as measured by the presence of 5% or less
dispersed phase by
volume after centrifuging. Preferably the compositions herein contain less
than about 5% of
dispersed phase volume, more preferably less than about 3% of dispersed phase
volume and even
more preferably less than about 1% dispersed phase volume, and most
preferably, are essentially
free of dispersed phase volume after high speed centrifugation for 16 hours.
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The pH of the compositions, especially those containing the preferred softener
actives
comprising an ester linkage, should be from about 1 to about 5, preferably
from about 2 to about
4, and more preferably from about 2.7 to about 3.5.
DETAILED DESCRIPTION OF THE INVENTION
A. POLYOUATERNARY AMMONIUM FABRIC SOFTENER ACTIVES
Typical levels of incorporation of the polyquaternary ammonium fabric
softening
compound (active) in the softening composition are of from about 1% to about
80% by weight,
preferably from about 5% to about 75%, more preferably from about 15% to about
70%, and
even more preferably from about 19% to about 65%, by weight of the
composition, and
preferably is biodegradable as disclosed hereinafter.
When formulating clear products it is advantageous to raise the level of the
polyquaternary ammonium active, as this aids in achieving a clear product with
lower solvent
levels. As has been previously disclosed in U. S. Pat. No. 5,759,990, issued
Jun. 2, 1998 in the
names of E. H. Wahl, H. B. Tordil, T. Trinh, E. R. Carr, R. O. Keys, and L. M.
Meyer, for
Concentrated Fabric Softening Composition with Good Freeze/Thaw Recovery and
Highly
Unsaturated Fabric Softener Compound Therefor, and in U. S. Pat. No.
5,747,443, issued May 5,
1998 in the names of Wahl, Trinh, Gosselink, Letton, and Sivik for Fabric
Softening
Compound/Composition, both patents being incorporated by reference, it has
been found that
softener actives with alkyl chains that are unsaturated and/or branched are
particularly well suited
for use in clear or translucent aqueous fabric softener compositions. An
indicator of the
suitability of softener actives for use in the compositions of this invention
is the phase transition
temperature. Preferably, the phase transition temperature of the softener
active or mixture of
actives, containing less than about 5% organic solvent or water, is less than
about 50°C, more
preferably less than about 35°C, even more preferably less than about
20°C, and yet even more
preferably less than about 10°C, or has no significant endothermic
phase transition in the region
from about -50°C to about 100°C.
The phase transition temperature can be measured with a Mettler TA 3000
differential
scanning calorimeter with Mettler TC 10A Processor.
Suitable polycationic softener compounds can be found in the art including:
European Patent Application EP 0,803,498, A1, Robert O. Keys and Floyd E.
Friedli, filed April
25, 1997;
British Pat. 808,265, issued Jan. 28, 1956 to Arnold Hoffman & Co.,
Incorporated;
British Pat. 1,161,552, Koebner and Potts, issued Aug. 13, 1969;
DE 4,203,489 A1, Henkel, published Aug. 12, 1993;
EP 0,221,855, Topfl, Heinz, and Jorg, issued Nov. 3, 1986;
EP 0,503,155, Rewo, issued Dec. 20, 1991;
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EP 0,507,003, Rewo, issued Dec. 20, 1991
EPA 0,803,498, published October 29, 1997:
French Pat. 2,523,606, Marie-Helene Fraikin, Alan Dillarstone, and Marc
Couterau, filed Mar.
22, 1983;
5 Japanese Pat. 84-273918, Terumi Kawai and Hiroshi Kitamura, 1986;
Japanese Pat. 2-011,545, issued to Kao Corp., Jan. 16, 1990;
U.S. Pat. 3,079,436, Hwa, issued Feb. 26, 1963;
U.S. Pat. 4,418,054, Green et al., issued Nov. 29, 1983;
U.S. Pat. 4,721,512, Topfl, Abel, and Binz, issued Jan. 26, 1988;
U.S. Pat. 4,728,337, Abel, Topfl, and Riehen, issued Mar. 1, 1988;
U.S. Pat. 4,906.413, Topfl and Binz, issued Mar. 6, 1990;
U.S. Pat. 5,194,667, Oxenrider et al., issued Mar. 16, 1993;
U.S. Pat. 5,235,082, Hill and Snow, issued Aug. 10. 1993;
U.S. Pat. 5,670,472, Keys, issued Sep. 23, 1997;
Weirong Miao, Wei Hou, Lie Chen, and Zongshi Li, Studies on Multifunctional
Finishing
Agents, Riyong Huaxue Gonye, No. 2, pp. 8-10, 1992;
Yokagaku, Vol 41, No. 4 (1992); and
Disinfection, Sterilization, and Preservation, 4'" Edition, published 1991 by
Lea & Febiger,
Chapter 13, pp. 226-30. All of these references are incorporated herein, in
their entirety, by
reference.
The fabric softening active portion of the composition can also comprise other
cationic,
nonionic, and/or amphoteric fabric softening compounds as disclosed
hereinafter.
B. STABILIZING SYSTEM
The stabilizing systems herein comprises solvent and/or bilayer modifier as
described
hereinafter.
(1) ORGANIC/PRINCIPAL SOLVENT
In compositions employing the bilayer modifier as part of the stabilization
system, a wide
range of organic solvents are effective including a broad range of solvents
that have been
characterized heretofore as "principal solvents" that fall within the broadest
Clog P limits used as
part of the definition of such principal solvents. However, in compositions
without bilayer
modifiers it is preferred to use principal solvents within the more preferred
Clog P ranges as
defined herein to reduce solvent level while maintaining stability.
Modifications of the ClogP
ranges can be achieved by adding electrolyte and/or phase stabilizers as
taught in copending
U.S.S.N. 09/309,128, filed May 10, 1999 by Frankenbach, et al. However, when
polyquaternary
ammonium fabric softening actives are used, inorganic salts are preferably
kept at a low level,
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e.g., less than about 10%. more preferably less than about 5 %, and even more
preferably less
than about 2%, by weight of the composition.
Compositions based on fabric softener actives containing at least some
components with
multiple hydrophobic chains often comprise a lipid bilayer. Not to be bound by
theory, but a
certain level and packing geometry of amphiphilic materials) are necessary to
construct a
bilayer of appropriate fluidity and curvature to achieve clear or translucent
compositions.
Solvents, especially principal solvent, and most especially principal solvents
in more preferred
Clog P ranges, are effective amphiphiles and fill in bilayer space when there
is not enough
fabric softener active to fill this space. This is believed to be the basis
for the surprising result
that solvent levels required are actually less as the polyquatemary ammonium
level is raised.
This result is illustrated in Table 1, hereinafter, by comparing examples 1,
2, and 5 as well as
comparing example 3 and 7.
The organic solvent and/or principal solvent and/or mixtures thereof are used
at effective
levels with the lower limits typically set at or above about,0.25%, preferably
at or above about
0.5%, more preferably at or above about 1%, and most preferably at or above
about I.5% by
weight of the composition and with higher limits typically set at levels at or
below about 13.5%,
preferably at or below about 10%, more preferably at or below about 7.5%, and
even more
preferably, at or below about 5% by weight of the composition.
An advantage of the bilayer modifiers disclosed herein is that lower levels of
principal
solvents and/or a wider range of organic and/or principal solvents can be used
to provide clarity.
E.g., without bilayer modifier, the CIogP of the principal solvent system as
disclosed hereinafter
would typically be limited to a range of from about 0.15 to about 0.64 as
disclosed in said '443
patent. It is known that higher CIogP compounds, up to about 1 can be used
when combined with
other solvents as disclosed in copending provisional application Serial No.
60/047,058, filed May
19, 1997 and re-filed PCT/IJS98/10167 on May 18, 1998, in the names of H. B.
Tordil, E. H.
Wahl, T. Trinh, M. Okamoto, and D. L. Duval, or with nonionic surfactants, and
especially with
the phase stabilizers disclosed herein as previously disclosed in Docket No.
7039P, filed March
2, 1998, Provisional Application S.N. 60/076,564, and re-filed as, the
inventors being D.L.
DuVal, G.M. Frankenbach, E.H. Wahl, T. Trinh, H.J.M. Demeyere, J.H. Shaw and
M. Nogami.
Title: Concentrated, Stable, Translucent or Clear Fabric Softening
Compositions, both of said
applications being incorporated herein by reference. With the bilayer modifier
present, the level
of principal solvent can be less and/or the ClogP range that is usable is
broadened to include from
about -2.0 to about 2.6, more preferably from about -1.7 to about 1.6, and
even more preferably
from about -1.0 to about 1Ø
With the bilayer modifier present, levels of principal solvent that are
substantially less
than about 10% by weight of the composition can be used, which is preferred
for odor, safety and
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economy reasons. The bilayer modifier as defined hereinafter, in combination
with a very low
level of principal solvent is sufficient to provide good clarity and/or
stability of the composition.
In preferred compositions, the level of principal solvent is insufficient to
provide the required
degree of clarity and/or stability and the addition of the bilayer modifier
provides the desired
clarity/stability. Said bilayer modifier can be used to either make a
composition translucent or
clear, or can be used to increase the temperature range at which the
composition is translucent or
clear.
Thus one can use the principal solvent, at the previously indicated levels, in
a method in
which the said principal solvent is added to a composition that is not
translucent, or clear, or
which has a temperature where phase instability occurs that is too high, to
make the composition
translucent or clear, or, when the composition is clear, e.g., at ambient
temperature, or down to a
specific temperature, to reduce the temperature at which phase instability
occurs, preferably by at
least about 5°C, more preferably by at least about 10°C. The
principal solvent is efficient in that
it provides the maximum advantage for a given weight of solvent. It is
understood that "solvent",
as used herein, refers to the effect of the principal solvent and not to its
physical form at a given
temperature, since some of the principal solvents are solids at ambient
temperature.
Principal solvents that can be present are selected to minimize solvent odor
impact in the
composition and to provide a low viscosity to the final composition. For
example, isopropyl
alcohol is flammable and has a strong odor. n-Propyl alcohol is more
effective, but also has a
distinct odor. Several butyl alcohols also have odors but can be used for
effective
clarity/stability, especially when used as part of a principal solvent system
to minimize their odor.
The alcohols are also selected for optimum low temperature stability, that is
they are able to form
compositions that are liquid with acceptable low viscosities and translucent,
preferably clear,
down to about 50°F (about 10°C), more preferably down to about
40°F (about 4.4°C) and are able
to recover after storage down to about 20°F (about 6.7°C).
Other suitable solvents can be selected based upon their octanol/water
partition
coefficient (P). Octanol/water partition coefficient of a solvent is the ratio
between its
equilibrium concentration in octanol and in water. The partition coefficients
of the solvent
ingredients of this invention are conveniently given in the form of their
logarithm to the base 10,
loge.
The loge of many ingredients has been reported; for example, the Pomona92
database,
available from Daylight Chemical Information Systems, Inc. (Daylight CIS),
Irvine, California,
contains many, along with citations to the original literature. However, the
loge values are most
conveniently calculated by the "CLOGP" program, also available from Daylight
CIS. This
program also lists experimental loge values when they are available in the
Pomona92 database.
The "calculated loge" (ClogP) is determined by the fragment approach of Hansch
and Leo (cf.,
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A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G.
Sammens, J. B. Taylor
and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990, incorporated herein by
reference). The
fragment approach is based on the chemical structure of each ingredient, and
takes into account
the numbers and types of atoms, the atom connectivity, and chemical bonding.
The ClogP
values, which are the most reliable and widely used estimates for this
physicochemical property,
are preferably used instead of the experimental loge values in the selection
of the principal
solvent ingredients which are useful in the present invention. Other methods
that can be used to
compute CIogP include, e.g., Crippen's fragmentation method as disclosed in J.
Chem. Inf.
Comput. Sci., 27, 21 (1987); Viswanadhan's fragmentation method as disclose in
J. Chem. Inf.
Comput. Sci., 29, 163 (1989); and Broto's method as disclosed in Eur. J. Med.
Chem. - Chim.
Theor., 19, 71 ( 1984).
The principal solvents herein are selected from those having a CIogP of from -
2.0 to 2.6,
preferably from -1.7 to 1.6, and more preferably from -1.0 to 1Ø,
The most preferred solvents can be identified by the appearance of the diluted
fabric
treatment compositions. These diluted compositions comprise vesicular
dispersions of fabric
softener which contain on average more uni-lamellar vesicles than conventional
fabric softener
compositions, which contain predominantly multilamellar vesicles. The larger
the proportion of
uni-lamellar vs. multilamellar vesicles, the better the compositions seem to
perform. These
compositions provide surprisingly good fabric softening as compared to similar
compositions
prepared in the conventional way with the same fabric softener active.
Operable solvents have been disclosed, listed under various listings, e.g.,
aliphatic and/or
alicyclic diols with a given number of carbon atoms; monols; derivatives of
glycerine;
alkoxylates of diols; and mixtures of all of the above can be found in said
U.S. Pats. Nos.
5,759,990 and 5,747,443 and PCT application WO 97/03169 published on 30
January 1997, said
patents and application being incorporated herein by reference, the most
pertinent disclosure
appearing at pages 24-82 and 94-108 (methods of preparation) of the said WO
97/03169
specification and in columns 11-54 and 66-78 (methods of preparation) of the
'443 patent. The
'443 and PCT disclosures contain reference numbers to the Chemical Abstracts
Service Registry
numbers (CAS No.) for those compounds that have such a number and the other
compounds have
a method described, that can be used to prepare the compounds. Some inoperable
solvents listed
in the '443 disclosure can be used in mixtures with operable solvents and/or
with the high
electrolyte levels and/or phase stabilizers, to make concentrated fabric
softener compositions that
meet the stability/clarity requirements set forth herein.
Many diol solvents that have the same chemical formula can exist as many
stereoisomers
and/or optical isomers. Each isomer is normally assigned with a different CAS
No. For
examples, different isomers of 4-methyl-2,3-hexanediol are assigned to at
least the following
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CAS Nos: 146452-51-9; 146452-50-8; 146452-49-5; 146452-48-4; 123807-34-1;
123807-33-0;
123807-32-9; and 123807-31-8.
In the '443 and PCT specifications, each chemical formula is listed with only
one CAS
No. This disclosure is only for exemplification and is sufficient to allow the
practice of the
invention. The disclosure is not limiting. Therefore, it is understood that
other isomers with
other CAS Nos, and their mixtures, are also included. By the same token, when
a CAS No.
represents a molecule which contains some particular isotopes, e.g.,
deuterium, tritium, carbon-
13, etc., it is understood that materials which contain naturally distributed
isotopes are also
included, and vice versa.
There is a clear similarity between the acceptability (formulatability) of a
saturated diol
and its unsaturated homologs, or analogs, having higher molecular weights. The
unsaturated
homologs/analogs have the same formulatability as the parent saturated solvent
with the
condition that the unsaturated solvents have one additional methylene (viz.,
CH2) group for each
double bond in the chemical formula. In other words, there is an apparent
"addition rule" in that
for each good saturated solvent of this invention, which is suitable for the
formulation of clear,
concentrated fabric softener compositions, there are suitable unsaturated
solvents where one, or
more, CH2 groups are added while, for each CH2 group added, two hydrogen atoms
are removed
from adjacent carbon atoms in the molecule to form one carbon-carbon double
bond, thus holding
the number of hydrogen atoms in the molecule constant with respect to the
chemical formula of
the "parent" saturated solvent. This is due to a surprising fact that adding a
-CH2- group to a
solvent chemical formula has an effect of increasing its ClogP value by about
0.53, while
removing two adjacent hydrogen atoms to form a double bond has an effect of
decreasing its
ClogP value by about a similar amount, viz., about 0.48, thus about
compensating for the -CH2-
addition. Therefore one goes from a preferred saturated solvent to the
preferred higher molecular
weight unsaturated analogs/homologs containing at least one more carbon atom
by inserting one
double bond for each additional CH2 group, and thus the total number of
hydrogen atoms is kept
the same as in the parent saturated solvent, as long as the ClogP value of the
new solvent remains
within the effective range. The following are some illustrative examples:
It is possible to substitute for part of the principal solvent mixture a
secondary solvent, or
a mixture of secondary solvents, which by themselves are not operable as a
principal solvent of
this invention, as long as an effective amount of the operable principal
solvents of this invention
is still present in the liquid concentrated, clear fabric softener
composition. An effective amount
of the principal solvents of this invention is at least greater than about 1
%, preferably more than
about 3%, more preferably more than about 5% of the composition, when at least
about 15% of
the softener active is also present.
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Principal solvents preferred for improved clarity at 50 °F are 2-ethyl-
1,3-hexanediol, 1,2-
hexanediol1,2-pentanediol; hexylene glycol; 1,2-butanediol; 1,4-
cyclohexanediol; pinacol; 1,5-
hexanediol; 1,6-hexanediol; and/or 2,4-dimethyl-2,4-pentanediol.
(2). BILAYER MODIFIERS
5 Bilayer modifiers are compounds that allow the formation of stable
formulations at lower
and substantially reduced solvent levels even to the point of, surprisingly,
eliminating solvent in
some compositions. Bilayer modifiers are chose form the group of 1 ) mono-
alkyl cationic amine
compounds, 2) polar and non-polar hydrophobic oils, 3) nonionic surfactants,
and 4) mixtures
thereof.
10 Fabric softening actives, especially those actives or compositions
comprising multiple
hydrophobes tend to form bilayers. Not to be bound by theory but, when these
bilayers and the
water between the bilayers are sufficiently flexible, the composition can
become a single-phase
isotropic system comprising a bicontinuous bilayer or sponge phase.
Not to be bound by theory but, there are many ways to improve flexibility such
that
single-phase isotropic bicontinuous systems with improved stability are
achieved. Using fabric
softening actives with low phase transition temperatures enhances flexibility
of the bilayer since
the actives are fluid. The phase transition temperature can be lowered by
several means, for
instance by incorporating branching and/or unsaturation in the hydrophobe of
fabric softener
actives and employing mixtures of fabric softener actives. Using principal
solvents, particularly
those within the most preferred Clog P ranges enhances the flexibility of both
the water and the
bilayer because these principal solvents, especially in the more preferred
ranges, have the ability
to migrate between the water where they can break up the water hydrogen bond
structure and the
bilayer interface where they can promote net zero curvature at the bilayer
interface. Not to be
bound by theory but, net zero curvature is more readily achieved when the head
group of an
amphiphile (or group of amphiphiles) and the tail moiety of a amphiphile (or
group of
amphiphiles ) occupy equal or nearly equal volume areas. When the head group
and tail moiety
area volumes are nearly equal, there is no driving force to cause the
surfactant interface to curve
in either direction and then the surfactant interface becomes bicontinuous
(Surfactants and
Interfacial Phenomena, 2°d , M. J. Rosen). Often cosurfactants are used
to make oil in water
bicontinuous micro-emulsions (Surfactants and Interfacial Phenomena,
2°a , M. J. Rosen). A
similar principle operates with fabric softener bilayers. Diquats, by their
very nature have large
head groups because the two charged amine moieties are both very water
miscible and therefore,
it is helpful to have a principal solvent that can migrate to the interface
acting to 'fill in' for the
tail volume, to achieve zero curvature necessary to drive the system into the
isotropic
bicontinuous phase. Bilayer modifiers can also act as 'fillers' that together
with the fabric
softener active push the system into a state of zero curvature necessary to
drive the system into
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11
the isotropic bicontinuous phase. With the appropriate bilayer modifier, the
principal solvent or
organic solvent can be substantially reduced even to the point, in some cases,
of surprisingly
eliminating the need to add solvent that is not a part of the polyquaternary,
preferably
diquaternary, ammonium fabric softening active raw material because the
solvent is only
necessary to break the water structure and no longer necessary to act as a
filler at the fabric
softener bilayer surface. Unsaturation and/or branching in the components
improves flexibility,
thus facilitating the bending of the surface of the bilayer, when necessary.
Bilayer modifiers are highly desired optional components of clear compositions
with low
solvent or zero added solvent. Preferably these compounds are amphiphilic with
a water miscible
head group attached to a hydrophobic moiety. When bilayer modifiers are added
they are
incorporated at effective levels having lower limits typically set at levels
of at or above about
0.25%, preferably at or above about 0.5%, more preferably at or above about
1%, even more
preferably at or above about 2.5% by weight of the composition and with higher
limits typically
set at levels at or below about 20%, preferably at or below about 15%, more
preferably at or
below about 12%, even more preferably, at or below about 10% and still more
preferably at or
below about 8% and most preferably at or below about 7.5% by weight of the
composition.
Suitable bilayer modifiers include:
(1) Mono-Alkyl Cationic Amine Compounds
One of the more preferred classes of bilayer modifiers includes mono-alkyl
cationic
amine compounds and especially the preferred mono-alkyl quaternary ammonium
compounds.
Preferably, the phase transition temperature of the mono-alkyl cationic amine,
or the mixture of
mono-alkyl cationic amines, containing less than about 5% organic solvent or
water, is less than
about 50°C, more preferably less than about 35°C, even more
preferably less than about 20°C,
and yet even more preferably less than about 10°C, or has no
significant endothermic phase
transition in the region from about -50°C to about 100°C. These
generally include mono-alkyl
cationic amine compounds having hydrophobes derived from saturated and/or
unsaturated
primary, secondary, and/or branched hydrocarbons. or mixtures of such amines
having a broad
distribution of hydrophobe lengths to lower phase transition temperatures. The
phase transition
temperature can be measured with a Mettler TA 3000 differential scanning
calorimeter with
Mettler TC 10A Processor.
Mono-alkyl cationic amine compounds useful in the present invention are,
preferably,
cationic amine salts of the general formula:
~R4N+(R5)3~ A_
wherein:
R4 is Cg-C22 alkyl or alkenyl group, preferably C 10-C 1 g alkyl or alkenyl
group, or mixtures of
these groups;
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12
each R5 is hydrogen or Cl-C6 alkyl or substituted alkyl group (e.g., hydroxy
alkyl or an alkyl
group with a carboxylate moiety, or an alkyl group with a sulfonate or sulfate
moiety attached),
preferably C1-C3 alkyl group, e.g., methyl (most preferred), ethyl, propyl,
and the like, benzyl
group, polyethoxylated chain with from about 2 to about SO oxyethylene units,
preferably from
about 2.5 to about 20 oxyethylene units, more preferably from about 3 to about
10 oxyethylene
units, and/or mixtures thereof; and A- is fabric softener compatible
counterion. When the mono-
alkyl cationic amine derives its cationic charge from protonation (e.g. one or
more of each RS is a
hydrogen) these compounds can be added to the composition as either the
protonated or free
amine with the assumption that the free amine will become cationic at the
preferred low pH's for
these compositions.
An especially preferred example, of mono-alkyl cationic amine compound
particularly
for use as a bilayer modifier, is a cocoalkyl trimethylammonium chloride
available from Witco
under the trade name Adogen 461. Other examples for mono-alkyl cationic amine
compounds
are monolauryl trimethyl ammonium chloride and monotallow trimethyl ammonium
chloride
available from Witco under the trade name Varisoft~ 471 and monooleyl
trimethyl ammonium
chloride available from Witco under the tradename Varisoft~ 417. Amphoterics
such as
Armeen Z from Akzo Nobel can also be used.
The R4 group can also be attached to the cationic nitrogen atom through a
group
containing one, or more, ester, amide, ether, amine, etc., linking groups.
Such linking groups are
preferably within from about one to about three carbon atoms of the nitrogen
atom.
Mono-alkyl cationic amine compounds also include Cg-C22 alkyl choline esters.
The
preferred compounds of this type have the formula:
~R1X-~+(R)3 ~ A_
wherein R1 is Cg-C22 alkyl or alkenyl group, preferably C10-Clg alkyl or
alkenyl group, or
mixtures of these groups; X is a linking group containing heteroatoms (e.g.
oxygen, nitrogen,
sulfur) with some nonlimititng linking groups including ethers, esters, and
amides with esters
being a preferred linking group; Y is a hydrocarbon based linking group
containing about 0 to
about 4 carbons. R is hydrogen or C1-C6 alkyl or substituted alkyl group
(e.g., hydroxy alkyl or
an alkyl group with a carboxylate moiety, or an alkyl group with a sulfonate
or sulfate moiety
attached), preferably C1-C3 alkyl group, e.g., methyl (most preferred), ethyl,
propyl, and the like,
benzyl group, polyethoxylated chain with from about 2 to about SO oxyethylene
units, preferably
from about 2.5 to about 20 oxyethylene units, more preferably from about 3 to
about 10
oxyethylene units, and/or mixtures thereof; and A- is fabric softener
compatible counterion for
example, but not limited to CI- or methyl sulfate.
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13
Highly preferred compounds include C12-C14 coco choline ester and C16-Clg
tallow
choline ester.
Suitable biodegradable single-long-chain alkyl compounds containing an ester
linkage in
the long chains are described in U.S. Pat. No. 4.840,738, Hardy and Walley,
issued June 20,
1989. said patent being incorporated herein by reference.
Suitable mono-long chain materials correspond to the preferred biodegradable
softener
actives disclosed above, where only one R1 group is present in the molecule.
The R1 group or
YR1 group, is replaced normally by an R group.
Mono-alkyl quaternary compounds are also useful as softness performance
boosters,
charge booster, and they scavenge anionic surfactant in the rinse. These
quaternary compounds
having only a single long alkyl chain, can protect the cationic softener from
interacting with
anionic surfactants and/or detergent builders that are carried over into the
rinse from the wash
solution. It is highly desirable to have sufficient single long chain
quaternary compound, or
cationic polymer to tie up the anionic surfactant. This provides improved
softness and wrinkle
control.
When the mono-long chain alkyl cationic amine compound is present, to boost
softness
performance, its levels should also be consistent with, and effective for,
achieving a clear, stable
formulation.
(2) Polar and Non-Polar Hydrophobic Oils
Polar hydrophobic oils are suitable as bilayer modifiers. An especially
preferred, class
of polar oils includes substituted, e.g., esterified, and/or non-substituted
carboxylic acids,
especially dicarboxylic acids. Nonlimiting examples from this class include
dioctyl adipate
available from Alzo Inc. under the trade name Wickenol~ 158, dioctyl succinate
available from
Alzo Inc. under the trade name Wickenol~ 159, and oleyl oleate available from
Alzo Inc. under
the trade name Dermol~ OLO. Other useful polar oils can be selected from
emollients such as
fatty esters, e.g. methyl oleates, Wickenols~, derivatives of myristic acid
such as isopropyl
myristate, and triglycerides such as canola oil; free fatty acids such as
those derived from canola
oils, fatty alcohols such as oleyl alcohol, bulky esters such as benzyl
benzoate and benzyl
salicylate, diethyl or dibutyl phthalate; bulky alcohols or diols; and perfume
oils particularly low-
odor perfume oils such as linalool; mono or poly sorbitan esters; and/or
mixtures thereof. Non-
polar hydrophobic oils can be selected from petroleum derived oils such as
hexane, decane,
pentadecane, dodecane, isopropyl citrate and perfume bulky oils such as
limonene, and/or
mixtures thereof. In particular, the free fatty acids such as partially
hardened canola oil can
provide increased softness benefits.
(3) Nonionic surfactants
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14
Nonionic surfactants are also useful as bilayer modifiers and preferred
bilayer modifiers
within this group, are nonionic surfactants containing amine or amide
moieties, with ethoxylated
amides being especially preferred. Nonionic surfactants derived from saturated
and/or
unsaturated primary, secondary, and/or branched, amine, amide, amine-oxide,
fatty alcohol, fatty
acid. alkyl phenol, and/or alkyl aryl carboxylic acid compounds, each
preferably having from
about 6 to about 22. more preferably from about 8 to about 18, carbon atoms in
a hydrophobic
chain. more preferably an alkyl or alkylene chain. wherein at least one active
hydrogen of said
compounds is ethoxylated with <_ 50, preferably 5 30, more preferably from
about 5 to about 15,
and even more preferably from about 6 to about 12, ethylene oxide moieties to
provide an HLB
of from about 8 to about 20, preferably from about 10 to about 18, and more
preferably from
about 11 to about 15 are useful as bilayer modifiers..
Nonionic surfactants suitable as bilayer modifiers can be selected from the
set of
nonlimiting classes below:
(a)- Alkyl amide alkoxylated nonionic surfactants
Suitable surfactants have the formula:
R - C(~) - N(R4)n - L(R~~)X(R~~)vR3~m
wherein R is C7_2, linear alkyl, C~_2, branched alkyl, C,_z, linear alkenyl,
C,_z, branched
alkenyl, and/or mixtures thereof. Preferably R is C8_,8 linear alkyl or
alkenyl.
R' is -CHz-CHI- , RZ is C3-C4 linear alkyl, C3-C4 branched alkyl, and/or
mixtures thereof;
preferably RZ is -CH(CH3)-CHI-. Surfactants which comprise a mixture of R' and
Rz units
preferably comprise from about 4 to about 12 -CHZ-CHI- units in combination
with from about 1
to about 4 -CH(CH3)-CHz- units. The units can be alternating or grouped
together in any
combination suitable to the formulator. Preferably the ratio of R' units to RZ
units is from about 4
1 to about 8 : 1. Preferably an RZ unit (i.e. -C(CH3)H-CHI-) is attached to
the nitrogen atom
followed by the balance of the chain comprising from about 4 to 8 -CHI-CHZ-
units.
R3 is hydrogen, C,-C4 linear alkyl, C3-C4 branched alkyl, and/or mixtures
thereof;
preferably hydrogen or methyl, more preferably hydrogen.
R4 is hydrogen, C,-C4 linear alkyl, C3-Ca branched alkyl, and/or mixtures
thereof;
preferably hydrogen. When the index m is equal to 2 the index n must be equal
to 0 and the R4
unit is absent.
The index m is 1 or 2, the index n is 0 or 1, provided that m + n equals 2;
preferably m is
equal to 1 and n is equal to 1, resulting in one - [(R'O)X(Rz0)yR3] unit and
R4 being present on
the nitrogen. 'The index x is from 0 to about 50, preferably from about 3 to
about 25, more
preferably from about 3 to about 10. The index y is from 0 to about 10,
preferably 0, however
when the index y is not equal to 0, y is from 1 to about 4. Preferably all the
alkyleneoxy units are
ethyleneoxy units.
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Examples of suitable ethoxylated alkyl amide surfactants are Rewopal~ C6 from
Witco,
Amidox~ C5 from Stepan, and Ethomid° O / 17 and Ethomid~ HT l 60
from Akzo.
(b)- Alkvl or alkyl-aryl nonionic alkoxylated surfactants
Suitable alkyl alkoxylated nonionic surfactants with amine functionality are
generally
5 derived from saturated or unsaturated, primary, secondary, and branched
fatty alcohols, fatty
acids, fatty methyl esters, alkyl phenol, alkyl benzoates, and alkyl benzoic
acids that are
converted to amines, amine-oxides, and optionally substituted with a second
alkyl or alkyl-aryl
hydrocarbon with one or two alkylene oxide chains attached at the amine
functionality each
having _< about 50 moles alkylene oxide moieties (e.g. ethylene oxide andlor
propylene oxide) per
10 mole of amine. The amine or amine-oxide surfactants for use herein have at
least one
hydrophobe with from about 6 to about 22 carbon atoms, and are in either
straight chain and/or
branched chain configuration, preferably there is one hydrocarbon in a
straight chain
configuration having about 8 to about 18 carbon atoms with one or two alkylene
oxide chains
attached to the amine moiety. in average amounts of _< 50 about moles of
alkylene oxide per
15 amine moiety, more preferably from about S to about 15 moles of alkylene
oxide, and most
preferably a single alkylene oxide chain on the amine moiety containing from
about 8 to about 12
moles of alkylene oxide per amine moiety. Preferred materials of this class
also have pour points
about 70°F and/or do not solidify in these clear formulations. Examples
of ethoxylated amine
surfactants include Berol~ 397 and 303 from Rhone Poulenc and Ethomeens~ C/20,
C25, T/25,
S/20, S/25 and Ethodumeens~ T/20 and T25 from Akzo.
Suitable alkyl alkoxylated nonionic surfactants are generally derived from
saturated or
unsaturated primary, secondary, and branched fatty alcohols, fatty acids,
alkyl phenols, or alkyl
aryl (e.g., benzoic) carboxylic acid, where the active hydrogen(s) is
alkoxylated with <_ about 30
alkylene, preferably ethylene, oxide moieties (e.g. ethylene oxide and/or
propylene oxide). These
nonionic surfactants for use herein preferably have from about 6 to about 22
carbon atoms on the
alkyl or alkenyl chain, and are in either straight chain or branched chain
configuration, preferably
straight chain configurations having from about 8 to about 18 carbon atoms,
with the alkylene
oxide being present, preferably at the primary position, in average amounts of
<_ about 30 moles
of alkylene oxide per alkyl chain, more preferably from about 5 to about 15
moles of alkylene
oxide, and most preferably from about 8 to about 12 moles of alkylene oxide.
Preferred materials
of this class also have pour points of about 70°F and/or do not
solidify in these clear
formulations. Examples of alkyl alkoxylated surfactants with straight chains
include Neodol~ 91-
8, 25-9, 1-9, 25-12, 1-9, and 45-13 from Shell, Plurafac B-26 and C-17 from
BASF, and Brij~ 76
and 35 from ICI Surfactants. Examples of branched alkyl alkoxylated
surfactants include
Tergitol~ 15-S-12, 15-S-15, and 15-S-20 from Union Carbide and Emulphogene BC-
720 and
BC-840 from GAF. Examples of alkyl-aryl alkoxylated surfactants include
Igepal~ CO-620 and
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CO-710, from Rhone Poulenc, Triton N-111 and N-150 from Union Carbide, DowfaX
9N5
from Dow and Lutensol~ AP9 and AP 14, from BASF.
Preferably, the compounds of the alkyl or alkyl-aryl alkoxylated surfactants
and alkyl or
alkyl-aryl amine and amine-oxide alkoxylated surfactants have the following
general formula:
R'm - Y - URZ-O)z - Hip
wherein each R~ is selected from the group consisting of saturated or
unsaturated,
primary, secondary or branched chain alkyl or alkyl-aryl hydrocarbons; said
hydrocarbon chain
preferably having a length of from about 6 to about 22, more preferably from
about 8 to about 18
carbon atoms, and even more preferably from about 8 to about 15 carbon atoms,
preferably,
linear and with no aryl moiety; wherein each RZ is selected from the following
groups or
combinations of the following groups: -(CHZ)n ; wherein about 1 < n <_ about
3, preferably from
2-3, more preferably 2; Y is selected from the following groups: -O-; -N(A)q-;
-C(O)O-; -
(Of-)N(A)q-; -B-R3-O-; -B-R3-N(A)q-; -B-R3-C(O)O-; -B-R3-N(-~O)(A)-; and/or
mixtures
thereof; wherein A is selected from the following groups: H; R'; -(RZ-O)Z H; -
(CHz)xCH3;
phenyl, or substituted aryl, wherein 0 <_ x <_ about 3 and B is selected from
the following groups:
-O-; -N(A)-; -C(O)O-;and/or mixtures thereof in which A is as defined above;
and wherein each
R3 is selected from the following groups: R2; phenyl; or substituted aryl. The
terminal hydrogen
in each alkoxy chain can be replaced by a short chain C,~ alkyl or acyl group
to "cap" the alkoxy
chain. z is from about 5 to about 30. p is the number of ethoxylate chains,
typically one or two,
preferably one and m is the number of hydrophobic chains, typically one or
two, preferably one,
and q is a number that indicates the number of moieties that completes the
structure, usually one.
Preferred structures are those in which m = 1, p = 1 or 2, and 5 <_ z <_ 30,
and q can be 1
or 0, but when p = 2, q must be 0; more preferred are structures in which m =
1, p = 1 or 2, and 7
<_ z <_ 20; and even more preferred are structures in which m = 1, p = 1 or 2,
and 9 <_ z <_ 12. The
preferred y is 0.
(c)- Alkoxylated and non alkoxylated nonionic surfactants with bulky head
~rouns
Suitable alkoxylated and non-alkoxylated phase stabilizers with bulky head
groups are
generally derived from saturated or unsaturated, primary, secondary, and
branched fatty alcohols,
fatty acids, alkyl phenol, and alkyl benzoic acids that are derivatized with a
carbohydrate group
or heterocyclic head group. This structure can then be optionally substituted
with more alkyl or
alkyl-aryl alkoxylated or non-alkoxylated hydrocarbons. The heterocyclic or
carbohydrate is
alkoxylated with one or more alkylene oxide chains (e.g. ethylene oxide and/or
propylene oxide)
each having <_ about 50, preferably <_ about 30, moles per heterocyclic or
carbohydrate head
group. The hydrocarbon groups on the carbohydrate or heterocyclic surfactant
for use herein
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17
have from about 6 to about 22 carbon atoms, and are in either straight chain
and/or branched
chain configuration. Preferably there is one hydrocarbon having from about 8
to about 18 carbon
atoms with one or two alkylene oxide chains carbohydrate or heterocyclic
moiety with each
alkylene oxide chain present in average amounts of <_ about S0, preferably <_
about 30, per
carbohydrate or heterocyclic moiety, more preferably from about 5 to about 15
moles of alkylene
oxide per alkylene oxide chain, and most preferably between about 8 and about
12 moles of
alkylene oxide total per surfactant molecule including alkylene oxide on both
the hydrocarbon
chain and on the heterocyclic or carbohydrate moiety. Examples of phase
stabilizers in this class
are Tween'~ 40, 60, and 80 available from ICI Surfactants.
Preferably the compounds of the alkoxylated and non-alkoxylated nonionic
surfactants
with bulky head groups have the following general formulas:
R'-C(O)-Y'-[C(R5)]m CH~O(R~O)ZH
wherein R~ is selected from the group consisting of saturated or unsaturated,
primary, secondary
or branched chain alkyl or alkyl-aryl hydrocarbons; said hydrocarbon chain
having a length of
from about 6 to about 22; Y' is selected from the following groups: -O-; -N(A)-
; and/or mixtures
thereof; and A is selected from the following groups: H; R'; -(R~-O)Z H; -
(CHz)XCH3; phenyl, or
substituted aryl, wherein 0 <_ x <_ about 3 and z is from about 5 to about 30;
each R' is selected
from the following groups or combinations of the following groups: -(CHz)n
and/or -
[CH(CH3)CHZ]-; and each RS is selected from the following groups: -OH; and -
O(R20)Z H ; and
m is from about 2 to about 4;
Another useful general formula for this class of surfactants is
R5 _ ,.. R5
R5 Y" R5
R~ R5
R5 R5
wherein Y" = N or O; and each RS is selected independently from the following:
-H, -OH, -(CHZ)xCH3, -(ORZ)Z-H, -OR', - OC(O)R', and -CHZ(CHz-(ORz)Z»-H)-CHZ-
(ORz)Z.-C(O)
R'. With x, R~, and RZ as defined above in section D above and z, z', and z"
are all from about 5
<_ to _< about 20, more preferably the total number of z + z' + z" is from
about 5 <_ to <_ about 20.
In a particularly preferred form of this structure the heterocyclic ring is a
five member ring with
Y" = O, one RS is -H, two RS are -O-(R20)z H, and at least one RS has the
following structure -
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CH(CHI-(ORz)Z~~-H)-CHz-(ORZ)Z~-OC(O) R' with the total z + z' + z" = to from
about 8 <_ to <_
about 20 and R' is a hydrocarbon with from about 8 to about 20 carbon atoms
and no aryl group.
Another group of surfactants that can be used are polyhydroxy fatty acid amide
surfactants
of the formula:
R6 - C(O) - N(R7) - Z
wherein: each R7 is H, C1-C4 hydrocarbyl, C1-C4 alkoxyalkyl, or hydroxyalkyl,
e.g., 2-
hydroxyethyl, 2-hydroxypropyl, etc., preferably C1-C4 alkyl, more preferably
C1 or C2 alkyl,
most preferably C1 alkyl (i.e., methyl) or methoxyalkyl; and R6 is a C5-C31
hydrocarbyl moiety,
preferably straight chain C7-C 1 g alkyl or alkenyl, more preferably straight
chain Cg-C 17 alkyl or
alkenyl, most preferably straight chain C11-C17 alkyl or alkenyl, or mixture
thereof; and Z is a
polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least
3 hydroxyls
directly connected to the chain, or an alkoxylated derivative (preferably
ethoxylated or
propoxylated) thereof. Z preferably will be derived from a reducing sugar in a
reductive
amination reaction; more preferably Z is a glycityl moiety. Z preferably will
be selected from the
group consisting of -CH2-(CHOH)n-CH20H, -CH(CH20H)-(CHOH)n-CH20H, -CH2-
(CHOH)2(CHOR')(CHOH)-CH20H, where n is an integer from 3 to 5, inclusive, and
R' is H or a
cyclic mono- or poly- saccharide, and alkoxylated derivatives thereof. Most
preferred are
glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH20. Mixtures of the
above Z moieties
are desirable.
R6 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-
isobutyl, N-
2-hydroxyethyl, N-1-methoxypropyl, or N-2-hydroxypropyl.
R6- .CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide,
myristamide,
capricamide, palmitamide, tallowamide, etc.
Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl,
1-
deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
(d)- Block copolymers obtained by copolymerization of ethylene oxide and
propylene oxide
Suitable polymers include a copolymer having blocks of terephthalate and
polyethylene
oxide. More specifically, these polymers are comprised of repeating units of
ethylene and/or
propylene terephthalate and polyethylene oxide terephthalate at a preferred
molar ratio of
ethylene terephthalate units to polyethylene oxide terephthalate units of from
about 25:75 to
about 35:65, said polyethylene oxide terephthalate containing polyethylene
oxide blocks having
molecular weights of from about 300 to about 2000. The molecular weight of
this polymer is in
the range of from about 5,000 to about 55,000.
Another preferred polymer is a crystallizable polyester with repeat units of
ethylene
terephthalate units containing from about 10% to about 15% by weight of
ethylene terephthalate
units together with from about 10% to about 50% by weight of polyoxyethylene
terephthalate
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units, derived from a polyoxyethylene glycol of average molecular weight of
from about 300 to
about 6.000, and the molar ratio of ethylene terephthalate units to
polyoxyethylene terephthalate
units in the crystallizable polymeric compound is between 2:1 and 6:1.
Examples of this
polymer include the commercially available materials Zelcon~ 4780 (from
DuPont) and
Milease~ T (from ICI).
Highly preferred polymers have the generic formula:
X-(OCH2CH2)n-U-C(~)-R1-C(~)-~-R2)u-U-C(~)-R1-C(~)-0)-(CH2CH20)n X (1)
in which X can be any suitable capping group, with each X being selected from
the group
consisting of H. and alkyl or acyl groups containing from about 1 to about 4
carbon atoms,
preferably methyl, n is selected for water solubility and generally is from
about 6 to about 113,
preferably from about 20 to about 50, and a is critical to formulation in a
liquid composition
having a relatively high ionic strength. There should be very little material
in which a is greater
than 10. Furthermore, there should be at least 20%, preferably at least 40%,
of material in which
a ranges from about 3 to about 5.
The R1 moieties are essentially 1,4-phenylene moieties. As used herein, the
term "the
R1 moieties are essentially 1,4-phenylene moieties" refers to compounds where
the R1 moieties
consist entirely of 1,4-phenylene moieties, or are partially substituted with
other arylene or
alkarylene moieties, alkylene moieties, alkenylene moieties, or mixtures
thereof. Arylene and
alkarylene moieties which can be partially substituted for 1,4-phenylene
include 1,3-phenylene,
1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2-biphenylene, 4,4-
biphenylene and/or
mixtures thereof. Alkylene and alkenylene moieties which can be partially
substituted include
ethylene, 1,2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1,7-
heptamethylene,
1,8-octamethylene, 1,4-cyclohexylene, and/or mixtures thereof.
For the Rl moieties, the degree of partial substitution with moieties other
than
1,4-phenylene should be such that the desired properties of the compound are
not adversely
affected to any great extent. Generally, the degree of partial substitution
which can be tolerated
will depend upon the backbone length of the compound, i.e., longer backbones
can have greater
partial substitution for 1,4-phenylene moieties. Usually, compounds where the
R1 comprise
from about 50% to about 100% 1,4-phenylene moieties (from 0 to about 50%
moieties other than
1,4-phenylene) are adequate. Preferably, the R1 moieties consist entirely of
(i.e., comprise
100%) 1,4-phenylene moieties, i.e., each R1 moiety is 1,4-phenylene.
For the R2 moieties, suitable ethylene or substituted ethylene moieties
include ethylene,
1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1,2-propylene and/or
mixtures thereof.
Preferably, the R2 moieties are essentially ethylene moieties, 1,2-propylene
moieties or mixture
thereof. Inclusion of a greater percentage of 1,2-propylene moieties tends to
improve the water
solubility of the compounds.
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Therefore, the use of 1,2-propylene moieties or a similar branched equivalent
is
desirable for incorporation of any substantial part of the polymer in the
liquid fabric softener
compositions. Preferably, from about 75% to about 100%, more preferably from
about 90% to
about 100%, of the R2 moieties are 1,2-propylene moieties.
5 The value for each n is at least about 6, and preferably is at least about
10. The value for
each n usually ranges from about 12 to about 113. Typically, the value for
each n is in the range
of from about 12 to about 43.
A more complete disclosure of these polymers is contained in European Patent
Application 185,427, Gosselink, published June 25, 1986, incorporated herein
by reference.
10 Other preferred copolymers include surfactants, such as the
polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block
polymers.
The copolymer can optionally contain propylene oxide in an amount up to about
15% by
weight. Other preferred copolymer surfactants can be prepared by the processes
described in
U.S. Patent 4,223,163, issued September 16, 1980, Builloty, incorporated
herein by reference.
15 Suitable block polyoxyethylene-polyoxypropylene polymeric compounds that
meet the
requirements described hereinbefore include those based on ethylene glycol,
propylene glycol,
glycerol, trimethylolpropane and ethylenediamine as initiator reactive
hydrogen compound.
Certain of the block polymer surfactant compounds designated PLURONIC~ and
TETRONIC~
by the BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in compositions
of the
20 invention.
A particularly preferred copolymer contains from about 40% to about 70% of a
polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend
comprising about
75%, by weight of the blend, of a reverse block copolymer of polyoxyethylene
and
polyoxypropylene containing 17 moles of ethylene oxide and 44 moles of
propylene oxide; and
about 25%, by weight of the blend, of a block copolymer of polyoxyethylene and
polyoxypropylene initiated with trimethylolpropane and containing 99 moles of
propylene oxide
and 24 moles of ethylene oxide per mole of trimethylolpropane.
Suitable for use as copolymer are those having relatively high hydrophilic-
lipophilic
balance (HLB).
Other polymers useful herein include the polyethylene glycols having a
molecular weight
of from about 950 to about 30,000 which can be obtained from the Dow Chemical
Company of
Midland, Michigan. Such compounds for example, have a melting point within the
range of from
about 30°C to about 100°C, can be obtained at molecular weights
of 1,450, 3,400, 4,500, 6,000,
7,400, 9,500, and 20,000. Such compounds are formed by the polymerization of
ethylene glycol
with the requisite number of moles of ethylene oxide to provide the desired
molecular weight and
melting point of the respective polyethylene glycol.
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21
Other block copolymers include the polyalkylene oxide polysiloxanes having a
dimethyl
polysiloxane hydrophobic moiety and one or more hydrophilic polyalkylene side
chains, and
having the general formula:
R1-(CH3)2Si0-[(CH3)2Si0]a-[(CH3)(R1)Si0]b-Si(CH3)2-R1
wherein a + b are from about 1 to about 50, preferably from about 3 to about
30, more preferably
from about 10 to about 25, and each R1 is the same or different and is
selected from the group
consisting of methyl and a poly(ethyleneoxide/propyleneoxide) copolymer group
having the
general formula:
-(CH2)n O(C2 H4 O)c (C3 H6 O)d R2
with at least one R1 being a poly(ethyleneoxy/propyleneoxy) copolymer group,
and wherein n is 3
or 4, preferably 3; total c (for all polyalkyleneoxy side groups) has a value
of from 1 to about 100,
preferably from about 6 to about 100; total d is from 0 to about 14,
preferably from 0 to about 3;
and more preferably d is 0; total c+d has a value of from about 5 to about
150, preferably from
about 9 to about 100 and each R2 is the same or different and is selected from
the group consisting
of hydrogen, an alkyl having 1 to 4 carbon atoms, and an acetyl group,
preferably hydrogen and
methyl group. Each polyalkylene oxide polysiloxane has at least one R1 group
being a
poly(ethyleneoxide/propyleneoxide) copolymer group.
Nonlimiting examples of this type of surfactants are the Silwet~ surfactants
which are
available from CK-Witco are listed below. Representative Silwet surfactants
which contain only
ethyleneoxy (C2H40) groups are as follows.
Name Average MW Average a+b Average total c
L-7608 600 1 9
L-7607 1,000 2 17
L-77 600 1 9
L-76056,000 20 99
L-7604 4,000 21 53
L-7600 4,000 11 68
L-7657 5,000 20 76
L-7602 3,000 20 29
L-762210,000 88 75
Nonlimiting examples
of surfactants
which contain
both ethyleneoxy
(C2 H4 O) and
propyleneoxy
(C3 H6
O) groups
are as
follows.
Name Average MW EO/PO ratio
Silwet 50/50
L-720
12,000
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Silwet L-7001 20.000 40/60
Silwet L-7002 8,000 50/50
Silwet L-7210 13,000 20/80
Silwet L-7200 19,000 75/25
Silwet L-7220 17,000 20/80
Some nonlimiting preferred Dow Corning polyethylene oxide polysiloxanes
include Dow
Corning 190 Dow Corning Q2-5211. Other nonlimiting examples of polyethylene
oxide
polysiloxanes useful in the present invention include the following compounds
available from Dow
Corning 193, FF-400 Fluid, Q2-5220, Q4-3667, as well as compounds available
from Toray Dow
Corning Silicone Co., Ltd. know as SH3771C, SH3772C, SH3773C, SH3746, SH3748,
SH3749,
SH8400, SF8410, and SH8700, KF351 (A), KF352 (A), KF354 (A), and KF615 (A) of
Shin-Etsu
Chemical Co., Ltd., TSF4440, TSF4445, TSF4446, TSF4452 of Toshiba Silicone Co.
The molecular weight of the polyalkyleneoxy group (R1) is less than or equal
to about
10,000. If propyleneoxy groups are present in the polyalkylenoxy chain, they
can be distributed
randomly in the chain or exist as blocks. Surfactants which contain only
propyleneoxy groups
without ethyleneoxy groups are not preferred. Besides surface activity,
polyalkylene oxide
polysiloxane surfactants can also provide other benefits, such as antistatic
benefits, lubricity and
softness to fabrics.
The preparation of polyalkylene oxide polysiloxanes is well known in the art.
Polyalkylene oxide polysiloxanes of the present invention can be prepared
according to the
procedure set forth in U.S. Pat. No. 3,299,112, incorporated herein by
reference. Typically,
polyalkylene oxide polysiloxanes of the surfactant blend of the present
invention are readily
prepared by an addition reaction between a hydrosiloxane (i.e., a siloxane
containing silicon-
bonded hydrogen) and an alkenyl ether (e.g., a vinyl, allyl, or methallyl
ether) of an alkoxy or
hydroxy end-blocked polyalkylene oxide). The reaction conditions employed in
addition
reactions of this type are well known in the art and in general involve
heating the reactants (e.g.,
at a temperature of from about 85° C. to 110° C.) in the
presence of a platinum catalyst (e.g.,
chloroplatinic acid) and a solvent (e.g., toluene) and;
(4) Mixtures thereof.
In terms of principal solvent reduction, with the invention compositions, a
reduction of at
least 50% can be made without impairing the performance of the composition
compared to
compositions without the phase stabilizers hereinbefore described. Using a
preferred sub-class, a
reduction of more than 80% is possible, and in some cases 100% reduction of
added solvent is
possible.
C. OPTIONAL INGREDIENTS
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2J
(a). Perfume
The present invention can contain any softener compatible perfume. Suitable
perfumes
are disclosed in U.S. Pat. Nos. 5,500,138 and 5.652,206, Bacon et al., issued
March 19, 1996 and
July 29, 1997 respectively, said patents being incorporated herein by
reference.
As used herein, perfume includes fragrant substance or mixture of substances
including
natural (i.e., obtained by extraction of flowers, herbs, leaves, roots, barks,
wood, blossoms or
plants), artificial (i.e., a mixture of different nature oils or oil
constituents) and synthetic (i.e.,
synthetically produced) odoriferous substances. Such materials are often
accompanied by
auxiliary materials, such as fixatives, extenders, stabilizers and solvents.
These auxiliaries are
also included within the meaning of "perfume", as used herein. Typically,
perfumes are complex
mixtures of a plurality of organic compounds.
Examples of perfume ingredients useful in the perfumes of the present
invention
compositions include, but are not limited to, those materials disclosed in
said patents.
The perfumes useful in the present invention compositions are preferably
substantially
free of halogenated materials and nitromusks.
Suitable solvents, diluents or carriers for perfumes ingredients mentioned
above are for
examples, ethanol, isopropanol, diethylene glycol, monoethyl ether,
dipropylene glycol, diethyl
phthalate, triethyl citrate, etc. The amount of such solvents, diluents or
carriers incorporated in
the perfumes is preferably kept to the minimum needed to provide a homogeneous
perfume
solution.
Perfume can be present at a level of from 0% to about 15%, preferably from
about 0.1%
to about 8%, and more preferably from about 0.2% to about 5%, by weight of the
finished
composition. Fabric softener compositions of the present invention provide
improved fabric
perfume deposition.
(b). Additional Fabric Softener Actives and/or Cationic Charge Boosters
(i). Additional Fabric Softener Actives
The category of additional fabric softener actives includes, but is not
limited to
conventional monoquaternary amines especially, but not limited to,
compositions comprising
actives with two or more hydrophobes and preferably, but not limited to,
monoquaternary amines
with multiple hydrophobes and low transition temperatures as disclosed below.
Additional fabric
softener actives also includes, but is not limited to, amphiphilic hydrophobes
with nonionic and
zwitterionic moieties.
Additional fabric softening agents useful herein are described in U.S.
5,643,865
Mermelstein et al., issued July 1, 1997; U.S. 5,622,925 de Buzzaccarini et
al., issued April 22,
1997; U.S. 5,545,350 Baker et al., issued August 13, 1996; U.S. 5,474,690 Wahl
et al., issued
December 12, 1995; U.S. 5,417,868 Turner et al., issued January 27, 1994; U.S.
4,661,269 Trinh
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24
et al.issued April 28, 1987; U.S. 4.439.335 Burns, issued March 27, 1984; U.S.
4.401,578
Verbruggen; issued August 30, 1983: U.S. 4,308.151 Cambre, issued December 29,
1981; U.S.
4,237.016 Rudkin et al., issued October 27. 1978; U.S. 4,233,164 Davis, issued
November 11,
1980: U.S. 4,045,361 Watt et al., issued August 30, 1977; U.S. 3,974,076
Wiersema et al., issued
August 10, 1976; U.S. 3,886,075 Bernadino, issued May 6, 1975; U.S. 3,861,870
Edwards et al.,
issued January 21 1975; and European Patent Application publication No.
472,178, by
Yamamura et al., all of said documents being incorporated herein by reference.
The compounds
of U.S. Pats. 5,759,990 and 5,757,443, incorporated herein by reference, are
especially desirable.
The following are examples of preferred softener actives according to the
present
invention.
N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N.N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl
sulfate;
N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl
sulfate;
N,N-di(tallowylamidoethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl
sulfate;
N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium chloride;
N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium
chloride;
N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-ethyl)-N,N-dimethy1 ammonium
chloride;
N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;
N,N,N-tri(canolyl-oxy-ethyl)-N-methyl ammonium chloride;
N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dimethyl ammonium chloride;
N-(2-canolyloxy-2-oxoethyl)-N-(canolyl)-N,N-dimethyl ammonium chloride;
1,2-ditallowyloxy-3-N,N,N-trimethylammoniopropane chloride; and
1,2-dicanolyloxy-3-N,N,N-trimethylammoniopropane chloride;
and mixtures of the above actives.
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Particularly preferred is N.N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium
chloride,
where the tallow chains are at least partially unsaturated and N,N-di(canoloyl-
oxy-ethyl)-N,N-
dimethvl ammonium chloride, N,N-di(tallowyl-oxy-ethyl)-N-methyl. N-(2-
hydroxyethyl)
ammonium methyl sulfate; N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-
hydroxyethyl) ammonium
5 methyl sulfate; and/or mixtures thereof.
iii). Cationic Charge Boosters
Cationic charge boosters can be added to the rinse-added fabric softening
compositions
of the present invention if needed. Some of the charge boosters serve other
functions as
described hereinbefore. Typically, ethanol is used to prepare many of the
below listed
10 ingredients and is therefore a source of solvent into the final product
formulation. The
formulator is not limited to ethanol, but instead can add other solvents inter
alia hexyleneglycol
to aid in formulation of the final composition. As disclosed hereinbefore, the
cationic amine
bilaver modifier can serve this function. Thus the same material can serve two
functions, but
should only be counted in the formula once. Some of the charge boosters do not
function as
15 bilayer modifiers and therefore are "additional" ingredients.
The preferred cationic charge boosters of the present invention are described
herein
below.
Polyvin~ Amines
A preferred composition according to the present invention contains at least
about 0.2%,
20 preferably from about 0.2% to about 5%, more preferably from about 0.2% to
about 2% by
weight, of one or more polyvinyl amines having the formula
__~__CHZ-CH(NHz)-]v--
wherein y is from about 3 to about 10,000, preferably from about 10 to about
5,000, more
preferably from about 20 to about 500. Polyvinyl amines suitable for use in
the present invention
25 are available from BASF. The polyvinyl amine can further comprise polyvinyl
formamide units
resulting from (intended or unintended) incomplete hydrolysis of the parent
polyvinylformamide
polymer during synthesis. These polyvinylamines have the formula:
--[--CHz-CH(NHz)-Jy--[--CHzCH(NHC(O)H~--JZ
where y+z is from about 3, more preferably from about 5, most preferably from
about 10 to
about10,000, more preferably to about 5000, most preferably to about 500 and
the y:z is from
100:0 to 10:90.
Optionally, one or more of the polyvinyl amine backbone -NH2 unit hydrogens
can be
substituted by an alkyleneoxy unit having the formula:
-~1 ~)xR2
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26
wherein RI is C2-C4 linear or branched alkyl , R2 is hydrogen, CI-C4 alkyl,
and/or mixtures
thereof: x is from I to 50. In one embodiment or the present invention the
polyvinyl amine is
reacted first with a substrate which places a 2-propyleneoxy unit directly on
the nitrogen
followed by reaction of one or more moles of ethylene oxide to form a unit
having the general
formula:
---[CHzC(CH3)HO]-(CHzCHzO)xH
wherein x has the value of from I to about 50. Substitutions such as the above
are represented by
the abbreviated formula PO-EOx-. However, more than one propyleneoxy unit can
be
incorporated into the alkyleneoxy substituent.
Polyvinyl amines are especially preferred for use as cationic charge booster
in liquid
fabric softening compositions since the greater number of amine moieties per
unit weight
provides substantial charge density. In addition. the cationic charge is
generated in situ and the
level of cationic charge can be adjusted by the formulator.
_Polyalkyleneimines
A preferred composition of the present invention comprises at least about
0.2%,
preferably from about 0.2% to about 10%, more preferably from about 0.2% to
about 5% by
weight, of a polyalkyleneimine charge booster having the formula:
(HEN-R)°+t-LN(H)-R]m [N(-)-R]-~z
wherein the value of m is from 2 to about 700 and the value of n is from 0 to
about 350.
Preferably the compounds of the present invention comprise polyamines having a
ratio of m : n
that is at least I:l but can include linear polymers (n equal to 0) as well as
a range as high as
10:1, preferably the ratio is 2:1. When the ratio of m:n is 2:1, the ratio of
primaryaecondaryaertiary amine moieties, that is the ratio of -RNH2, -RNH, and
-RN moieties,
is 1:2:1.
R units are C2-Cg alkylene, C3-Cg alkyl substituted alkylene, and/or mixtures
thereof,
preferably ethylene, 1,2-propylene, 1,3-propylene, and/or mixtures thereof,
more preferably
ethylene. R units serve to connect the amine nitrogen atoms of the backbone.
The polyamine backbones have the general formula:
[EzN-R]w~(E)-R]x[I'l(B~R]Y~z
said backbones prior to subsequent modification, comprise primary, secondary
and tertiary amore
nitrogens connected by R "linking" units. The backbones are comprised of
essentially three types
of units, which can be randomly distributed along the chain.
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27
The units which make up the polyalkyleneimine backbones are primary amore
units
having the formula:
H2N-R- and -NH2
which terminate the main backbone and any branching chains. secondary amine
units having the
formula:
__~(H)_R~__
which propagate the backbone and tertiary amine units having the formula:
__~(g)_R~__
which are the branching points of the main and secondary backbone chains, B
representing a
continuation of the chain structure by branching. The tertiary units have no
replaceable hydrogen
atom and are therefore not modified by substitution. During the formation of
the polyamine
backbones cyclization may occur, therefore, an amount of cyclic polyamine can
be present in the
parent polyalkyleneimine backbone mixture. Each primary and secondary amine
unit of the
cyclic alkyleneimines undergoes modification in the same manner as linear and
branched
polyalkyleneimines.
R is C2-C6 linear alkylene, C3-C6 branched alkylene, and/or mixtures thereof,
preferred
branched alkylene is 1,2-propylene; preferred R is ethylene. The preferred
polyalkyleneimines of
the present invention have backbones which comprise the same R unit, for
example, all units are
ethylene. Most preferred backbone comprises R groups which are all ethylene
units.
The polyalkyleneimines of the present invention are preferably modified by
substitution
of each N-H unit hydrogen with an alkyleneoxy unit having the formula:
-(R 1 p)nR2
wherein Rl is ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-
butylene, and/or mixtures
thereof, preferably ethylene and 1,2-propylene, more preferably ethylene. R2
is hydrogen, Cl-C4
alkyl, and/or mixtures thereof, preferably hydrogen or methyl, more preferably
hydrogen. The
value of the index n is dependent upon the benefits and properties which the
formulator wishes to
provide. The value of the index n is from 1 to about 100. Further, any or all
of the nitrogens
which comprise the polyalkyleneimine backbone can be optionally "modified" by
quaternization
(for example with methyl groups) or by oxidation to the N-oxide. Mixtures of
these substitutions
can be employed.
The polyamines of the present invention can be prepared, for example, by
polymerizing
ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium
bisulfate, sulfuric acid,
hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for
preparing these
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28
polyamine backbones are disclosed in U.S. Patent 2.182,306, Ulrich et al.,
issued December 5,
1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent
2,208,095, Esselmann
et al.; issued July 16, 1940; U.S. Patent 2,806.839, Crowther, issued
September 17, 1957; and
LT.S. Patent 2,553,696. Wilson, issued May 21, 1951; all herein incorporated
by reference. In
addition to the linear and branched PEI's, the present invention also includes
the cyclic amines
that are typically formed as artifacts of synthesis. The presence of these
materials can be
increased or decreased depending on the conditions chose by the formulator.
A further description of polyamine compounds is found in U.S. 4,891,160 Vander
Meer,
issued January 2, 1990; U.S.4,597,898, Vander Meer, issued July 1, 1986;
European Patent
Application 111.965, Oh and Gosselink, published June 27, 1984; European
Patent Application
111,984, Gosselink, published June 27, 1984; European Patent Application
112,592, Gosselink,
published July 4, 1984; U.S. 4,548,744, Connor, issued October 22, 1985; and
U.S. 5,565,145
Watson et al., issued October 15, 1996; all of which are included herein by
reference.
The above alkoxylated compounds can also function as dispersants.
The preferred polyamine cationic charge boosters suitable for use in rinse-
added fabric
softener compositions comprise backbones wherein less than 50% of the R groups
comprise more
than 3 carbon atoms. The use of two and three carbon spacers as R moieties
between nitrogen
atoms in the backbone is advantageous for controlling the charge booster
properties of the
molecules. More preferred embodiments of the present invention comprise less
than 25%
moieties having more than 3 carbon atoms. Yet more preferred backbones
comprise less than
10% moieties having more than 3 carbon atoms.
The cationic charge boosting polyamines of the present invention comprise
homogeneous
or non-homogeneous polyamine backbones, preferably homogeneous backbones. For
the
purpose of the present invention the term "homogeneous polyamine backbone" is
defined as a
polyamine backbone having R units that are the same (i.e., all ethylene).
However, this sameness
definition does not exclude polyamines that comprise other extraneous units
comprising the
polymer backbone that are present due to an artifact of the chosen method of
chemical synthesis.
For example, it is known to those skilled in the art that ethanolamine can be
used as an "initiator"
in the synthesis of polyethyleneimines, therefore a sample of
polyethyleneimine that comprises
one hydroxyethyl moiety resulting from the polymerization "initiator" would be
considered to
comprise a homogeneous polyamine backbone for the purposes of the present
invention.
The term "non-homogeneous polymer backbone" refers to polyamine backbones that
are
a composite of one or more alkylene or substituted alkylene moieties, for
example, ethylene and
1,2-propylene units taken together as R units
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29
However, not all of the suitable charge booster agents belonging to this
category of
polyamine comprise the above described polyamines. Other polyamines that
comprise the
backbone of the compounds of the present invention are generally
polyalkyleneamines (PAA's),
polyalkyleneimines (PAI's), preferably polyethyleneamine (PEA'S), or
polyethyleneimines
(PEI's). A common polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are
obtained by
reactions involving ammonia and ethylene dichloride, followed by fractional
distillation. The
common PEA's obtained are triethylenetetramine (TETA) and
tetraethylenepentamine (TEPA).
Above the pentamines, i.e., the hexamines, heptamines, octamines and possibly
nonamines, the
cogenerically derived mixture does not appear to separate by distillation and
can include other
materials such as cyclic amines and particularly piperazines. There can also
be present cyclic
amines with side chains in which nitrogen atoms appear. See U.S. 2,792,372,
Dickinson, issued
May 14. 1957, which describes the preparation of PEA's.
Cationic Polymers
Composition herein can contain from about 0.001% to about 10%, preferably from
about
0.01 % to about 5%, more preferably from about 0.1 % to about 2%, of cationic
polymer, typically
having a molecular weight of from about 500 to about 1,000,000, preferably
from about 1,000 to
about 500,000, more preferably from about 1,000 to about 250,000, and even
more preferably
from about 2,000 to about 100,000 and a charge density of at least about 0.01
meq/gm.,
preferably from about 0.1 to about 8 meq/gm., more preferably from about 0.5
to about 7, and
even more preferably from about 2 to about 6.
The cationic polymers of the present invention can be amine salts or
quaternary ammonium
salts. Preferred are quaternary ammonium salts. They include cationic
derivatives of natural
polymers such as some polysaccharide, gums, starch and certain cationic
synthetic polymers such
as polymers and copolymers of cationic vinyl pyridine or vinyl pyridinium
halides. Preferably the
polymers are water soluble, for instance to the extent of at least 0.5% by
weight at 20°C.
Preferably they have molecular weights of from about 600 to about 1,000,000,
more preferably
from about 600 to about 500,000, even more preferably from about 800 to about
300,000, and
especially from about 1000 to 10,000. As a general rule, the lower the
molecular weight the higher
the degree of substitution (D.S.) by cationic, usually quaternary groups,
which is desirable, or,
correspondingly, the lower the degree of substitution the higher the molecular
weight which is
desirable, but no precise relationship appears to exist. In general, the
cationic polymers should
have a charge density of at least about 0.01 meq/gm., preferably from about
0.1 to about 8
meq/gm., more preferably from about 0.5 to about 7, and even more preferably
from about 2 to
about 6.
Suitable desirable cationic polymers are disclosed in "CTFA International
Cosmetic
Ingredient Dictionary, Fourth Edition, J. M. Nikitakis, et al, Editors,
published by the Cosmetic,
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Toiletry, and Fragrance Association, 1991, incorporated herein by reference.
The list includes the
following nonlimiting examples:
Of the polysaccharide gums, guar and locust bean gums, which are galactomannam
gums are
available commercially, and are preferred. Thus guar gums are marketed under
Trade Names
5 CSAA M/200, CSA 200/50 by Meyhall and Stein-Hall, and hydroxyalkylated guar
gums are
available from the same suppliers. Other polysaccharide gums commercially
available include:
Xanthan Gum; Ghatti Gum; Tamarind Gum; Gurn Arabic; and Agar.
Cationic guar gums and methods for making them are disclosed in British Pat.
No. 1,136,842
and U.S. Pat. No. 4,031,307. Preferably they have a D.S. of from 0.1 to about
0.5.
10 An effective cationic guar gum is Jaguar C-13S (Trade Name--Meyhall).
Cationic guar
gums are a highly preferred group of cationic polymers in compositions
according to the invention
and act both as scavengers for residual anionic surfactant and also add to the
softening effect of
cationic textile softeners even when used in baths containing little or no
residual anionic surfactant.
The other polysaccharide-based gums can be quaternized similarly and act
substantially in the
15 same way with varying degrees of effectiveness. Suitable starches and
derivatives are the natural
starches such as those obtained from maize, wheat, barley etc., and from roots
such as potato,
tapioca etc., and dextrins, particularly the pyrodextrins such as British gum
and white dextrin.
Other effective cationic polymers include polyamines formed via the
condensation of epi-
chlorohydrin and dialkyl amines depicted by the general formula below:
-[N'(R')(Rz)-CHz-CH(OH)CHz]x-
With R1 and R1 being the same or different and comprising carbon backbones
with 1 to about 22
carbons. The carbon backbones can contain interrupters or substituents
comprising heteroatoms
such as nitrogen, oxygen, sulfur, and halogens; preferably, R'=Rz= a methyl
radical; typical
molecular weights are greater than about 10,000, and preferably greater than
about 20,000, but
below about 500,000 and preferably below about 300,000. Some nonlimitng
commercial
materials include Cypro~ 514, Cypro~ 515, and Cypro~ 516 from Cytec
Industries, Inc, West
Patterson, NJ.
Some nonlimiting examples of very effective individual cationic polymers are
the following:
Polyvinyl pyridine, molecular weight about 40,000, with about 60% of the
available pyridine
nitrogen atoms are quaternized.; Copolymer of 70/30 molar proportions of vinyl
pyridine/styrene,
molecular weight about 43,000, with about 45% of the available pyridine
nitrogen atoms
quaternized as above; Copolymers of 60/40 molar proportions of vinyl
pyridine/acrylamide, with
about 35% of the available pyridine nitrogens quaternized as above. Copolymers
of 77/23 and
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31
57/43 molar proportions of vinyl pyridine/methyl methacrylate, molecular
weight about 43,000,
with about 97% of the available pyridine nitrogen atoms quaternized as above.
These cationic polymers are effective in the compositions at very low
concentrations for
instance from 0.001 % by weight to 0.2% especially from about 0.02% to 0.1 %.
In some instances
the effectiveness seems to fall off, when the content exceeds some optimum
level, such as for
polyvinyl pyridine and its styrene copolymer about 0.05%.
Some other nonlimiting examples of effective cationic polymers are: Copolymer
of vinyl
pyridine and N-vinyl pyrrolidone (63/37) with about 40% of the available
pyridine nitrogens
quaternized.; Copolymer of vinyl pyridine and acrylonitrile (60/40),
quaternized as above.;
Copolymer of N,N-dimethyl amino ethyl methacrylate and styrene (55/45)
quatemized as above at
about 75% of the available amino nitrogen atoms. Eudragit E (Trade Name of
Rohm GmbH)
quaternized as above at about 75% of the available amino nitrogen atoms.
Eudragit E is believed to
be copolymer of N,N-dialkyl amino alkyl methacrylate and a neutral acrylic
acid ester, and to have
molecular weight about 100,000 to 1,000,000.; Copolymer of N-vinyl pyrrolidone
and N,N-diethyl
amino methyl methacrylate (40/50), quaternized at about 50% of the available
amino nitrogen
atoms.; These cationic polymers can be prepared in a known manner by
quaternizing the basic
polymers.
Yet other nonlimiting examples of cationic polymeric salts are quaternized
polyethyleneimines. These have at least 10 repeating units, some or all being
quaternized.
Commercial examples of polymers of this class are also sold under the generic
Trade Name
Alcostat by Allied Colloids.
Another nonlimiting example of effective cationic polymers include the
polydiallydimethyl
ammonium chlorides. Typically these have molecular weights greater than about
10,000 K and
less than about 1,000,000. Some nonlimiting commercial examples of these
materials include
Magnifloc~ 587, Magnifloc~ 589, Magnifloc~ 591, and Magnifloc~ 592 from Cytec
Industries,
Inc.
Typical examples of polymers are disclosed in U.S. Pat. No. 4,179,382,
incorporated herein
by reference.
Each polyamine nitrogen whether primary, secondary or tertiary, is further
defined as
being a member of one of three general classes; simple substituted,
quaternized or oxidized.
The polymers are made neutral by water soluble anions such as chlorine (C1-),
bromine
(Br ), iodine (I-) or any other negatively charged radical such as sulfate
(S042-) and methosulfate
(CH3 S03-)
Specific polyamine backbones are disclosed in U.S. Patent 2,182,306, Ulrich et
al.,
issued December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8,
1962; U.S. Patent
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32
2.208.095. Esselmann et al.; issued July 16, 1940: U.S. Patent 2,806,839.
Crowther, issued
September 17, 1957; and U.S: Patent 2,553,696, Wilson, issued May 21, 1951;
all herein
incorporated by reference.
An example of modified polyamine cationic polymers of the present invention
comprising PEI's comprising a PEI backbone wherein all substitutable nitrogens
are modified by
replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH2O)7H. Other
suitable
polyamine cationic polymers comprise this molecule which is then modified by
subsequent
oxidation of all oxidizable primary and secondary nitrogen atoms to N-oxides
and/or some
backbone amine units are quaternized, e.g. with methyl groups.
Of course, mixtures of any of the above described cationic polymers can be
employed,
and the selection of individual polymers or of particular mixtures can be used
to control the
physical properties of the compositions such as viscosity and stability
(c). Other Optional Ingredients
(i). Bri~hteners
The compositions herein can also optionally contain from about 0.005% to about
5% by
weight of certain types of hydrophilic optical brighteners which also provide
a dye transfer
inhibition action. If used, the compositions herein will preferably comprise
from about 0.001
to about 1% by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those
described in
said U. S. Pat. No. 5,759,990 at column 21, lines 15-60.
(ii). Chemical Stabilizers
Chemical stabilizers can be present in the compositions of the present
invention. The
term "stabilizer," as used herein, includes antioxidants and reductive agents.
These agents are
present at a level of from 0% to about 2%, preferably from about 0.01% to
about 0.2%, more
preferably from about 0.035% to about 0.1% for antioxidants, and, preferably,
from about 0.01%
to about 0.2% for reductive agents. These assure good odor stability under
long term storage
conditions. Antioxidants and reductive agent stabilizers are especially
critical for unscented or
low scent products (no or low perfume).
Examples of antioxidants that can be added to the compositions and in the
processing of
this invention include a mixture of ascorbic acid, ascorbic palmitate, propyl
gallate, available
from Eastman Chemical Products, Inc., under the trade names Tenox~ PG and
Tenor 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, lnc., as Tenor
TBHQ; natural
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33
tocopherols, Eastman Chemical Products, Inc., as Tenox~ GT-1/GT-2; and
butylated
hydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chain esters (C8-
C22) of gallic
acid. e.g., dodecyl gallate; Irganox~ 1010; Irganox~ 1035; IrganoX B 1171;
IrganoX 1425;
Irganox~ 3114; IrganoX 3125; and/or mixtures thereof; preferably Irganox~
3125, IrganoX
1425. Irganox~ 3114, and/or mixtures thereof; more preferably Irganox~ 3125
alone or mixed
with citric acid and/or other chelators such as isopropyl citrate, Dequest~
2010, available from
Monsanto with a chemical name of 1-hydroxyethylidene-1, 1-diphosphonic acid
(etidronic acid),
and Tirori , 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.
(iii). Soil Release Agent
Suitable soil release agents are disclosed in the U.S. Pat. No. 5,759,990 at
column 23,
line 53 through column 25, line 41. The addition of the soil release agent can
occur in
combination with the premix, in combination with the acid/water seat, before
or after electrolyte
addition, or after the final composition is made. The softening composition
prepared by the
process of the present invention herein can contain from 0% to about 10%,
preferably from 0.2%
to about 5%, of a soil release agent. Preferably, such a soil release agent is
a polymer. Polymeric
soil release agents useful in the present invention include copolymeric blocks
of terephthalate and
polyethylene oxide or polypropylene oxide, and the like.
A preferred soil release agent is a copolymer having blocks of terephthalate
and
polyethylene oxide. More specifically, these polymers are comprised of
repeating units of
ethylene terephthalate and polyethylene oxide terephthalate at a molar ratio
of ethylene
terephthalate units to polyethylene oxide terephthalate units of from 25:75 to
about 35:65, said
polyethylene oxide terephthalate containing polyethylene oxide blocks having
molecular weights
of from about 300 to about 2000. The molecular weight of this polymeric soil
release agent is in
the range of from about 5,000 to about 55,000.
Another preferred polymeric soil release agent is a crystallizable polyester
with repeat
units of ethylene terephthalate units containing from about 10% to about 15%
by weight of
ethylene terephthalate units together with from about 10% to about 50% by
weight of
polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of
average molecular
weight of from about 300 to about 6,000, and the molar ratio of ethylene
terephthalate units to
polyoxyethylene terephthalate units in the crystallizable polymeric compound
is between 2:1 and
6:1. Examples of this polymer include the commercially available materials
Zelcon 4780~ (from
Dupont) and Milease T~ (from ICI).
These soil release agents can also act as a scum dispersant.
(iv). Bactericides
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34
Examples of bactericides used in the compositions of this invention include
glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-diol sold by Inolex
Chemicals,
located in Philadelphia, Pennsylvania, under the trade name Bronopol~, and a
mixture of 5-
chloro-2-methyl-4-isothiazoline-3-one and 2-methyl-4-isothiazoline-3-one sold
by Rohm and
Haas Company under the trade name Kathon~ about I to about 1.000 ppm by weight
of the
agent.
(v). Chelatin~ Agents
The compositions and processes herein can optionally employ one or more copper
and/or
nickel chelating agents ("chelators"). Such water-soluble chelating agents can
be selected from
the group consisting of amino carboxylates, amino phosphonates,
polyfunctionally-substituted
aromatic chelating agents and/or mixtures thereof, all as hereinafter defined.
The whiteness
andlor brightness of fabrics are substantially improved or restored by such
chelating agents and,
as discussed before, the stability of the materials in the compositions are
improved.
The chelating agents disclosed in said U. S. Pat. No. 5,759,990 at column 26,
line 29
through column 27, line 38 are suitable.
The chelating agents are typically used in the present rinse process at levels
from about 2
ppm to about 25 ppm, for periods from 1 minute up to several hours' soaking.
A preferred EDDS chelator that can be used herein (also known as
ethylenediamine-
N,N'-disuccinate) is the material described in U.S. Patent 4,704,233, cited
hereinabove, and has
the formula (shown in free acid form):
HN(L)C2H4N(L)H
wherein L is a CH2(COOH)CH2(COOH) group.
A wide variety of chelators can be used herein. Indeed, simple
polycarboxylates such as
citrate, oxydisuccinate, and the like, can also be used, although such
chelators are not as effective
as the amino carboxylates and phosphonates, on a weight basis. Accordingly,
usage levels can be
adjusted to take into account differing degrees of chelating effectiveness.
The chelators herein
will preferably have a stability constant (of the fully ionized chelator) for
copper ions of at least
about 5, preferably at least about 7. Typically, the chelators will comprise
from about 0.5% to
about 10%, more preferably from about 0.75% to about 5%, by weight of the
compositions
herein, in addition to those that are stabilizers. Preferred chelators include
DETMP,
diethylenediaminepentaacetic acid (DETPA), nitrilotriacetate (NTA),
ethylenediamine
disuccinate (EDDS), TPED, and/or mixtures thereof. Such materials can also
provide crystal
growth inhibition.
(vi). Color Care AgLnt
The composition can optionally comprise from about 0.1 % to about 50% of by
weight of the
composition of a color care agent having the formula:
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(R 1 )(R2)N(CX2)nN(R3)(R4)
wherein X is selected from the group consisting of hydrogen, linear or
branched, substituted or
5 unsubstituted alkyl having from 1 to 10 carbons atoms and substituted or
unsubstituted aryl
having at least 6 carbon atoms: n is an integer from 0 to 6; R1, R2, R3, and
R4 are independently
selected from the group consisting of alkyl; aryl; alkaryl; arylalkyl;
hydroxyalkyl;
polyhydroxyalkyl; polyalkylether having the formula -((CH2)y0)zR~ where R~ is
hydrogen or a
linear, branched, substituted or unsubstituted alkyl chain having from 1 to 10
carbon atoms and
10 where y is an integer from 2 to 10 and z is an integer from 1 to 30;
alkoxy; polyalkoxy having the
formula: -(O(CH2)y)zR~; the group -C(O)Rg where Rg is alkyl; alkaryl;
arylalkyl; hydroxyalkyl;
polyhydroxyalkyl and polyalkylether as defined in R1, R2, R3, and R4;
(CX2)"N(RS)(R6) with
no more than one of R1, R2, R3, and R4 being (CX2)"N(RS)(R6) and wherein R5
and R6 are
alkyl; alkaryl; arylalkyl; hydroxyalkyl; polyhydroxyalkyl; polyalkylether;
alkoxy and polyalkoxy
15 as defined in R1, R2, R3, and R4; and either of R1 + R3 or R4 or R2 + R3 or
R4 can combine to
form a cyclic substituent.
Preferred agents include those where R1, R2, R3, and R4 are independently
selected from
the group consisting of alkyl groups having from 1 to 10 carbon atoms and
hydroxyalkyl groups
having from 1 to 5 carbon atoms, preferably ethyl, methyl, hydroxyethyl,
hydroxypropyl and iso-
20 hydroxypropyl. Also preferred are agents wherein one of R1, R2, R3, R4 is
(CX2)"N(RS)(R6),
n=3, 4, 6, or mixtures thereof, and remaining R's are independently selected
from H, linear or
branched C1-10 alkyl, preferably H or methyl. The color care agent has more
than about 1%
nitrogen by weight of the compound, and preferably more than 7%. A preferred
agent is tetrakis-
(2-hydroxylpropyl) ethylenediamine (TPED). These compounds can also function
as chelants.
25 (vii). Silicones
The silicone herein can be either a polydimethyl siloxane (polydimethyl
silicone or
PDMS), or a derivative thereof, e.g., amino silicones, ethoxylated silicones,
etc. The PDMS, is
preferably one with a low molecular weight, e.g., one having a viscosity of
from about 2 to about
5000 cSt, preferably from about 5 to about 500 cSt, more preferably from about
25 to about 200
30 cSt Silicone emulsions can conveniently be used to prepare the compositions
of the present
invention. However, preferably, the silicone is one that is, at least
initially, not emulsified. Le.,
the silicone should be emulsified in the composition itself. In the process of
preparing the
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36
compositions, the silicone is preferably added to the "water seat", which
comprises the water and,
optionally, any other ingredients that normally stay in the aqueous phase.
Low molecular weight PDMS is preferred for use in the fabric softener
compositions of
this invention. The low molecular weight PDMS is easier to formulate without
pre
y emulsification.
Silicone derivatives such as amino-functional silicones, quaternized
silicones, and
silicone derivatives containing Si-OH, Si-H, andlor Si-Cl bonds, can be used.
However, these
silicone derivatives are normally more substantive to fabrics and can build up
on fabrics after
repeated treatments to actually cause a reduction in fabric absorbency.
When added to water, the fabric softener composition deposits the
biodegradable cationic
fabric softening active on the fabric surface to provide fabric softening
effects. However, in a
typical laundry process, using an automatic washer, cotton fabric water
absorbency can be
appreciably reduced at high softener levels and/or after multiple cycles. The
silicone improves
the fabric water absorbency, especially for freshly treated fabrics, when used
with this level of
fabric softener without adversely affecting the fabric softening performance.
The mechanism by
which this improvement in water absorbency occurs is not understood, since the
silicones are
inherently hydrophobic. It is very surprising that there is any improvement in
water absorbency,
rather than additional loss of water absorbency.
The amount of PDMS needed to provide a noticeable improvement in water
absorbency
is dependent on the initial rewettability performance, which, in tum, is
dependent on the
detergent type used in the wash. Effective amounts range from about 2 ppm to
about 50 ppm in
the rinse water, preferably from about 5 to about 20 ppm. The PDMS to softener
active ratio is
from about 2:100 to about 50:100, preferably from about 3:100 to about 35:100,
more preferably
from about 4:100 to about 25:100. As stated hereinbefore, this typically
requires from about
0.2% to about 20%, preferably from about 0.5% to about 10%, more preferably
from about 1% to
about 5% silicone.
The PDMS also improves the ease of ironing in addition to improving the
rewettability
characteristics of the fabr7cs. When the fabric care composition contains an
optional soil release
polymer, the amount of PDMS deposited on cotton fabrics increases and PDMS
improves soil
release benefits on polyester fabrics. Also, the PDMS improves the rinsing
characteristics of the
fabric care compositions by reducing the tendency of the compositions to foam
during the rinse.
Surprisingly, there is little, if any, reduction in the softening
characteristics of the fabric care
compositions as a result of the presence of the relatively large amounts of
PDMS.
The present invention can include other optional components conventionally
used in
textile treatment compositions, for example: colorants; preservatives;
surfactants; anti-shrinkage
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J7
agents; fabric crisping agents; spotting agents; germicides; fungicides; anti-
corrosion agents;
enzymes such as proteases, cellulases, amylases, lipases, etc.; and the like.
The present invention can also include other compatible ingredients, including
those
disclosed U.S. Pat. No. 5,686,376, Rusche, et al.; issued November 11, 1997,
Shaw, et al.; and
U.S. Pat. No. 5,536,421, Hartman, et al., issued July 16, 1996, said patents
being incorporated
herein by reference.
All parts, percentages, proportions, and ratios herein are by weight unless
otherwise
specified and all numerical values are approximations based upon normal
confidence limits. All
documents cited are, in relevant part, incorporated herein by reference.
(viii). Fabric Abrasion Reducing Polymers
The compositions of the present invention comprise from about 0.01%,
preferably from
about 0.1% to about 20%, preferably to about 10% by weight, of a fabric
abrasion reducing
polymer.
The fabric abrasion reducing polymers useful in the present invention have the
formula:
[-P(D)m ~~
wherein the unit P is a polymer backbone which comprises units which are
homopolymeric or
copolymeric. D units are defined herein below. For the purposes of the present
invention the
term "homopolymeric" is defined as "a polymer backbone which is comprised of
units having the
same unit composition, i.e., formed from polymerization of the same monomer".
For the
purposes of the present invention the term "copolymeric" is defined as "a
polymer backbone
which is comprised of units having a different unit composition, i.e., formed
from the
polymerization of two or more monomers".
P backbones preferably comprise units having the formula:
-[CR2-CRz]- or -[(CR2)X L]-
wherein each R unit is independently hydrogen, C,-C,Z alkyl, C6-C,2 aryl, and
D units as
described herein below; preferably C,-C4 alkyl.
Each L unit is independently selected from heteroatom-containing moieties, non-
limiting
examples of which are selected from the group consisting of:
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38
R' O O O O
-N- ' -O- ' -O-C- ' -C-O- ' -O-C-O- , -C
O O O O
~~
II _/I_ _ ~~_ _ _ _
' S ' _ II _ ~ ' II
~ ' II ~
~I O O O
O
polysiloxane having the formula:
Rz
-O Si-O
Rz
P
wherein the index p is from 1 to about 6; units which have dye transfer
inhibition activity:
4
R O O
-N- -N-C- -C-N-
I ,
R3 R3
and mixtures thereof; wherein R' is hydrogen, C,-C,2 alkyl, C6-C,z aryl, and
mixtures thereof. R2
is C,-C,Z alkyl, C,-C,Z alkoxy, C6-C,z aryloxy, and mixtures thereof;
preferably methyl and
methoxy. R3 is hydrogen C,-C,~ alkyl, C6-C,z aryl, and mixtures thereof;
preferably hydrogen or
C,-Ca alkyl, more preferably hydrogen. R4 is C,-C,Z alkyl, C6-C,~ aryl, and
mixtures thereof.
The backbones of the fabric abrasion reducing polymers of the present
invention
comprise one or more D units which are units which comprise one or more units
which provide a
dye transfer inhibiting benefit. The D unit can be part of the backbone itself
as represented in the
general formula:
[-P(D)m ]"
or the D unit may be incorporated into the backbone as a pendant group to a
backbone unit
having, for example, the formula:
-[CR-CRZ]- or -[(CR)X L]-
D D
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39
However, the number of D units depends upon the formulation. For example, the
number of D
units will be adjusted to formula stability as well as efficacy of any
optional dye transfer
inhibition while providing a polymer which has fabric abrasion reducing
properties. The
molecular weight of the fabric abrasion reducing polymers of the present
invention are from
about 500, preferably from about 1,000; to about 6,000,000, preferably to
about 2,000,000
daltons. Therefore the value of the index n is selected to provide the
indicated molecular weight.
Polymers Comprising Amide Units
Non-limiting examples of preferred D units are D units which comprise an amide
moiety.
Examples of polymers wherein an amide unit is introduced into the polymer via
a pendant group
includes polyvinylpyrrolidone having the formula:
- ( i H-CHZ]n
N O
polyvinyloxazolidone having the formula:
- (CH-CHZ]n-
N
~O
O
polyvinylmethyloxazolidone having the formula:
- (CH-CHZ]n-
N
~O
O
H3C
polyacrylamides and N-substituted polyacrylamides having the formula:
- (CH-CHZ]n-
C=O
N(R )z
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wherein each R' is independently hydrogen, C,-C6 alkyl, or both R' units can
be taken together to
form a ring comprising 4-6 carbon atoms; polymethacrylamides and N-substituted
polymethacrylamides having the general formula:
CH3
-( i -CHzJn-
C=O
N(R )z
5
wherein each R' is independently hydrogen, C,-C6 alkyl, or both R' units can
be taken together to
form a ring comprising 4-6 carbon atoms; poly(N-acrylylglycinamide) having the
formula:
-(CH-CHZJn-
C=O O
NH-CHz-C-N(R')z
10 wherein each R' is independently hydrogen, C~-C6 alkyl, or both R' units
can be taken together to
form a ring comprising 4-6 carbon atoms; poly(N-methacrylylglycinamide) having
the formula:
CH3
-( i -CHzJn-
C=O O
NH-CHz-C-N(R')z
wherein each R' is independently hydrogen, C,-C6 alkyl, or both R' units can
be taken together to
15 form a ring comprising 4-6 carbon atoms; polyvinylurethanes having the
formula:
- (CH-CH2Jn-
O
C=O
N(R')z
wherein each R' is independently hydrogen, C,-C6 alkyl, or both R' units can
be taken together to
form a ring comprising 4-6 carbon atoms.
20 An example of a D unit wherein the nitrogen of the dye transfer inhibiting
moiety is
incorporated into the polymer backbone is a poly(2-ethyl-2-oxazoline) having
the formula:
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41
-[CHZ CHI-N]n-
C=O
CHZCH3
wherein the index n indicates the number of monomer residues present.
The fabric abrasion reducing polymers of the present invention can comprise
any mixture
of dve transfer inhibition units which provides the product with suitable
properties.
~ The preferred polymers which comprise D units which are amide moieties are
those
which have the nitrogen atoms of the amide unit highly substituted so the
nitrogen atoms are in
effect shielded to a varying degree by the surrounding non-polar groups. This
provides the
polymers with an amphiphilic character. Non-limiting examples include
polyvinyl-pyrrolidones,
poly~inyloxazolidones; N,N-disubstituted polyacrylamides, and N,N-
disubstituted
polymethacrylamides. A detailed description of physico-chemical properties of
some of these
polymers are given in "Water-Soluble Synthetic Polymers: Properties and
Behavior". Philip
Molyneux, Vol. I, CRC Press, (1983) included herein by reference.
The amide containing polymers may be present partially hydrolyzed and/or
crosslinked
forms. A preferred polymeric compound for the present invention is
polyvinylpyrrolidone (PVP).
This polymer has an amphiphilic character with a highly polar amide group
conferring
hydrophilic and polar-amacting properties, and also has non-polar methylene
and methine
groups, in the backbone and/or the ring, conferring hydrophobic properties.
The rings may also
provide planar alignment with the aromatic rings in the dye molecules. PVP is
readily soluble in
aqueous and organic solvent systems. PVP is available ex ISP, Wayne, New
Jersey, and BASF
Corp., Parsippany, New Jersey, as a powder or aqueous solutions in several
viscosity grades,
designated as, e.g., K-12, K-15, K-25, and K-30. These K-values indicate the
viscosity average
molecular weight, as shown below:
PVP viscosity average K-12 K-15 K-25 K-30 K-60 K-90
molecular
weight (in thousands 2.5 10 24 40 160 360
of daltons)
PVP K-12, K-15, and K-30 are also available ex Polysciences, Inc. Warrington,
Pennsylvania,
PVP K-15, K-25, and K-30 and poly(2-ethyl-2-oxazoline) are available ex
Aldrich Chemical Co.,
Inc., Milwaukee, Wisconsin. PVP K30 (40,000) through to K90 (360,000) are also
commercially
available ex BASF under the tradename Luviskol or commercially available ex
ISP. Still higher
molecular PVP like PVP I.3MM, commercially available ex Aldrich is also
suitable for use
herein. Yet further PVP-type of material suitable for use in the present
invention are
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42
polyvinylpyrrolidone-co-dimethylaminoethylmethacrylate, commercially available
commercially
ex ISP in a quaternised form under the tradename Gafquat~ or commercially
available ex
Aldrich Chemical Co. having a molecular weight of approximately 1.OMM;
polyvinylpyrrolidone=co-vinyl acetate, available ex BASF under the tradename
Luviskol~.
available in vinylpyrrolidone:vinylacetate ratios of from 3:7 to 7:3.
Polymers Comprisin~~N-oxide Units
Another D unit which provides dye transfer inhibition enhancement to the
fabric abrasion
reducing polymers described herein, are N-oxide units having the formula:
O
R1-N-R'
R2
wherein R', Rz, and R' can be any hydrocarbyl unit (for the purposes of the
present invention the
term "hydrocarbyl" does not include hydrogen atom alone). The N-oxide unit may
be part of a
polymer, such as a polyamine, i.e., polyalkyleneamine backbone, or the N-oxide
may be part of a
pendant group attached to the polymer backbone. An example of a polymer which
comprises an
the N-oxide unit as a part of the polymer backbone is polyethyleneimine N-
oxide. Non-limiting
examples of groups which can comprise an N-oxide moiety include the N-oxides
of certain
heterocycles inter alia pyridine, pyrrole, imidazole, pyrazole, pyrazine,
pyrimidine, pyridazine,
piperidine, pyrrolidine, pyrrolidone, azolidine, morpholine. A preferred
polymer is poly(4
vinylpyriding N-oxide, PVNO). In addition, the N-oxide unit may be pendant to
the ring, for
example, aniline oxide.
N-oxide comprising polymers of the present invention will preferably have a
ration of N-
oxidized amine nitrogen to non-oxidized amine nitrogen of from about 1:0 to
about 1:2,
preferably to about 1:1, more preferably to about 3:1. The amount of N-oxide
units can be
adjusted by the formulator. For example, the formulator may co-polymerize N-
oxide comprising
monomers with non N-oxide comprising monomers to arrive at the desired ratio
of N-oxide to
non N-oxide amino units, or the formulator may control the oxidation level of
the polymer during
preparation. The amine oxide unit of the polyamine N-oxides of the present
invention have a Pka
less than or equal to 10, preferably less than or equal to 7, more preferably
less than or equal to 6.
The average molecular weight of the N-oxide comprising polymers which provide
a dye transfer
inhibitor benefit to reduced fabric abrasion polymers is from about 500
daltons, preferably from
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43
about 100,000 daltons, more preferably from about 160,000 daltons to about
6,000,000 daltons,
preferably to about 2,000,000 daltons, more preferably to about 360,000
daltons.
Polymers Comprising Amide Units and N-oxide Units
A further example of polymers which are fabric abrasion reducing polymers
which have
dye transfer inhibition benefits are polymers which comprise both amide units
and N-oxide units
as described herein above. Non-limiting examples include co-polymers of two
monomers
wherein the first monomer comprises an amide unit and the second monomer
comprises an N-
oxide unit. In addition, oligomers or block polymers comprising these units
can be taken together
to form the mixed amide/N-oxide polymers. However, the resulting polymers must
retain the
water solubility requirements described herein above.
Molecular weight
For all the above described polymers of the invention, it is most preferred
that they have
a molecular weight in the range as described herein above. This range is
typically higher than the
range for polymers which render only dye transfer inhibition benefits alone.
Indeed, the higher
molecular weight of the abrasion reducing polymers provides for reduction of
fabric abrasion
which typically occurs subsequent to treatment, for example during garment
use, or in a washing
procedure. Not to be bound by theory, it is believed that the high molecular
weight enables the
deposition of the polymer on the fabric surface and provides sufficient
substantivity so that the
polymer is capable of remaining on the fabric during subsequent use and
subsequent laundering
of the fabric. Further, it is believed that for a given charge density,
increasing the molecular
weight will increase the substantivity of the polymer to the fabric surface.
Ideally the balance of
charge density and molecular weight will provide both a sufficient attraction
to the fabric during
subsequent wash cycles. Increasing molecular weight is considered preferable
to increasing
charge density as it allows a greater choice in the range of materials which
can provide the
desired benefit and avoids the negative impact that increasing charge density
may have on the
amaction of soil and residue onto treated fabrics. It should be noted,
however, that a similar
benefit may be predicted from the approach of increasing charge density while
retaining a lower
molecular weight material.
(ix). Malodor Control Agents
_Cyclodextrin
As used herein, the term "cyclodextrin" includes any of the known
cyclodextrins such as
unsubstituted cyclodextrins containing from six to twelve glucose units,
especially, alpha-
cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and/or their derivatives
and/or mixtures
thereof. The alpha-cyclodextrin consists of six glucose units, the beta-
cyclodextrin consists of
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seven glucose units, and the gamma-cyclodextrin consists of eight glucose
units arranged in
donut-shaped rings. The specific coupling and conformation of the glucose
units give the
cyclodextrins a rigid. conical molecular structures with hollow interiors of
specific volumes. The
"lining" of each internal cavity is formed by hydrogen atoms and glycosidic
bridging oxygen
atoms; therefore, this surface is fairly hydrophobic. The unique shape and
physical-chemical
properties of the cavity enable the cyclodextrin molecules to absorb (form
inclusion complexes
with) organic molecules or parts of organic molecules which can fit into the
cavity. Many
odorous molecules can fit into the cavity including many malodorous molecules
and perfume
molecules. Therefore, cyclodextrins, and especially mixtures of cyclodextrins
with different size
cavities, can be used to control odors caused by a broad spectrum of organic
odoriferous
materials, which may, or may not, contain reactive functional groups. The
complexation between
cyclodextrin and odorous molecules occurs rapidly in the presence of water.
However, the extent
of the complex formation also depends on the polarity of the absorbed
molecules. In an aqueous
solution, strongly hydrophilic molecules (those which are highly water-
soluble) are only partially
absorbed, if at all. Therefore, cyclodextr-in does not complex effectively
with some very low
molecular weight organic amines and acids when they are present at low levels
on wet fabrics.
As the water is being removed however, e.g., the fabric is being dried off,
some low molecular
weight organic amines and acids have more affinity and will complex with the
cyclodextrins
more readily.
The cavities within the cyclodextrin in the solution of the present invention
should
remain essentially unfilled (the cyclodextrin remains uncomplexed) while in
solution, in order to
allow the cyclodextrin to absorb various odor molecules when the solution is
applied to a surface.
Non-derivatised (normal) beta-cyclodextrin can be present at a level up to its
solubility limit of
about 1.85% (about 1.85g in 100 grams of water) at room temperature. Beta-
cyclodextrin is not
preferred in compositions which call for a level of cyclodextrin higher than
its water solubility
limit. Non-derivatised beta-cyclodextrin is generally not preferred when the
composition
contains surfactant since it affects the surface activity of most of the
preferred surfactants that are
compatible with the derivatised cyclodextr-ins.
Preferably, the odor absorbing solution of the present invention is clear. The
term "clear"
as defined herein means transparent or translucent, preferably transparent, as
in "water clear,"
when observed through a layer having a thickness of less than about 10 cm.
Preferably, the cyclodextrins used in the present invention are highly water-
soluble such
as, alpha-cyclodextrin and/or derivatives thereof, gamma-cyclodextrin and/or
derivatives thereof,
derivatised beta-cyclodextrins, and/or mixtures thereof. The derivatives of
cyclodextrin consist
mainly of molecules wherein some of the OH groups are converted to OR groups.
Cyclodextrin
derivatives include, e.g., those with short chain alkyl groups such as
methylated cyclodextrins,
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and ethylated cyclodextrins, wherein R is a methyl or an ethyl group; those
with hydroxyalkyl
substituted groups, such as hydroxypropyl cyclodextrins and/or hydroxyethyl
cyclodextrins,
wherein R is a -CH2-CH(OH)-CH3 or a -CH2CH2-OH group; branched cyclodextrins
such as
maltose-bonded cyclodextrins; cationic cyclodextrins such as those containing
2-hydroxy-3-
5 (dimethylamino)propyl ether, wherein R is CH2-CH(OH)-CH2-N(CH3)2 which is
cationic at low
pH; quaternary ammonium, e.g., 2-hydroxy-3-(trimethylammonio)propyl ether
chloride groups,
wherein R is CH2-CH(OH)-CH2-N+(CH3)3C1-; anionic cyclodextrins such as
carboxymethyl
cyclodextrins, cyclodextrin sulfates, and cyclodextrin succinylates;
amphoteric cyclodextrins
such as carboxymethyl/quaternary ammonium cyclodextrins; cyclodextrins wherein
at least one
10 glucopvranose unit has a 3-6-anhydro-cyclomalto structure, e.g., the mono-3-
6-
anhydrocyclodextrins, as disclosed in "Optimal Performances with Minimal
Chemical
Modification of Cyclodextrins", F. Diedaini-Pilard and B. Perly, The 7th
International
Cyclodextrin Symposium Abstracts, April 1994, p. 49, said references being
incorporated herein
by reference; and mixtures thereof. Other cyclodextrin derivatives are
disclosed in U.S. Pat.
15 Nos.: 3,426,011, Parmerter et al., issued Feb. 4, 1969; 3,453,257;
3,453,258; 3,453,259; and
3,453,260, all in the names of Parmerter et al., and all issued July 1, 1969;
3,459,731, Gramera et
al., issued Aug. 5, 1969; 3,553,191, Parmerter et al., issued Jan. 5, 1971;
3,565,887, Parmerter et
al., issued Feb. 23, 1971; 4,535,152, Szejtli et al., issued Aug. 13, 1985;
4,616,008, Hirai et al.,
issued Oct. 7, 1986; 4,678,598, Ogino et al., issued Jul. 7, 1987; 4,638,058,
Brandt et al., issued
20 Jan. 20, 1987; and 4,746,734, Tsuchiyama et al., issued May 24, 1988; all
of said patents being
incorporated herein by reference.
Highly water-soluble cyclodextrins are those having water solubility of at
least about 10
g in 100 ml of water at room temperature, preferably at least about 20 g in
100 ml of water, more
preferably at least about 25 g in 100 ml of water at room temperature. The
availability of
25 solubilized, uncomplexed cyclodextrins is essential for effective and
efficient odor control
performance. Solubilized, water-soluble cyclodextrin can exhibit more
efficient odor control
performance than non-water-soluble cyclodextrin when deposited onto surfaces,
especially fabric.
Examples of preferred water-soluble cyclodextrin derivatives suitable for use
herein are
hydroxypropyl alpha-cyclodextrin, methylated alpha-cyclodextrin, methylated
beta-cyclodextrin,
30 hydroxyethyl beta-cyclodextrin, and hydroxypropyl beta-cyclodextrin.
Hydroxyalkyl
cyclodextrin derivatives preferably have a degree of substitution of from
about 1 to about 14,
more preferably from about 1.5 to about 7, wherein the total number of OR
groups per
cyclodextrin is defined as the degree of substitution. Methylated cyclodextrin
derivatives
typically have a degree of substitution of from about 1 to about 18,
preferably from about 3 to
35 about 16. A lrnown methylated beta-cyclodextrin is heptakis-2,6-di-O-methyl-
(3-cyclodextrin,
commonly lrnown as DIMEB, in which each glucose unit has about 2 methyl groups
with a
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46
degree of substitution of about 14. A preferred, more commercially available,
methylated beta-
cyclodextrin is a randomly methylated beta-cyclodextrin, commonly latown as
RAMEB, having
different degrees of substitution, normally of about 12.6. RAMEB is more
preferred than
DIMEB, since DIMEB affects the surface activity of the preferred surfactants
more than
RAMEB. The preferred cyclodextrins are available, e.g., from Cerestar USA,
Inc. and blacker
Chemicals (USA), Inc.
It is also preferable to use a mixture of cyclodextrins. Such mixtures absorb
odors more
broadly by complexing with a wider range of odoriferous molecules having a
wider range of
molecular sizes. Preferably at least a portion of the cyclodextrins is alpha-
cyclodextrin and its
derivatives thereof, gamma-cyclodextrin and its derivatives thereof, and/or
derivatised beta
cyclodextrin, more preferably a mixture of alpha-cyclodextrin, or an alpha-
cyclodextrin
derivative, and derivatised beta-cyclodextrin, even more preferably a mixture
of derivatised
alpha-cyclodextrin and derivatised beta-cyclodextrin, most preferably a
mixture of hydroxypropyl
alpha-cyclodextrin and hydroxypropyl beta-cyclodextrin, andlor a mixture of
methylated alpha
cyclodextrin and methylated beta-cyclodextrin.
It is preferable that the usage compositions of the present invention contain
low levels of
cyclodextrin so that a visible stain does not appear on the fabric at normal
usage levels.
Preferably, the solution used to treat the surface under usage conditions is
virtually not
discernible when dry. Typical levels of cyclodextrin in usage compositions for
usage conditions
are from about 0.01 % to about 5%, preferably from about 0.1 % to about 4%,
more preferably
from about 0.5% to about 2% by weight of the composition. Compositions with
higher
concentrations can leave unacceptable visible stains on fabrics as the
solution evaporates off of
the fabric. This is especially a problem on thin, colored, synthetic fabrics.
In order to avoid or
minimize the occurrence of fabric staining, it is preferable that the fabric
be treated at a level of
less than about 5 mg of cyclodextrin per gram of fabric, more preferably less
than about 2 mg of
cyclodextrin per gram of fabric. The presence of the surfactant can improve
appearance by
minimizing localized spotting.
Concentrated compositions can also be used in order to deliver a less
expensive product.
When a concentrated product is used, i.e., when the level of cyclodextrin used
is from about 3%
to about 20%, more preferably from about 5% to about 10%, by weight of the
concentrated
composition, it is preferable to dilute the concentrated composition before
treating fabrics in
order to avoid staining. Preferably the concentrated cyclodextrin composition
is diluted with
about 50% to about 6000%, more preferably with about 75% to about 2000%, most
preferably
with about 100% to about 1000% by weight of the concentrated composition of
water. The
resulting diluted compositions have usage concentrations of cyclodextrin as
discussed
hereinbefore, e.g., of from about 0.1% to about 5%, by weight of the diluted
composition.
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47
Low Molecular Weight Polyols
Low molecular weight polyols with relatively high boiling points, as compared
to water,
such as ethylene glycol, propylene glycol andlor glycerol are preferred
optional ingredients for
improving odor control performance of the composition of the present invention
when
cyclodextrin is present. Not to be bound by theory, it is believed that the
incorporation of a small
amount of low molecular weight glycols into the composition of the present
invention enhances
the formation of the cyclodextrin inclusion complexes as the fabric dries.
It is believed that the polyols' ability to remain on the fabric for a longer
period of time
than water, as the fabric dries allows it to form ternary complexes with the
cyclodextrin and some
malodorous molecules. The addition of the glycols is believed to fill up void
space in the
cyclodextrin cavity that is unable to be filled by some malodor molecules of
relatively smaller
sizes. Preferably the glycol used is glycerin, ethylene glycol, propylene
glycol, diethylene glycol,
dipropylene glycol or mixtures thereof, more preferably ethylene glycol and/or
propylene glycol.
Cyclodextrins prepared by processes that result in a level of such polyols are
highly desirable,
since they can be used without removal of the polyols.
Some polyols, e.g., dipropylene glycol, are also useful to facilitate the
solubilization of
some perfume ingredients in the composition of the present invention.
Typically, glycol is added to the composition of the present invention at a
level of from
about 0.01% to about 3%, by weight of the composition, preferably from about
0.05% to about
1%, more preferably from about 0.1% to about 0.5%, by weight of the
composition. The
preferred weight ratio of low molecular weight polyol to cyclodextrin is from
about 2:1,000 to
about 20:100, more preferably from about 3:1,000 to about 15:100, even more
preferably from
about 5:1,000 to about 10:100, and most preferably from about 1:100 to about
7:100.
Metal Salts
Optionally, but highly preferred, the present invention can include metallic
salts for
added odor absorption and/or antimicrobial benefit for the cyclodextrin
solution when
cyclodextrin is present. The metallic salts are selected from the group
consisting of copper salts,
zinc salts, and mixtures thereof.
Copper salts have some antimicrobial benefits. Specifically, cupric abietate
acts as a
fungicide, copper acetate acts as a mildew inhibitor, cupric chloride acts as
a fungicide, copper
lactate acts as a fungicide, and copper sulfate acts as a germicide. Copper
salts also possess some
malodor control abilities. See U. S. Pat. No. 3,172,817, Leupold, et al.,
which discloses
deodorizing compositions for treating disposable articles, comprising at least
slightly water
soluble salts of acylacetone, including copper salts and zinc salts, all of
said patents are
incorporated herein by reference.
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The preferred zinc salts possess malodor control abilities. Zinc has been used
most often
for its ability to ameliorate malodor, e.g., in mouth wash products, as
disclosed in U.S. Pat. Nos.
4,325,939, issued Apr. 20, 1982 and 4,469.674, issued Sept. 4, 1983, to N. B.
Shah, et al., all of
which are incorporated herein by reference. Highly-ionized and soluble zinc
salts such as zinc
chloride, provide the best source of zinc ions. Zinc borate functions as a
fungistat and a mildew
inhibitor. zinc caprylate functions as a fungicide, zinc chloride provides
antiseptic and deodorant
benefits, zinc ricinoleate functions as a fungicide, zinc sulfate heptahydrate
functions as a
fungicide and zinc undecylenate functions as a fungistat.
Preferably the metallic salts are water-soluble zinc salts, copper salts or
mixtures thereof,
and more preferably zinc salts, especially ZnCl2. These salts are preferably
present in the present
invention primarily to absorb amine and sulfur-containing compounds that have
molecular sizes
too small to be effectively complexed with the cyclodextrin molecules. Low
molecular weight
sulfur-containing materials, e.g., sulfide and mercaptans, are components of
many types of
malodors, e.g., food odors (garlic, onion), body/perspiration odor, breath
odor, etc. Low
molecular weight amines are also components of many malodors, e.g., food
odors, body odors,
urine, etc.
When metallic salts are added to the composition of the present invention they
are
typically present at a level of from about 0.1 % to about 10%, preferably from
about 0.2% to
about 8%, more preferably from about 0.3% to about 5% by weight of the usage
composition.
When zinc salts are used as the metallic salt, and a clear solution is
desired, it is preferable that
the pH of the solution is adjusted to less than about 7, more preferably less
than about 6, most
preferably, less than about 5, in order to keep the solution clear.
Soluble Carbonate and/or Bicarbonate Salts
Water-soluble alkali metal carbonate and/or bicarbonate salts, such as sodium
bicarbonate, potassium bicarbonate, potassium carbonate, cesium carbonate,
sodium carbonate,
and mixtures thereof can be added to the composition of the present invention
in order to help to
control certain acid-type odors. Preferred salts are sodium carbonate
monohydrate, potassium
carbonate, sodium bicarbonate, potassium bicarbonate, and mixtures thereof.
When these salts
are added to the composition of the present invention, they are typically
present at a level of from
about 0:1% to about 5%, preferably from about 0.2% to about 3%, more
preferably from about
0.3% to about 2%, by weight of the composition. When these salts are added to
the composition
of the present invention it is preferably that incompatible metal salts not be
present in the
invention. Preferably, when these salts are used the composition should be
essentially free of
zinc and other incompatible metal ions, e.g., Ca, Fe, Ba, etc. which form
water-insoluble salts.
Enzymes
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Enzymes can be used to control certain types of malodor, especially malodor
from urine
and other types of excretions, including regurgitated materials. Proteases are
especially
desirable. The activity of commercial enzymes depends very much on the type
and purity of the
enzyme being considered. Enzymes that are water soluble proteases like pepsin,
tripsin, ficin,
bromelin, papain, rennin, and mixtures thereof are particularly useful.
Enzymes are normally incorporated at levels sufficient to provide up to about
5 mg by
weight, preferably from about 0.001 mg to about 3 mg, more preferably from
about 0.002 mg to
about 1 mg, of active enzyme per gram of the aqueous compositions. Stated
otherwise, the
aqueous compositions herein can comprise from about 0.0001% to about 0.5%,
preferably from
about 0.001% to about 0.3%, more preferably from about 0.005% to about 0.2% by
weight of a
commercial enzyme preparation. Protease enzymes are usually present in such
commercial
preparations at levels sufficient to provide from 0.0005 to 0.1 Anson units
(AU) of activity per
gram of aqueous composition.
Nonlimiting examples of suitable, commercially available, water soluble
proteases are
pepsin, tripsin, ficin, bromelin, papain, rennin, and mixtures thereof. Papain
can be isolated, e.g.,
from papaya latex, and is available commercially in the purified form of up
to, e.g., about 80%
protein, or cruder, technical grade of much lower activity. Other suitable
examples of proteases
are the subtilisins which are obtained from particular strains of B. subtilis
and B. licheniforms.
Another suitable protease is obtained from a strain of Bacillus, having
maximum activity
throughout the pH range of 8-12, developed and sold by Novo Industries A/S
under the registered
trade name ESPER.ASE~. The preparation of this enzyme and analogous enzymes is
described
in British Patent Specification No. 1,243,784 of Novo. Proteolytic enzymes
suitable for
removing protein-based stains that are commercially available include those
sold under the trade
names ALCALASE~ and SAVINASE~ by Novo Industries A/S (Denmark) and MAXATASE~
by International Bio-Synthetics, Inc. (The Netherlands). Other proteases
include Protease A (see
European Patent Application 130,756, published January 9, 1985); Protease B
(see European
Patent Application Serial No. 87303761.8, filed April 28, 1987, and European
Patent Application
130,756, Bott et al, published January 9, 1985); and proteases made by
Genencor International,
Inc., according to one or more of the following patents: Caldwell et al, U.S.
Patent Nos.
5,185,258, 5,204,015 and 5,244,791.
A wide range of enzyme materials and means for their incorporation into liquid
compositions are also disclosed in U.S. Patent 3,553,139, issued January 5,
1971 to McCarty et
al. Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al,
issued July 18, 1978, and
in U.S. Patent 4,507,219, Hughes, issued March 26, 1985. Other enzyme
materials useful for
liquid formulations, and their incorporation into such formulations, are
disclosed in U.S. Patent
4,261,868, Hora et al, issued April 14, 1981. Enzymes can be stabilized by
various techniques,
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e.g., those disclosed and exemplified in U.S. Patent 3,600,319. issued August
17, 1971 to Gedge,
et al., European Patent Application Publication No. 0 199 405, Application No.
86200586.5,
published October 29, 1986, Venegas, and in U.S. Patent 3,519,570. All of the
above patents and
applications are incorporated herein, at least in pertinent part.
5 Enzyme-polyethylene glycol conjugates are also preferred. Such polyethylene
glycol
(PEG) derivatives of enzymes, wherein the PEG or alkoxy-PEG moieties are
coupled to the
protein molecule through, e.g., secondary amine linkages. Suitable
derivatization decreases
immunogenicity, thus minimizes allergic reactions, while still maintaining
some enzymatic
activity. An example of protease-PEG's is PEG-subtilisin Carlsberg from B.
lichenniformis
10 coupled to methoxy-PEGS through secondary amine linkage, and is available
from Sigma-Aldrich
Corp., St. Louis, Missouri.
Zeolites
When the clarity of the solution is not needed, and the solution is not
sprayed on fabrics,
other optional odor absorbing materials, e.g., zeolites and/or activated
carbon, can also be used.
15 A preferred class of zeolites is characterized as "intermediate"
silicate/aluminate zeolites. The
intermediate zeolites are characterized by Si02/A102 molar ratios of less than
about 10.
Preferably the molar ratio of Si02/A102 ranges from about 2 to about 10. The
intermediate
zeolites have an advantage over the "high" zeolites. The intermediate zeolites
have a higher
affinity for amine-type odors, they are more weight efficient for odor
absorption because they
20 have a larger surface area, and they are more moisture tolerant and retain
more of their odor
absorbing capacity in water than the high zeolites. A wide variety of
intermediate zeolites
suitable for use herein are commercially available as Valfor~ CP301-68,
Valfor~ 300-63,
Valfor~ CP300-35, and Valfor~ CP300-56, available from PQ Corporation, and the
CBV100~
series of zeolites from Conteka.
25 Zeolite materials marketed under the trade name Abscents~ and Smellrite~,
available
from The Union Carbide Corporation and UOP are also preferred. These materials
are typically
available as a white powder in the 3-5 micron particle size range. Such
materials are preferred
over the intermediate zeolites for control of sulfur-containing odors, e.g.,
thiols, mercaptans.
Activated Carbon
30 The carbon material suitable for use in the present invention is the
material well known
in commercial practice as an absorbent for organic molecules and/or for air
purification purposes.
Often, such carbon material is referred to as "activated" carbon or
"activated" charcoal. Such
carbon is available from commercial sources under such trade names as; Calgon-
Type CPG~;
Type PCB~; Type SGL~; Type CAL~; and Type OL~.
35 Mixtures Thereof
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51
Mixtures of the above materials are desirable, especially when the mixture
provides
control over a broader range of odors.
(x). Mixtures of Optional Ingredients
Any mixtures of optional ingredients are also suitable for the present
invention.
D. METHOD FOR TESTING PRODUCT STABILITY
The amount of dispersed phase in the clear or translucent product is a measure
of the
product stability. Generally a small amount of secondary phases) will remain
dispersed in the
clear product. However, when the amount of the secondary phases) becomes too
high, particles
of secondary phases) are likely to agglomerate or coalesce and separate from
the primary phase
resulting in inhomogeniety. The rate at which separation occurs is dependent
on the density
difference between the clear product and the dispersed phase, and the number
of collisions
between dispersed particles and this is dependent on the size and number of
dispersed particles.
Therefore, when the amount of secondary phases) is too high, the product
should be consider
unstable because it will rapidly separate. When the amount of secondary
phases) is small or
nonexistent. the clear products are generally stable for long periods of time.
A rapid method of
determining if a product is unstable is ultra-high speed centrifugation. Ultra-
high speed
centrifugation forces collisions between dispersed particles and thus forces
product separation.
The lower the amount of secondary phases) present and the more stable the
dispersion, the
smaller the volume of separated material will be after a reasonable period of
ultra-centrifugation.
When only small or ideally no separation occurs during ultra-centrifugation a
product is
considered stable for the uses disclosed within.
To test a composition for phase separation, the composition is loaded into a
Beclanan
polyallomer centrifuge tube until the combined weight of the tube and the
composition is 13.5 +
or - 0.02g. Six tubes with equal weights of different compositions are placed
in rotor buckets and
placed on the rotor. The rotor is placed into the vacuum chamber. The rotor is
placed under
vacuum and the compositions are spun at 40,000 rpm for 16 hrs at 25 °C.
At the end of 16 hrs.,
the tubes are removed and examined for separation. When separation is
detected, the length of
the total composition in the tube is measured. The length of each phase is
measured The length
of the longest phase is substracted from the entire length of the composition
in the tube and then
the result is divided by the entire length of the composition and multiplied
by 100 to compute the
%phase volume of the phase separation. Formulas are considered stable if the
%phase volume is
at or below 5%.
EXAMPLES
TABLE 1. Samples with conventional principal solvent levels.
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Component Wt.% 1 2 3 4 5 6 7
Diquat' 85% 23.34 23.34 23.34 27.64 27.64 27.64 27.64
in
Ethanol (EtOH)
EtOH from softener3.5 3.5 3.5 4.1 4.1 4.1 4.1
Hexvlene Glvcol7.5 7.5 2.0 7.5 7.5 7.5 2.0
TMPDZ 7.5 5.0 7.5 7.5 4.5 2.0 7.5
Perfume 1.0 1.0 1.0 1.0 1.0 1.0 1.0
Water bal. bal. bal. bal. bal. bal. bal.
Total Solvent 18.5 16.0 13.0 19.1 16.1 13.6 13.4
Level
Appearance SlightlyCloudyCloudy Clear Clear CloudyCloudy
Hazv
phase split none 12.2% 8.3% none none 25% 2.4%
1. Diquat softener = The products formed by quatemization of reaction products
of fatty acid
with N, N, N',N', tetraakis(hydroxyethyl)-1,6-diaminohexane. 2. TMPD =2,2,4-
trimethyl
pentane-1,3-diol.
TABLE 2. Examples of Monoalkyl quat used to reduce the level of the principal
solvent 1,2-
hexanediollevel.
Corn onent Wt.% 1 2 3
Diquat' softener 27.6423.34 32.9
- 85% in
Ethanol (EtOH)
EtOH from Softener 4.14 3.5 4.9
Ado en 4613 - 6.0 4.5
IPA from Adogen 461 - 1.8 0.9
1,2-Hexanediol 9.0 2.0 5.0
Perfume 1.0 2.0 1.0
Water bal. bal. bal.
Total Solvent Level 13.1 7.3 10.8
A earance ClearClear Clear
phase s lit none none none
Adogen 461 = cocoalkyl trimethyl quaternary ammonium chloride.
TABLE 3. Monoalkyl quat used to reduce the level of various principal solvents
and to eliminate
principal solvent
2 ~ 3 ~ 4 ( 5 ~ 6 ~ 7
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Wt.%
Diquat' 85% 23.3423.3423.3423.3423.3423.3423.3423.3423.34
in
EtOH
EtOH from 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5
Softener ~
Adogen 4613 7.0 7.0 6.3 6.5 6.0 6.7 7.6 7.0 -
Adogen 41 - - - - - - - - 17.5
T'
IPA from 2.1 2.1 1.9 2.0 1.8 2.0 2.3 2.1 5.3
Adogens
TMPD2 2.0 - - - - - - -
methvl lactate 2.0 -
2,5-hexanediol- 2.0 - - - - - -
EHDiols - - - 2.0 - - - - 2.0
Propylene - - - - 2.0 - - - -
Carbonate
Hexylene - - - - - 2.0 - - -
Glycol
2-butyl-2-ethyl-- - - - - - 2.0 - -
1,3- ro anediol
EtOH - - - - - - - 2.0 -
Total Solvent7.6 7.6 7.4 7.5 7.3 7.5 7.8 7.6 10.8
Level
Perfume 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
Water bal. bal. bal. bal.bal. bal. bal. bal. bal.
A earance clearclearclearclearclearclearclearclearclear
phase split none none none nonenone none none none none
4. Adogen 417 = C16-18 unsaturated alkyl trimethyl quaternary ammonium
chloride.
5. EHDioI = 2-ehtyl-1,3-hexanediol.
TABLE 4. Monoalkyl quat used to reduce the level of various principal solvents
in formulas
with higher diquat levels vs. Table 3.
Com onent W 1 2 3 4 5 6
Diquat' 85% 32.9 32.9 32.9 32.9 32.9 32.9
in
EtOH
EtOH from Softener4.9 4.9 4.9 4.9 4.9 4.9
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Adoeen 4613 7.0 7.0 7.0 7.0 7.0 7.0
IPA from Adogen2.1 2.1 2.1 2.1 2.1 2.1
4613
TMPD2 2.0 - - - - -
Methvllactate - 2.0 - - - -
2,5-hexanediol - - 2.0 - - -
EHDiolS - - 2.0 - -
Pro ylene Carbonate- - - - 2.0 -
Hexvlene Glycol- - - - - 2.0
Total Solvent 9.0 9.0 9.0 9.0 9.0 9.0
Level
Perfume 2.0 2.0 2.0 2.0 2.0 2.0
Water bal. Bal. bal. bal. bal. bal.
A earance clear clear clearclear clear clear
phase split none none none none none none
TABLE 5. Formulation with monoalkyl quat and no added organic and/or principal
solvent .
Com onent Wt.% 1
Quat 85% in 23.34
EtOH
EtOH from Softener3.5
Adogen 4613 8.0
IPA from Adogen2.4
461'
Total Solvent 5.9
Level
Perfume 2.0
Water bal.
A earance clear
phase split none
TABLE 6. Cocamide and polar oil used to reduce the principal solvent and the
total solvent
level.
Com onent Wt.% 1 2 3
Di uat' 85% in 27.64 27.64 27.64
EtOH
EtOH from Softener4.1 4.1 4.1
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Rewopal~' C66 8.0 8.0
Wickenol158' - - 6.5
1,2-Hexanediol - - 8.6
Hexylene Glycol 7.5 2.0
TMPDz 2.0 7.5 -
Total Solvent 13.6 13.6 12.7
Level
Perfume 1.0 1.0 1.0
Water bal. bal. bal.
Ap earance clear clear clear
phase split none none none
6. Rewopal~ C6 = an ethoxylated cocomonoethanolamide sold by Witco Corporation
7. Wickenol 1586 = dioctyl adipate from Akzo, Inc.
TABLE 7. Mixtures of Diquat softeners and conventional monoquat softeners
Com onent Wt.
TEA Diester QuatB 85% in solvent10.0
Ethanol (from TEA Quats) 0.75
Hex lene 1 col (from TEA Diester0.75
Quat)
Di uat' 85% in EtOH 10.0
EtOH (from Di uat') 1.5
Ado en 4613 9.8
IPA (from Ado en 4613) 2.9
1,2 Hexanediol 2.0
Total Solvent Level 7.9
Perfume 2.50
Water balance
A earance clear
phase split none
8. TEA Diester Quat = Methyl sulfate Quaternized condensation reaction of
about 1.9 moles of
canola fatty acid with one mole of triethanolamine.
